CN1379740A - Method for making nanocrystalline glass-ceramic fibers - Google Patents

Method for making nanocrystalline glass-ceramic fibers Download PDF

Info

Publication number
CN1379740A
CN1379740A CN 00814320 CN00814320A CN1379740A CN 1379740 A CN1379740 A CN 1379740A CN 00814320 CN00814320 CN 00814320 CN 00814320 A CN00814320 A CN 00814320A CN 1379740 A CN1379740 A CN 1379740A
Authority
CN
China
Prior art keywords
glass
core
ceramic
precursor
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN 00814320
Other languages
Chinese (zh)
Inventor
G·比尔
L·平克尼
W·D·沃克劳斯
王吉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Corning Inc
Original Assignee
Corning Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Corning Inc filed Critical Corning Inc
Publication of CN1379740A publication Critical patent/CN1379740A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/02—Optical fibres with cladding with or without a coating
    • G02B6/0229—Optical fibres with cladding with or without a coating characterised by nanostructures, i.e. structures of size less than 100 nm, e.g. quantum dots
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
    • C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
    • C03B37/01—Manufacture of glass fibres or filaments
    • C03B37/012—Manufacture of preforms for drawing fibres or filaments
    • C03B37/01205—Manufacture of preforms for drawing fibres or filaments starting from tubes, rods, fibres or filaments
    • C03B37/01211—Manufacture of preforms for drawing fibres or filaments starting from tubes, rods, fibres or filaments by inserting one or more rods or tubes into a tube
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
    • C03B37/01—Manufacture of glass fibres or filaments
    • C03B37/02—Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor
    • C03B37/025—Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor from reheated softened tubes, rods, fibres or filaments, e.g. drawing fibres from preforms
    • C03B37/027—Fibres composed of different sorts of glass, e.g. glass optical fibres
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C13/00—Fibre or filament compositions
    • C03C13/006—Glass-ceramics fibres
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C13/00—Fibre or filament compositions
    • C03C13/04—Fibre optics, e.g. core and clad fibre compositions
    • C03C13/045—Silica-containing oxide glass compositions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C13/00—Fibre or filament compositions
    • C03C13/04—Fibre optics, e.g. core and clad fibre compositions
    • C03C13/045—Silica-containing oxide glass compositions
    • C03C13/046—Multicomponent glass compositions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/64—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing aluminium
    • C09K11/646—Silicates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
    • C09K11/68—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals containing chromium, molybdenum or tungsten
    • C09K11/685—Aluminates; Silicates
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2201/00—Type of glass produced
    • C03B2201/06—Doped silica-based glasses
    • C03B2201/08—Doped silica-based glasses doped with boron or fluorine or other refractive index decreasing dopant
    • C03B2201/10—Doped silica-based glasses doped with boron or fluorine or other refractive index decreasing dopant doped with boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2201/00—Type of glass produced
    • C03B2201/06—Doped silica-based glasses
    • C03B2201/20—Doped silica-based glasses doped with non-metals other than boron or fluorine
    • C03B2201/28—Doped silica-based glasses doped with non-metals other than boron or fluorine doped with phosphorus
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2201/00—Type of glass produced
    • C03B2201/06—Doped silica-based glasses
    • C03B2201/30—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi
    • C03B2201/31—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with germanium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2201/00—Type of glass produced
    • C03B2201/06—Doped silica-based glasses
    • C03B2201/30—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi
    • C03B2201/34—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with rare earth metals, i.e. with Sc, Y or lanthanides, e.g. for laser-amplifiers
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2201/00—Type of glass produced
    • C03B2201/06—Doped silica-based glasses
    • C03B2201/30—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi
    • C03B2201/40—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with transition metals other than rare earth metals, e.g. Zr, Nb, Ta or Zn
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2203/00—Fibre product details, e.g. structure, shape
    • C03B2203/10—Internal structure or shape details
    • C03B2203/22—Radial profile of refractive index, composition or softening point
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2205/00—Fibre drawing or extruding details
    • C03B2205/56—Annealing or re-heating the drawn fibre prior to coating
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2205/00—Fibre drawing or extruding details
    • C03B2205/60—Optical fibre draw furnaces
    • C03B2205/72—Controlling or measuring the draw furnace temperature

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Optics & Photonics (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • General Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Glass Compositions (AREA)
  • Re-Forming, After-Treatment, Cutting And Transporting Of Glass Products (AREA)
  • Manufacture, Treatment Of Glass Fibers (AREA)

Abstract

A method for making a glass ceramic, optoelectronic material such as a clad optical fiber or other component for use in an optoelectronic device. The method comprises preparing a glass composition batch to yield a precursor glass for a nanocrystalline glass-ceramic that is doped with at least one kind of optically active ion, such as a transition metal or lanthanide element; melting the batch; forming a glass cane; surrounding the cane with a chemically inert cladding material shaped in the form of a tube; drawing a glass fiber from the combined precursor-glass 'cane-in-tube' at a temperature slightly above the liquidus of the precursor glass composition, and heat treating at least a portion of the drawn clad glass fiber under conditions to develop nanocrystals within the core composition and thereby forming a glass ceramic.

Description

Make the method for nanocrystalline glass-ceramic fibers
The right of priority that requires
The U.S. Provisional Application No.60/160 that is entitled as " nanocrystalline glass-ceramic fibers and its manufacture method " that the application's requirement is submitted on October 18th, 1999 with the name of George H.Beall, Linda R.Pinckney, William Vockroth and Ji Wang, 052 right.
FIELD OF THE INVENTION
A kind of method of making the glass-ceramic photoelectric material, described material comprise the nanocrystal (nanocrystal) that is doped with at least a optical activity metal.
The background of invention
In the past few decades, fiber optic system has become the standard of telecommunications.This dominant status connects owing to its optics has some advantages with respect to more traditional metal matrix system, they comprise lower loss, higher information content, the cost on each passage low, to the resistance of cross-talk and electrical interference and less material mass.At present, fibre system can be transmitted hundreds of trillion bits p.s. on greater than the distance of 1000km.Even the capacity of optical fiber surpasses the capacity that metal connects on the order of magnitude, but that the requirement of global communication is just promoting the capacity of this system is all double every year.
Transition metal because they fluoresce, has corresponding big bandwidth as the optically active doping agent in the crystalline matrix simultaneously near infrared (1000-1500nm) zone for a long time.For example, be can be disclosed in the U.S. Patent No. 4,987,575 of Alfano etc. at the Cr that sends laser near 1.3 mum wavelengths 4+Doped crystal.Another example is titanium doped sapphire (Ti: Al 2O 3), it provides optical gain in the scope of about 650-1100nm.
Under the situation of useful wavelength region that has provided many transition metal dopant and bandwidth, people can understand that its favourable characteristic can be advantageously applied to the telecommunication purposes.Yet, patent 4,987,575 crystalline matrix transition metal technology also is not suitable for these purposes, because main optical communication medium is the optical fiber of glass-based.Although logical expansion can be that transition metal dopant is added in the glass, find that unfortunately their performance (especially their efficient) descends in non-crystalline state matrix, wherein crystal field strength much smaller than in the single crystal substrate.Transition metal ion all is only to be dispersed in the amorphous substance, to provide promote to amplify or the effect of delivery quality very little.
Alfano etc. are in U.S. Patent No. 5,717, once propose another kind of method in 517, promptly make the active Cr of many granular laser + 4(or V + 3) doped crystal, it is dispersed in " on-gaseous " medium.Like this, doping agent keeps the laser activity in crystalline matrix, and bigger surrounding medium and optical fiber technology adapt.In order to make the optical loss in this complex media reduce to minimum, particle and its difference with the specific refractory power of surrounding medium are necessary little.These require to have realized that in the patent of Alfano etc. thereby granularity is defined as 0.05-500 μ m that the difference of stipulating specific refractory power simultaneously is less than 0.1.
Although the idea that crystalline particle is dispersed in the non-crystalline state medium is that effectively this method has several serious defectives, main difficulty is manufacturing and its uniform distribution in suitable matrix of subparticle.Loss reduces along with particle size reduction really, so wish particle minimum (0.05 μ m).Material is ground the particle that is difficult to usually produce less than 1 μ m, yet, also be difficult to obtain particle even make the sol-gel method of forsterite less than this granularity.Although some method has obtained the particle of about 0.5 μ m, yet it seems that an again little order of magnitude be difficult to obtain.Even for this minimum granularity of 0.05 μ m, the simple analysis of scattering loss shows that also this method has another main shortcoming.
In order to overcome the defective of above-mentioned materials and method, we have proposed a kind of method of making glass-ceramic optical fiber.The advantage that glass-ceramic has is disclosed in the name of George H.Beall, Nicholas F.Borrelli, Linda R.Pinckney, Eric J.Mozdy in the U.S. Patent application of submitting on October 11st, 2000 that is entitled as " transition-metal glass-ceramic gain media (TRANSITION-METAL GLASS-CERAMIC GAINMEDIA) ", and the full content of this application is with reference to being incorporated into this.The process of inner nucleation has formed glass-ceramic, and wherein the crystallization site is again little and be evenly distributed in the whole glass core.As U.S. Patent No. 5,717,517 is described, is the constituent material formation crystal from the pristine glass melt, and need not to add new material.And optically active dopant distribution contrasts with the particle that only scatters in whole medium.
During from glass ceramic material manufacturing optical fiber, the person's character of glass ceramic material needs earlier this material is drawn into glass fibre usually, subsequently fiber is carried out proper heat treatment, so that form crystallization phases.Present known most of glass-ceramic fibre adopts " double crucible method " to make.Therefore, make in its process that is transformed into glass-ceramic, use the equipment that is called two crucibles usually at drawn glass.Two crucibles contain the pipe core of the core glass that is useful on fiber.Larger-diameter Guan Ze around pipe core provides cladding glass.These two kinds of glass keep molten state in crucible separately, flow out from pipe-type outlet, pull into clad fibre.
From the process of glass ceramic composition drawing optical fiber, the problem of the most critical of being paid close attention to is how glass to be processed when forming glass fibre composite inhibiting generation crystalline strong tendency.This phenomenon be since will be used for glass-ceramic especially the precursor glass composition of the useful high temp glass pottery of the object of the invention have a mind to be designed to be can crystalline.Therefore, drawing for the object of the invention in the process of cladding glass, crucial problem is how to suppress this intensive crystallization tendency, thereby keeps fiber to be glassy.
We have found the various shortcomings in adopting double crucible method.But the main drawback of this method that the present invention is intended to improve is each glass ingredient to be had between core material and clad material intensive chemistry mutual diffusion and/or interactional tendency takes place, because two kinds of glass all is that to be in tangible fluid be liquid state.Core composition and covering composition generally comprise a large amount of unit prices and divalent ion, and described ion moves the interface of passing core-covering probably.Diffusion problem can seriously change the composition of core glass pottery, even makes it can not be by potteryization in heat treatment process subsequently.
Therefore, just there is problem to be solved by this invention.The invention provides and a kind ofly in making the process of optical fiber, make the interdiffusion phenomenon between core and the clad material reduce to minimum method.The described method of the application is a kind of very different Fibrotic method of glass ceramic material that makes, and as described below, it especially can be for covering provides some advantage, so it is the fiber process of one-tenth preferably of some glass ceramic composition.
The general introduction of invention
The present invention relates to a kind of method of making cladded-fiber and be used for other material of photoelectricity purposes, these purposes comprise laser apparatus and amplifier, and are forming and during drawing optical fiber, and the present invention can not make fiber core suffer bad pollution from clad material.More particularly, the invention provides a kind of peculiar methods of making photoelectric material, its way is to improve " pipe bag rod " method to make cladded-fiber.Pollutant component is entered be used for the diffusion of the precursor glass composition of glass-ceramic fibre core to be kept minimum.The purity of holding core and its light transmission are being necessary and favourable aspect the photoelectricity purposes.This method can be described as " pipe bag viscous liquid " method, is used to make the precursor glass composition that comprises the glass ceramic material that is doped with optical activity ionic nanocrystal in this method and uses with the clad material of infusibility or heatproof.By method of the present invention, at first prepare the precursor glass composition, form it into rod.Secondly, the unreactiveness clad material that will comprise as improved silica forms pipe, wrap in glass stick around.Again secondly, matrix material from pipe package front body glass stick a little more than the temperature of the liquidus line of fiber-core glass composition the time draws out glass fibre, the clad fiberglass that at least a portion is drawn is heat-treated subsequently, produces nanocrystal in core composition, thereby makes glass-ceramic.
Brief description of drawings
Figure 1A. explanation is used for differential thermal analysis (DTA) curve of the temperature range of present pipe bag rod (RIT) method and two crucible (DC) method fiber drawings respectively.
Figure 1B. illustrate that the fibrosis of implementing the used glass-ceramic fibre of the present invention promptly manages differential thermal analysis (DTA) curve of scope in each self-forming zone of bag " viscosity " liquid method.
Fig. 2. the sectional view of cladded-fiber of the present invention.
The description of invention
As mentioned above, the previous method from most of glass ceramic composition drawing optical fiber is to adopt double crucible method.This method is often aggravated the pollution that the used precursor glass composition of fiber core is subjected to clad material.Pollute the composition that can obviously change the glass-ceramic core material that forms subsequently.In the present invention, we have proposed a kind of peculiar methods of making cladded-fiber He other optoelectronic equipment used in the telecommunication.The present invention is that the cladded-fiber that is used as such as an element in the optoelectronic equipment of the laser apparatus of present application and amplifier describes here.Yet, might not be so limited, the technology skilful person in clad material field can expect other purposes undoubtedly at an easy rate.
The present invention relates to utilize the thermal properties of material to make the transparent glass ceramics fiber core that is used in combination with durable covering.Figure 1A and 1B have illustrated thermodynamic principles involved in the present invention.Be shown in second-order transition temperature (T with at present used as Figure 1A g) and Tc (T x) between lower temperature range " pipe bag rod " the stretching method difference of operating, method of the present invention is to carry out when higher temperature.Than the lower temperature of the used temperature of the present invention the time, the core glass composition tends to crystallization, and the crystal that forms is too big usually, so that printing opacity effectively.Therefore, when drawn glass fiber and covering, wish to avoid to take place therein uncontrolled crystallization.Early stage formation crystal in manufacturing processed is unallowed, and it can occasion a great deal of trouble subsequently.The core glass composition should keep vitreous state in this manufacturing stage.From Figure 1B as can be seen, in order to avoid glass ceramic composition generation crystallization fully when making the preliminary shaping tensioning member, stretching should be at the liquidus temperature (T just above the candidate's glass ceramic material that is used as fiber core l) temperature under carry out.And when being applicable to other temperature end value of present double crucible method, it is too soft that outsourcing layer can become, and the material of forming can become mobile easily.Like this, as mentioned above, between core composition and covering composition too many chemical reaction can take place.Stand comparatively high temps and clad material unlikely and core glass composition generation chemical reaction or diffusion can be used to the covered fiber core, begin then to draw.Like this, novel method mainly is that the temperature dynamics separately of core material and clad material is changed.In other words, even two kinds of materials all experience identical temperature in drawing process, but temperature is a little more than the liquidus temperature (T of core glass l), keep below the kinetic control Tc (T of the much bigger cladding glass of viscosity simultaneously x).This method also can be considered between pipe excellent method of bag and the double crucible method in notional combination.
Fig. 2 is the sectional view of clad fibre of the present invention.In the figure, clad fibre is represented with numeral 10.Clad fibre 10 comprises core fibre 12, and this core fibre 12 has on the surface that is deposited on fiber 12 and encases the covering 14 of fiber 12.For clarity sake, size is special the amplification among the figure.
Fiber core 12 is made by the high temp glass stupalith of liquidus viscosity in about 100-200-2500 pool scope.Although glass standard routinely, the viscosity of glass core composition when liquidus temperature can be low, in any case core material should have sufficiently high viscosity when liquidus temperature, makes the diffusion of component element reduce to minimum.The softening temperature that has the glass ceramic composition of fine making performance in the present invention makes the method for fiber generally is higher than about 900 ℃.The object lesson of the glass composition of these kinds comprises the α of substantial transparent-and β-willemite glass-ceramic, it can be doped with transition metal and obtain optical activity, this material be disclosed in the name of Linda R.Pinckney submit to and transfer being entitled as of the application's common assignee " with α-and β-willemite be the glass-ceramic of base " U.S. Patent application in; Perhaps having the name submission that its transient metal doped glass ceramic material that is suitable for the performance of making optical amplifier and/or laser diode pump gain media, this material are described in George H.Beall and Linda R.Pinckney also transfers in the U.S. Patent application that is entitled as " transparent (lithium, zinc, magnesium) ortho-silicate glass-ceramic " of the application's common assignee equally.These two patent applications are all submitted on October 11st, 2000, and their full content is with reference to being incorporated into this.These glass ceramic compositions are characterised in that contained crystal is being nanocrystal by nature, and in other words, the crystalline diameter can be from being not more than about 50nm, to 25nm, and to 10nm, or even it is little to 5nm.In addition, these compositions are doped with at least a optically active ion.Optically active ion for example can be selected from transition metal or lanthanon.
The nanocrystalline glass-ceramic of containing transition metal is used novel laser and an optical amplifying materials of a kind of photoelectricity purposes of uniqueness.More particularly, spendable transition metal dopant can comprise titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), cobalt (Co), nickel (Ni), copper (Cu) or or even iron (Fe).Containing transition metal ionic glass ceramic material can not only keep its typical broadband emission feature, and compares with the pure glass matrix of similar adulterated non-crystalline state, often demonstrates the high-quantum efficiency as the allomeric.Like this, they can provide pure crystalline advantage on spectroscopic signature.And aspect materials processing, they can provide the advantage of glass.When doping lanthanon such as erbium (Er) in glass-ceramic, thulium (Tm), neodymium (Nd), praseodymium (Pr), ytterbium (Yb), dysprosium (Dy), holmium (Ho), can see similar effects.
In some cases, may lose a spot of basic metal or halide-ions in core material, this point can easily be compensated by add the volatile constituent of minute quantity in the raw batch of core glass composition.
Practices well in making the optical fiber process is to apply covering on fiber cores.This covering wrap in fiber around, covering 14 as shown in Figure 2.This covering plays a part to keep optical signal in the fiber core, because its refractive index ratio core is little.Yet, for fear of stress and potential fracture, the approaching coupling of the thermal expansivity of clad material (CTE) Ying Yuxin.The CTE of covering is better a little less than the CTE of core, the physical strength that caused so little stress under compression can provide.
Then just having produced such problem, promptly is clad material how to select the present invention used.We think that when the clad material of having selected suitable optical fiber to use the present invention just can satisfy following two requirements.At first, clad material should have higher viscosity, and should not have movably material R of significant quantity in clad material +, R 2+, make the rate of diffusion of each composition in core material reduce to minimum.This feature can reduce the amount of mutual diffusion between core and the clad material.In addition, before core material became too fusion, softness or volatilization, covering should be enough soft and stretchable.In other words, covering must be viscous enough when the drawing temperature that can draw, and core glass should keep stable on forming simultaneously, and promptly it should have enough low vapour pressure to avoid tangible volatilization.By method of the present invention, the viscosity of clad material is about 3 orders of magnitude (covering: core～10 with the ratio of the viscosity of core material 6: 10 3), make diffusion reduce to minimum.
The liquid core material should remain viscous liquid, promptly has alap vapour pressure.Secondly, covering also should be chemically inert for core glass.In other words, the reaction of clad material and viscous liquid core should be very small, if take place.
The clad material that satisfies these two requirements can comprise with the leading composition of additive agent modified silica comprises.The appropriate addn that is used for improved silica comprises the oxide compound of boron (B), germanium (Ge), inferior phosphorus (P), aluminium (Al), gallium (Ga), tantalum (Ta), titanium (Ti) and antimony (Sb).These oxide additions are called to have ready conditions with silicon-dioxide and form the oxide compound of glass, and any in them can combine use separately or with another kind.
Use these elements, especially the earth silicon material of B, Ge and/or P modification has some relevant features.At first, do not had the oxygen of bridge joint effect in these clad materials, all keys all are fully saturated, and these materials just demonstrate very strong unreactiveness like this.The oxide compound of B, Ge and P is preferably, and B and Ge are better slightly.Phosphorus is comparatively effective on the reduction softening temperature, but its pair key can stay bigger space in glass structure.These spaces can allow alkali ion enter, thereby have weakened the unreactiveness of clad material.Usually, reduce the oxide content of basic metal and alkaline-earth metal as far as possible.The softening temperature that these compounds tend to reduce unreactiveness and can reduce glass inadequately.
Secondly, by avoiding the oxide compound of basic metal and alkaline-earth metal, the softening temperature of these materials can have very big variation in to height to the scope of pure silicon dioxide softening temperature from about 1200 ℃, depends on the requirement of the component characteristic of core material.By an embodiment of the inventive method, because the softening temperature height just can adopt the drawing temperature a little more than the core composition liquidus temperature.Secondly, the thermal expansivity of high temp glass pottery is in about 10-90 * 10 again -7In/℃ the scope, but usually in 20-70 * 10 -7In/℃ the scope, or 30-60 * 10 -7In/℃ the scope.The CTE of used clad material is better a shade below the CTE of core glass.For example, the CTE of covering is in about 5-70 * 10 -7In/℃ the scope, or in 15-60 * 10 -7In/℃ the scope, but better in 15-25 * 10 -7In/℃ the scope.As mentioned above, the such stress under compression that difference provided of thermal expansivity can help to strengthen clad fibre.
Another favorable characteristics of the inventive method is that the fibre technology of prepared fiber and silicon dioxide base adapts, and is easy to the fusion joint, because covering comprises a large amount of silicon-dioxide.
In other method of for example pipe bag particle method, because need a large amount of time heat fused glass cullet, in the clad material significant diffusion can take place.Since in the methods of the invention used core material be form good glass material, so the diffusion of component element tendency is just little.
After the characteristic of glass-ceramic core that nanocrystal has been discussed and improved silica clad material, just be not difficult to understand the Fibrotic novel method of the present invention.This method is similar with " pipe bag rod " method, but still significant difference is arranged, because method of the present invention has been utilized the thermal characteristics of these materials better.As previously mentioned, be clear that the present invention draws fiber and should carry out usually just above the temperature of the liquidus temperature of fiber glass core the time.Yet this does not get rid of if the kinetics of crystallisation process is enough slow, and fiber can draw under the temperature of the liquidus temperature that is lower than core glass.In addition, the improved silica covering has higher heatproof degree characteristic, so stand than the used much higher temperature of clad material of the previous conventional pipe excellent method of bag.In the method for the invention, the rod that derives from precursor glass that at first stretches also coats it with the covering of above-mentioned improved silica, makes clad fiberglass.The more handy externalizing of improved silica pipe is learned vapour deposition (CVD) method such as OVD or VAD method and is made, but also can adopt conventional fusion or flame method to make.The improved silica covering of CVD manufactured does not often contain unit price or divalent ion.Thereby can just mechanically core be placed in the covering covering is attached on the core.Shown in Figure 1B, pulling process carries out when being lower than the temperature of Tc of covering at the liquidus temperature that is higher than core.After drawing out clad fiberglass, to it in the process that draws or be more typically in and carry out suitable thermal treatment in subsequently the step and make it that crystallization take place.
Say that roughly a part of the present invention is to make the method for photoelectric material.This method comprises some steps: a) preparation glass composition, and acquisition is used to be doped with the precursor glass of at least a optical activity ionic nanocrystalline glass-ceramic; B) precursor glass is formed glass stick; C) encase glass stick with the chemically inert clad material of better making by improved silica; D) matrix material from glass stick and covering is made optical element such as fiber when the temperature of the kinetics Tc that is lower than viscosity covering (glass) material a little more than the liquidus temperature of the bigger precursor glass of flowability; E) at least a portion of optical element is heat-treated, crystallization goes out nanocrystal in precursor glass.Optically active doping agent is selected from transition metal and lanthanon.The size of the nanocrystal that forms in glass-ceramic is not more than about 50nm, can be as small as 5nm.
Making by method of the present invention in the process of glass optical fiber, cladding glass is viscous enough drawing under the temperature, and it can be drawn when core glass is the temperature of chemically stable (even core glass is bigger than covering flowability this moment).Adopt chemical Vapor deposition process the batch of material of cladding glass to be made the form of pipe.Cladding glass is suitable for making the glass that mainly comprises with the silicon-dioxide of the modified oxide modification of the oxide compound of at least a B of being selected from, Ge, P, G, Al, Ta, Ti or Sb.The softening temperature of the cladding glass of modification is at least 900-1000 ℃ like this, perhaps is 1200 ℃, or even high softening temperature (1640-1650 ℃) to pure fused silica.
In addition, the glass-ceramic fibre core that contains the nanocrystal that useful covering coats in the optical fiber that makes by present method, composition by controlling fiber process and core and clad material and the thermal parameter chemical transport that component element between core and the cladding glass carries out of make suring is reduced to minimum.And the migration of component element will be reduced to such degree, and promptly the refracting interface between core and covering can not have a negative impact to the transmission of core and the conveying of ripple.The thermal expansivity of fiber core is about 10-90 * 10 -7/ ℃, and the thermal expansivity of clad material is about 5-70 * 10 -7/ ℃.
Our experiment up to now shows that this method is operated very goodly, has made the gratifying optical fiber that can potteryization that interested optical communication purposes is had correct transition metal ion emmission spectrum under experimental conditions.Although for illustrative purposes better embodiment of the present invention has been done detailed disclosure, but the technology skilful person of this area can understand, under the situation that does not depart from the scope of the invention that appended claims and its equivalents limited, can make change or improvement to it, and can predict other embodiment.

Claims (21)

1. method of making the glass-ceramic photoelectric material, it comprises:
A) prepare a kind of glass composition, obtain to be used to be doped with the precursor glass of at least a optical activity ionic nanocrystalline glass-ceramic, this precursor glass has certain Tc;
B) precursor glass is formed glass stick;
C) encase glass stick with chemically inert clad material;
D) when being higher than the temperature of precursor glass crystallization temperature, form optical element from glass stick;
E) at least a portion of this optical element of thermal treatment, crystallization goes out nanocrystal in precursor glass, makes glass-ceramic.
2. the method for claim 1, wherein the optical activity ion is selected from transition metal and lanthanon.
3. method as claimed in claim 2 wherein is used for the transition metal of doped-glass pottery to be selected from Ti, V, Cr, Mn, Co, Ni, Cu or Fe.
4. method as claimed in claim 3 wherein is used for the transition metal of doped-glass pottery to be selected from Cr, Ni or Co.
5. method as claimed in claim 2 wherein is used for the lanthanon of doped-glass pottery to be selected from Er, Tm, Nd, Pr, Yb, Dy or Ho.
6. the method for claim 1, wherein the size of nanocrystal is not more than about 50nm.
7. the method for claim 1, wherein photoelectric material is the form of cladded-fiber.
8. method as claimed in claim 7, wherein the clad material of optical fiber adopts the silica glass that carries out modification through the oxide compound of at least a B of being selected from, Ge, P, Ga, Al, Ta, Ti or Sb.
9. method as claimed in claim 8, wherein optical fiber is with being selected from B 2O 3, GeO 2And P 2O 5The silica glass of oxide modifying.
10. method as claimed in claim 7, wherein glass-ceramic forms the core of optical fiber, and the CTE of core is 10-90 * 10 -7/ ℃, and the CTE of covering is 5-70 * 10 -7/ ℃.
11. method as claimed in claim 10, wherein the CTE of glass-ceramic core is 20-70 * 10 -1/ ℃, and the CTE of covering is 15-60 * 10 -7/ ℃.
12. a manufacturing has the method for the nanocrystalline glass-ceramic optical fiber that is doped with at least a optical activity ionic core, this method comprises:
A) make the precursor glass stick;
B) clad material of manufacturing improved silica;
C) the precursor glass stick is added in the clad material;
D) be lower than the matrix material of stretching precursor glass stick and clad material under the temperature of kinetics Tc of clad material being higher than the precursor glass crystallization temperature;
E) under the condition that can promote formation nanocrystal in core, the clad fibre that draws is heat-treated, make glass-ceramic.
13. method of making cladded-fiber, this method comprises founds batch of material, acquisition is used to be doped with the precursor glass of the nanocrystalline glass-ceramic of transition metal, form glass stick from this precursor glass melt, mechanically be added to glass stick in the cladding, under temperature, it is stretched, subsequently at least a portion of thermal treatment clad fiberglass under the condition that can produce nanocrystal therein a little more than the liquidus temperature of drawn glass fibre composite.
14. as claim 1 or 13 described methods, it also comprises cladding glass is applied on the glass fibre, described cladding glass has enough viscosity thereby can stretch under draft temperature, even core glass is mobile when this draft temperature, vapour pressure is also enough low, can avoid tangible volatilization.
15. as claim 1 or 13 described methods, it also comprises adopts chemical vapor deposition (CVD) manufactured cladding glass.
16. as claim 1 or 13 described methods, it comprises that also the softening temperature of the glass of Huo Deing is at least about 900 ℃ like this with the batch of material coating glass fibre that is suitable for making mainly the glass of being made up of silicon-dioxide and at least a modified oxide.
17. method as claimed in claim 16, it also comprises with a kind of glass fibre-coated, and described glass has mainly by silicon-dioxide and is selected from forming that at least a oxide compound of B, Ge and P constitutes.
18. an optical fiber, it comprises: the glass-ceramic fibre core of nanocrystal; Wrap in the covering around the described core, the thermal parameter by the controlling fiber process makes the migration of the component element between covering and the core composition reduce to minimum.
19. optical fiber as claimed in claim 18, wherein the migration of component element is reduced to such degree, makes that the interface between core and covering can not have a negative impact to the transmission of core and the conveying of ripple.
20. optical fiber as claimed in claim 18, this optical fiber are to be higher than the Tc of core composition, clad material are kept below to be drawn under the temperature of its Tc simultaneously.
21. a light communication system, it comprises the fiber that makes by the described method of claim 1.
CN 00814320 1999-10-18 2000-10-18 Method for making nanocrystalline glass-ceramic fibers Pending CN1379740A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US16005299P 1999-10-18 1999-10-18
US60/160,052 1999-10-18

Publications (1)

Publication Number Publication Date
CN1379740A true CN1379740A (en) 2002-11-13

Family

ID=22575315

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 00814320 Pending CN1379740A (en) 1999-10-18 2000-10-18 Method for making nanocrystalline glass-ceramic fibers

Country Status (6)

Country Link
EP (1) EP1240113A2 (en)
JP (1) JP2003512988A (en)
CN (1) CN1379740A (en)
AU (1) AU3633901A (en)
CA (1) CA2388707A1 (en)
WO (1) WO2001031367A2 (en)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1317574C (en) * 2005-03-04 2007-05-23 浙江工业大学 Nanocrystalline quantum dot optical fiber and optical fiber amplifier
CN102470546A (en) * 2009-08-03 2012-05-23 应用纳米结构方案公司 Incorporation of nanoparticles in composite fibers
US8784937B2 (en) 2010-09-14 2014-07-22 Applied Nanostructured Solutions, Llc Glass substrates having carbon nanotubes grown thereon and methods for production thereof
US8815341B2 (en) 2010-09-22 2014-08-26 Applied Nanostructured Solutions, Llc Carbon fiber substrates having carbon nanotubes grown thereon and processes for production thereof
US8951631B2 (en) 2007-01-03 2015-02-10 Applied Nanostructured Solutions, Llc CNT-infused metal fiber materials and process therefor
US8951632B2 (en) 2007-01-03 2015-02-10 Applied Nanostructured Solutions, Llc CNT-infused carbon fiber materials and process therefor
US9005755B2 (en) 2007-01-03 2015-04-14 Applied Nanostructured Solutions, Llc CNS-infused carbon nanomaterials and process therefor
CN104556678A (en) * 2015-01-19 2015-04-29 华南理工大学 Preparation method of quantum dot doped microcrystalline glass optical fiber
CN104556671A (en) * 2015-01-19 2015-04-29 华南理工大学 Preparation method of transition metal ion doped microcrystalline glass fibers
CN106483599A (en) * 2015-12-24 2017-03-08 南开大学 A kind of rare earth ion doped phosphate glass microcrystal fiber
US10138128B2 (en) 2009-03-03 2018-11-27 Applied Nanostructured Solutions, Llc System and method for surface treatment and barrier coating of fibers for in situ CNT growth
CN109160723A (en) * 2018-08-20 2019-01-08 华南理工大学 A kind of multi-mode optical sensing nanocomposite glass optical fiber and its preparation method and application
WO2020220924A1 (en) * 2019-04-30 2020-11-05 上海大学 Active microcrystalline optical fiber preparation method and device
CN114276023A (en) * 2021-11-17 2022-04-05 宁波大学 Infrared chalcogenide glass ceramic optical fiber and preparation method thereof
CN115182044A (en) * 2022-07-27 2022-10-14 山东铂锐激光科技有限公司 Method for preparing sesquioxide single crystal optical fiber cladding

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6297179B1 (en) * 1999-10-18 2001-10-02 Corning Incorporated Transition-metal, glass-ceramic gain media
US6632758B2 (en) 2001-05-03 2003-10-14 Corning Incorporated Transparent gallate glass-ceramics
CA3072672A1 (en) 2019-02-19 2020-08-19 Thorlabs, Inc. High efficiency emission in praseodymium doped conventional glass and fiber

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2727054A1 (en) * 1977-06-15 1978-12-21 Siemens Ag METHOD OF MANUFACTURING A GLASS FIBER LIGHT GUIDE
AU5316699A (en) * 1998-08-25 2000-03-14 Corning Incorporated Methods and apparatus for producing optical fiber

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1317574C (en) * 2005-03-04 2007-05-23 浙江工业大学 Nanocrystalline quantum dot optical fiber and optical fiber amplifier
US9574300B2 (en) 2007-01-03 2017-02-21 Applied Nanostructured Solutions, Llc CNT-infused carbon fiber materials and process therefor
US8951631B2 (en) 2007-01-03 2015-02-10 Applied Nanostructured Solutions, Llc CNT-infused metal fiber materials and process therefor
US8951632B2 (en) 2007-01-03 2015-02-10 Applied Nanostructured Solutions, Llc CNT-infused carbon fiber materials and process therefor
US9005755B2 (en) 2007-01-03 2015-04-14 Applied Nanostructured Solutions, Llc CNS-infused carbon nanomaterials and process therefor
US9573812B2 (en) 2007-01-03 2017-02-21 Applied Nanostructured Solutions, Llc CNT-infused metal fiber materials and process therefor
US10138128B2 (en) 2009-03-03 2018-11-27 Applied Nanostructured Solutions, Llc System and method for surface treatment and barrier coating of fibers for in situ CNT growth
CN102470546A (en) * 2009-08-03 2012-05-23 应用纳米结构方案公司 Incorporation of nanoparticles in composite fibers
CN102470546B (en) * 2009-08-03 2014-08-13 应用纳米结构方案公司 Incorporation of nanoparticles in composite fibers
US8969225B2 (en) 2009-08-03 2015-03-03 Applied Nano Structured Soultions, LLC Incorporation of nanoparticles in composite fibers
US8784937B2 (en) 2010-09-14 2014-07-22 Applied Nanostructured Solutions, Llc Glass substrates having carbon nanotubes grown thereon and methods for production thereof
US8815341B2 (en) 2010-09-22 2014-08-26 Applied Nanostructured Solutions, Llc Carbon fiber substrates having carbon nanotubes grown thereon and processes for production thereof
CN104556671A (en) * 2015-01-19 2015-04-29 华南理工大学 Preparation method of transition metal ion doped microcrystalline glass fibers
CN104556678A (en) * 2015-01-19 2015-04-29 华南理工大学 Preparation method of quantum dot doped microcrystalline glass optical fiber
CN106483599A (en) * 2015-12-24 2017-03-08 南开大学 A kind of rare earth ion doped phosphate glass microcrystal fiber
CN109160723A (en) * 2018-08-20 2019-01-08 华南理工大学 A kind of multi-mode optical sensing nanocomposite glass optical fiber and its preparation method and application
CN109160723B (en) * 2018-08-20 2021-11-23 华南理工大学 Multi-mode optical sensing nanocrystalline composite glass optical fiber and preparation method and application thereof
WO2020220924A1 (en) * 2019-04-30 2020-11-05 上海大学 Active microcrystalline optical fiber preparation method and device
US11502475B2 (en) 2019-04-30 2022-11-15 Shanghai University Method and device for processing active microcrystalline fiber by magnetic field induction and lasering
CN114276023A (en) * 2021-11-17 2022-04-05 宁波大学 Infrared chalcogenide glass ceramic optical fiber and preparation method thereof
CN114276023B (en) * 2021-11-17 2024-05-10 宁波大学 Infrared chalcogenide glass ceramic optical fiber and preparation method thereof
CN115182044A (en) * 2022-07-27 2022-10-14 山东铂锐激光科技有限公司 Method for preparing sesquioxide single crystal optical fiber cladding

Also Published As

Publication number Publication date
EP1240113A2 (en) 2002-09-18
WO2001031367A3 (en) 2001-09-13
JP2003512988A (en) 2003-04-08
WO2001031367A2 (en) 2001-05-03
AU3633901A (en) 2001-05-08
CA2388707A1 (en) 2001-05-03

Similar Documents

Publication Publication Date Title
CN1379740A (en) Method for making nanocrystalline glass-ceramic fibers
AU743385B2 (en) Composition for optical waveguide article and method for making continuous clad filament
US5735927A (en) Method for producing core/clad glass optical fiber preforms using hot isostatic pressing
JP3527707B2 (en) Optical fiber preform having OH blocking layer and method for manufacturing the same
US7844162B2 (en) Method for fabricating IR-transmitting chalcogenide glass fiber
CN1257584A (en) Fluorinated rare earth doped glass and glass-ceramic articles
ZA200101616B (en) Methods and apparatus for producing optical fiber.
CN107915400A (en) A kind of method that pipe melt method prepares graded index YAS glass core fibres
CN104609722B (en) Preparation method of tube-melt co-drawn bismuth-doped optical fiber
JP2002535238A (en) Optical fiber preform having OH barrier and method of manufacturing the same
US6792187B2 (en) Ca-Al-Si oxide glasses and optical components containing the same
US6698246B1 (en) Method for making nanocrystalline glass-ceramic fibers
CN1544964A (en) Rare earth ion doped oxyfluoride microcrystalline glass optical fiber and preparation method thereof
US20020041750A1 (en) Rare earth element-doped, Bi-Sb-Al-Si glass and its use in optical amplifiers
Miura et al. Fluorozirco-aluminate glass fiber
CN1919763A (en) Glass optical fibre capable of fusing with quartz glass optical fibre and manufacture method thereof
JP2882908B2 (en) Image fiber
JP3903689B2 (en) Optical fiber manufacturing method
CN1332703A (en) Tantala doped optical waveguide and method of manufacture
CN1657458A (en) Tellurium silicate glass with low expansion coefficient and its manufacturing method
TWI284750B (en) The glass fiber can be doped with silica glass fiber and its method for making
ITTO20090969A1 (en) "FIBER OPTIC DEVICE FOR LASER EMISSION"

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication