CN115385576B - Cesium-containing glass, polygonal gradient refractive index fiber lens and array preparation method thereof - Google Patents

Cesium-containing glass, polygonal gradient refractive index fiber lens and array preparation method thereof Download PDF

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CN115385576B
CN115385576B CN202210924568.7A CN202210924568A CN115385576B CN 115385576 B CN115385576 B CN 115385576B CN 202210924568 A CN202210924568 A CN 202210924568A CN 115385576 B CN115385576 B CN 115385576B
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polygonal
refractive index
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array
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CN115385576A (en
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吴青晴
邹快盛
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Suzhou University
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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C13/00Fibre or filament compositions
    • C03C13/04Fibre optics, e.g. core and clad fibre compositions
    • C03C13/045Silica-containing oxide glass compositions
    • C03C13/046Multicomponent glass compositions
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03BMANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B37/00Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
    • C03B37/01Manufacture of glass fibres or filaments
    • C03B37/012Manufacture of preforms for drawing fibres or filaments
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03BMANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B37/00Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
    • C03B37/01Manufacture of glass fibres or filaments
    • C03B37/02Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor
    • C03B37/025Manufacture 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
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C1/00Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/60Surface treatment of fibres or filaments made from glass, minerals or slags by diffusing ions or metals into the surface
    • C03C25/601Surface treatment of fibres or filaments made from glass, minerals or slags by diffusing ions or metals into the surface in the liquid phase, e.g. using solutions or molten salts
    • C03C25/602Surface treatment of fibres or filaments made from glass, minerals or slags by diffusing ions or metals into the surface in the liquid phase, e.g. using solutions or molten salts to perform ion-exchange between alkali ions
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00Simple or compound lenses
    • G02B3/0006Arrays
    • G02B3/0012Arrays characterised by the manufacturing method
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03BMANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2203/00Fibre product details, e.g. structure, shape
    • C03B2203/02External structure or shape details
    • C03B2203/04Polygonal outer cross-section, e.g. triangular, square

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Glass Compositions (AREA)

Abstract

The application belongs to the technical field of optical glass wiredrawing processing, and provides cesium-containing glass, a polygonal gradient refractive index fiber lens and an array preparation method thereof for further improving the pixel filling rate and the light energy utilization rate of an optical fiber array; the compound proportion of cesium-containing glass is as follows: 40% -60% Cs 2 O;25%‑40%SiO 2 ;5%‑10%B 2 O 3 ;3%‑8%Al 2 O 3 ;3%‑9%ZnO;5%‑10%Na 2 O+K 2 O;0.5%‑2%ZrO 2 ;3%‑5%InF 3 . The glass has high cesium content and can pass Cs in the glass + K in ion and high temperature molten salt + The ion concentration gradient change caused by ion replacement is larger, so that the refractive index of the center and the edge of the glass fiber is larger as a whole. Each unit pixel of the polygonal gradient refractive index lens array and the fiber array which are made based on cesium-containing glass is polygonal, so that triangular gaps existing during stacking between the pixels are reduced; the unit pixels are made of gradient refractive index materials, do not need a cladding layer, and can directly transmit light.

Description

Cesium-containing glass, polygonal gradient refractive index fiber lens and array preparation method thereof
Technical Field
The application belongs to the technical field of optical glass wiredrawing processing, and particularly relates to a glass formula, gradient refractive index fibers and an array preparation method.
Background
The fiber optical devices such as the optical fiber panel, the optical fiber image transmission beam, the light transmission rod, the fiber light cone, the optical fiber image inverter and the like are widely applied to image detection, biological identification and image light guide identification devices, and have important application prospects in the fields of consumer electronics, medical health, intelligent security, aerospace and the like.
The fiber optic device is internally composed of numerous sub-fibers, each sub-fiber being referred to as a unitary picture element. The cross section structure of the sub-optical fiber of the traditional fiber optical device is circular, and consists of a high-refractive-index central fiber core and a low-refractive-index outer cladding, wherein the diameter of a unit pixel is 3-10 microns, and the diameter of the cladding is 0.4-0.6 microns. Due to the existence of the low-refractive index cladding, the filling rate of the pixels on the whole fiber optic device layout is reduced, the pixel structure is circular, triangular gaps exist between the pixels when the pixels are piled up, the filling rate of the pixels is further reduced, and finally the overall filling rate of the pixels is about 70%, so that the light energy utilization rate and imaging quality of the fiber optic device are affected.
Disclosure of Invention
In order to further improve the pixel filling rate and the light energy utilization rate of the optical fiber array, the application provides cesium glass and a preparation method of the polygonal gradient refractive index cesium glass optical fiber array.
The cesium-containing glass is prepared from the following compounds in percentage by weight: 40% -60% Cs 2 O;25%-40%SiO 2 ;5%-10%B 2 O 3 ;3%-8%Al 2 O 3 ;3%-9%ZnO;5%-10%Na 2 O+K 2 O;0.5%-2%ZrO 2 ;3%-5%InF 3
Cs 2 O is a main component of glass and is used for realizing K in high-temperature molten salt + Ion exchange is carried out on ions to realize Cs from the center to the edge of the glass fiber + Ion concentration gradually decreases and K + The ion concentration gradually increases. Due to Cs + The unit refractive index of the ions in the glass is 1.76, K + The ion has a unit refractive index of 1.57 in the glass and passes through Cs in the glass + K in ion and high temperature molten salt + The ion concentration gradient change caused by ion replacement reduces the refractive index, so that the refractive index of the glass fiber from the center to the edge gradually reduces as a whole;
SiO 2 to ensure that the glass production temperature is not more than 1450 degrees, typically the content of the component is not more than 65% for glass forming bodies, the glass main component; the weight composition of 25-40% is selected, so that the glass smelting temperature can be ensured to be 1380-1420 ℃;
B 2 O 3 to ensure SiO as flux 2 And other glass components are sufficiently melted into a glass body;
Al 2 O 3 ZnO is a glass intermediate, structurally connected with Si 4+ Ions and Cs + Ion, na + Ions, K + Ions, in 3+ Bridge of monovalent and trivalent ions such as ions while ensuring Cs + K in ions and fused salts + The stability of the whole structure of the glass in the ion exchange process is improved, and the high-temperature corrosion resistance of the glass is improved;
Na 2 O+K 2 the O monovalent oxide is a glass structure network modifier and is used for reducing the glass forming temperature, and the mixing ratio of the components can regulate and control the ion exchange temperature and speed of cesium glass;
ZrO 2 is used for improving the crystallization resistance in the process of drawing glass or drawing optical fibers for multiple times.
InF 3 For Cs + Ion, na + Ions, K + Bridging of monovalent network modifier ions such as ions ensures stable structure of glass network, improves chemical stability of glass during high-temperature ion exchange, and simultaneously combines Cs 2 The mixed proportion of O is favorable for regulating and controlling the deviation between the refractive index distribution index generated by ion exchange and theoretical calculation.
As preferable: the weight percentages of the ingredients are as follows: 42% -55% Cs 2 O;25%-33%SiO 2 ;6%-8%B 2 O 3 ;3%-5%Al 2 O 3 ;4%-6%ZnO;5%-8%Na 2 O+K 2 O;1%-2%ZrO 2 ;3%-5%InF 3
The cesium-containing glass has the advantages that: high cesium content, passing Cs in glass + K in ion and high temperature molten salt + The difference value of ion concentration gradient change caused by ion replacement is larger, so that the gradual reduction amplitude of the refractive index from the center to the edge of the glass fiber is larger and the chromatic aberration is small.
A preparation method of polygonal gradient refractive index fiber comprises the following steps:
1) Mixing all the compounds to prepare cesium-containing glass batch;
2) Smelting the cesium-containing glass batch in a platinum crucible with the temperature of 1380-1420 ℃, and discharging from a furnace to form cylindrical glass;
3) Processing the cylindrical glass into polygonal cylindrical glass with a cross section, and polishing the side wall surfaces of the polygonal cylindrical glass;
4) Drawing the polygonal columnar glass into continuous polygonal glass fibers on a drawing machine;
5) Placing the polygonal glass fiber into 500-600 ℃ potassium nitrate molten salt for Cs + -K + Ion exchange to form a polygonal gradient index fiber with a gradually decreasing refractive index from the center to the edge.
The number of sides of the polygon is preferably: 2 (n+1), where n is a natural number. For example, in the case of four, six and eight, the refractive index of the polygonal glass fiber monofilament in cross section is symmetrically distributed about the center.
Preferably, the diameter of the cylindrical glass is 50-70 mm, the side length of the cross section of the polygonal cylindrical glass is 15-35 mm, and the length is 300-600 mm.
Preferably, the length of the polygonal gradient refractive index fiber is 200-600 mm, and the side length of the cross section is 1-5 mm.
The gradient refractive index fiber manufactured by the method can be manufactured into a polygonal gradient refractive index fiber lens by cutting a certain length and polishing two end faces.
The gradient refractive index fiber manufactured by the method has the cross section of a polygon, so that gaps among side walls can be effectively reduced, and the filling rate is improved. In addition, the refractive indexes of the polygonal gradient refractive index fibers are distributed in a gradient manner from the center to the edge, incident light rays with different incident angles are transmitted forwards in the polygonal gradient refractive index fibers according to a sine rule, the light ray transmission process is repeated according to a fixed period rule, if the period is marked as P, when the length L of the polygonal gradient refractive index fibers is 0.25P, the collimated light rays are incident from one end, and then the light rays can be automatically focused on the other end face; if the polygonal gradient index fiber length is selected to be an integer multiple of half period, for example, 0.5P, 1P, 1.5P, 2P, the light rays are emitted in parallel. The polygonal gradient refractive index fiber can be utilized to realize the functions of light collimation, image transmission and the like.
The preparation method of the polygonal gradient refractive index lens array further comprises the following steps of: 6) Arranging a plurality of polygonal gradient refractive index fibers into an array according to the cross section as a polygon to form a polygonal gradient refractive index fiber array rod;
further still include: 7) And (3) melting and pressing the polygonal gradient refractive index fiber array rod in a melting and pressing furnace at 750-850 ℃. Gaps among the polygonal gradient refractive index fibers can be removed through melt-press molding, so that a polygonal gradient refractive index fiber array mother rod is formed; cutting the polygonal gradient refractive index fiber array mother rod according to the optical imaging design length; and polishing the two end faces to obtain the polygonal gradient refractive index lens array.
And (3) performing secondary wire drawing on the polygonal gradient refractive index fiber array rod, and arranging the secondary wire drawing into a polygonal array again to perform tertiary wire drawing until the polygonal gradient refractive index fiber array with the whole preset diameter and the single core preset diameter is formed. The steps can be repeated as required, the rows are repeated after the wire drawing, and the wire drawing is performed again to obtain the expected array specification.
Has the following characteristics: 1) Each unit pixel is polygonal, so that triangular gaps existing in stacking between the pixels are reduced; 2) The unit pixels are made of gradient refractive index materials, do not need a cladding layer, and can directly transmit light; 3) The novel glass system is adopted, so that the manufacture of the polygonal gradient refractive index optical fiber is easy.
Drawings
FIG. 1 is a schematic diagram of the transmission track of the axis light of a polygonal gradient index fiber lens and the refractive index distribution of a cross section;
FIG. 2 shows a schematic diagram of a quadrilateral gradient index fiber lens array structure and a cross-sectional refractive index distribution;
FIG. 3 is a schematic diagram of a hexagonal gradient index fiber lens array structure and a cross-sectional refractive index distribution.
Detailed Description
The application is further described with reference to the accompanying drawings and examples:
example 1
A cesium-containing glass made from a compound comprising: 42% Cs 2 O,33%SiO 2 ,6%B 2 O 3 ,3%Al 2 O 3 ,4%Na 2 O,4%K 2 O,4%ZnO,1%ZrO 2 ,3%InF 3
Example two
A cesium-containing glass made from a compound comprising: 49% Cs 2 O,25%SiO 2 ,6%B 2 O 3 ,4%Al 2 O 3 ,4%Na 2 O,1%K 2 O,4%ZnO,2%ZrO 2 ,5%InF 3
Example III
A preparation method of quadrilateral gradient refractive index fiber comprises 1) mixing each compound to obtain a batch;
2) Melting cesium-containing glass in a platinum crucible with the temperature of 1380-1420 ℃, and discharging to form cylindrical glass with the diameter of 60 mm; 3) Processing the cylindrical glass into quadrangular cylindrical glass with the cross section of 30mm multiplied by 450mm, and polishing the side wall surfaces of the quadrangular cylindrical glass;
4) Putting quadrangular columnar glass on a wire drawing machine to be drawn into quadrangular glass fibers with continuous section side length of 1mm and length of 500mm;
5) Putting the quadrilateral glass fiber into 560 ℃ potassium nitrate molten salt for Cs + -K + Ion exchange to form gradient distribution with cross section with gradually lowered refractive index from the center to the edge.
After a certain length is intercepted, the two end faces are polished to be processed into a quadrilateral gradient refractive index fiber lens, the light ray track and the refractive index distribution of the quadrilateral gradient refractive index fiber lens are shown as figure 1, and incident light rays with different incident angles are transmitted forwards in the gradient refractive index fiber lens according to a sine rule; if the length of 0.25P is taken to be incident by collimated light, the light rays are automatically focused on the end face; if the length of the integral multiple half period of 0.5P, 1P, 1.5P, 2P is selected, the light rays are emitted in a nearly parallel mode.
Example IV
On the basis of the third embodiment, a preparation method of the quadrilateral gradient refractive index lens array further comprises the following steps:
step 6) arranging quadrilateral gradient refractive index fibers into an array according to a quadrilateral cross section, wherein the side length of the array cross section is 25mm after the quadrilateral gradient refractive index fibers are arranged into the array, and the array length is 500mm; and (3) carrying out melt-pressing molding in a melt-pressing furnace at 800 ℃ to remove gaps among the polygonal gradient refractive index fibers to form a quadrangular gradient refractive index fiber array mother rod.
The quadrangular gradient refractive index fiber array mother rod is cut according to the length of 0.5P-0.75P, two end faces are polished, so that a quadrangular gradient refractive index fiber lens array which can be imaged in a 1:1 positive mode and is shown in figure 2 is formed, and refractive index distribution changes on the cross section according to a periodic parabolic rule.
Example five
Based on the fourth embodiment, a preparation method of the quadrilateral gradient refractive index fiber array further comprises the steps of:
7) Arranging quadrilateral gradient refractive index fibers into an array according to a quadrilateral cross section, wherein the side length of the cross section of the array is 20mm after the quadrilateral gradient refractive index fibers are arranged into the array, and the length of the array is 500mm; and (3) carrying out secondary drawing on the arranged quadrilateral array on a drawing machine with the temperature of a drawing furnace being 760 ℃, drawing into quadrilateral glass filaments with the side length of 2mm and the length of 500mm, rearranging the quadrilateral glass filaments into quadrilateral arrays with the cross section side length of 20mm and the length of 500mm after the secondary drawing, carrying out tertiary drawing, drawing into quadrilateral glass filaments with the side length of 10 microns, rearranging the secondary drawing into polygonal arrays, and carrying out tertiary drawing until a quadrilateral gradient refractive index fiber array with the whole cross section side length of 4mm and the cross section side length of 3-5 microns of a single pixel core is formed. The steps can be repeated as required, the rows are repeated after the wire drawing, and the wire drawing is performed again to obtain the expected array specification.
The third to fifth embodiments are only one specific application example of the present invention, and the hexagonal gradient index fiber array shown in fig. 3, or the gradient index fiber array of other shapes, may be manufactured as required.

Claims (9)

1. The preparation method of the polygonal gradient refractive index fiber is characterized by comprising the following steps of:
1) Mixing all the compounds containing cesium glass to prepare a batch; the cesium-containing glass is prepared from the following compounds in percentage by weight: 40% -60% Cs 2 O;25%-40%SiO 2 ;5%-10%B 2 O 3 ;3%-8%Al 2 O 3 ;3%-9%ZnO;5%-10%Na 2 O+K 2 O;0.5%-2%ZrO 2 ;3%-5%InF 3
2) Melting cesium-containing glass in a platinum crucible at the temperature of 1380-1420 ℃, and discharging from a furnace to form cylindrical glass;
3) Processing the cylindrical glass into polygonal cylindrical glass with a cross section, and polishing the side wall surface of the polygonal cylindrical glass;
4) Drawing the polygonal columnar glass into continuous polygonal glass fibers on a drawing machine;
5) Placing the polygonal glass fiber into 500-600 ℃ potassium nitrate molten salt for Cs (carbon fiber) + -K + Ion exchange to form a polygonal gradient index fiber with a gradually decreasing refractive index from the center to the edge.
2. The method for preparing the polygonal gradient refractive index fiber according to claim 1, wherein the cesium-containing glass ingredients comprise: 42% -55% Cs 2 O;25%-33%SiO 2 ;6%-8%B 2 O 3 ;3%-5%Al 2 O 3 ;4%-6%ZnO;5%-8%Na 2 O+K 2 O;1%-2%ZrO 2 ;3%-5%InF 3
3. The method for preparing the polygonal gradient index fiber according to claim 1, wherein: the number of sides of the polygon is as follows: 2 (n+1), where n is a natural number.
4. The method for preparing the polygonal gradient index fiber according to claim 1, wherein: the diameter of the cylindrical glass is 50-70 mm, the length of the polygonal cylindrical glass is 300-600 mm, and the side length of the cross section is 15-35 mm.
5. The method for preparing the polygonal gradient index fiber according to claim 1, wherein: and arranging a plurality of polygonal gradient refractive index fibers into an array rod according to a cross-section polygonal mode.
6. A preparation method of a polygonal gradient refractive index lens is characterized by comprising the following steps: the polygonal gradient index fiber lens prepared by the method for preparing the polygonal gradient index fiber according to claim 1 is manufactured by cutting the polygonal gradient index fiber according to a preset length and polishing two end faces.
7. A preparation method of a polygonal gradient refractive index lens array is characterized by comprising the following steps: placing the array rod prepared by the polygonal gradient refractive index fiber preparation method of claim 5 into a melting furnace at 750-850 ℃ for melting and pressing to form a polygonal gradient refractive index fiber array master rod, cutting the polygonal gradient refractive index fiber array master rod according to the optical imaging design length, and polishing two end faces to obtain the polygonal gradient refractive index lens array.
8. A preparation method of a polygonal gradient refractive index fiber array is characterized by comprising the following steps: the array rod prepared by the preparation method of the polygonal gradient index fiber in claim 5 is subjected to secondary drawing, and the secondary drawing is rearranged into a polygonal array for three times of drawing until the whole polygonal gradient index fiber array with the preset diameter and the single core preset diameter is formed.
9. A polygonal gradient index fiber produced by the process of producing a polygonal gradient index fiber of claim 1.
CN202210924568.7A 2022-08-02 2022-08-02 Cesium-containing glass, polygonal gradient refractive index fiber lens and array preparation method thereof Active CN115385576B (en)

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WO2004028992A1 (en) * 2002-09-27 2004-04-08 Ericsson Telecomunicações S.A. Tellurite glass, optical fibre, optical amplifier and light source
CN107572776A (en) * 2017-08-01 2018-01-12 苏州端景光电仪器有限公司 A kind of gradient-index lens parent glass and gradient-index lens
CN107555784A (en) * 2017-08-04 2018-01-09 苏州端景光电仪器有限公司 A kind of optical glass containing caesium and preparation method and application
CN212134990U (en) * 2020-06-16 2020-12-11 山东泉兴银桥光电缆科技发展有限公司 Gradient refractive index optical fiber composite wire and image transmission bundle
CN112327406A (en) * 2020-12-04 2021-02-05 苏州德睿电力科技有限公司 High-filling-rate flexible optical fiber image transmission bundle, mold and image transmission bundle preparation method

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