CN111694090B

CN111694090B - Optical fiber leather pipe and preparation method and application thereof

Info

Publication number: CN111694090B
Application number: CN202010690012.7A
Authority: CN
Inventors: 王久旺; 周游; 王云; 付杨; 王叶; 蔡京生
Original assignee: China Building Materials Academy CBMA
Current assignee: China Building Materials Academy CBMA
Priority date: 2020-07-17
Filing date: 2020-07-17
Publication date: 2022-03-22
Anticipated expiration: 2040-07-17
Also published as: CN111694090A

Abstract

The invention relates to an optical fiber leather material pipe and a preparation method and application thereof, wherein the optical fiber leather material pipe sequentially comprises a body layer, an absorption layer and an oxidation layer from inside to outside; the bulk layer comprises a first oxide MO and M₂O₃Said first oxide MO is PbO; the first oxide M₂O₃Selected from Bi₂O₃、Cd₂O₃、Sn₂O₃、Sb₂O₃And As₂O₃At least one of; the absorbing layer contains the same M element as the body layer, and at least one part of the M element exists in the absorbing layer in a simple substance form; the oxide layer and the body layer have the same material composition. The preparation method comprises the following steps: carrying out reduction reaction on the raw leather pipe in a hydrogen environment; and in an air environment, precisely annealing the obtained cladding pipe to oxidize the outer surface of the absorption layer and part of the simple substance M in the area below the outer surface so as to form an oxidation layer. The optical fiber leather tube disclosed by the invention has full-angle absorption capability on stray light and has higher absorption performance.

Description

Optical fiber leather pipe and preparation method and application thereof

Technical Field

The invention relates to the technical field of optical fibers, in particular to an optical fiber leather material pipe and a preparation method and application thereof.

Background

The optical fiber is a core made of transparent materials such as glass, quartz or plastic, and the outer surface of the optical fiber is provided with a transparent leather tube with low refractive index. The finished component, single fiber diameter, is typically between a few microns and tens of microns.

The optical fiber image-transmitting element (such as optical fiber panel, image inverter, light cone, etc.) is made up by using several million or even tens of millions of optical fibers whose diameter is several micrometers, and making them pass through such processes of arranging them into a rod, melting-pressing, forming and optical processing. The numerical aperture can reach 1.0, and the optical film has the characteristic of optical zero thickness. The optical fiber image transmission element is used as an important element of photoelectric enhancement equipment such as a photomultiplier tube and the like, and is widely applied to high-end equipment such as night vision instruments, medical imaging equipment, energy detection and the like and the leading-edge field.

The quality of the imaging quality of the optical fiber image transmission element mainly depends on the relative optical performance parameters such as light transmittance, contrast and the like. However, in the conventional optical fiber preparation, as shown in fig. 1, a core rod 1 ', a sheath tube 2', an absorption filament 4 'and a filling filament 3' are combined to form a fiber structure (see fig. 1); and multiple materials are finally fused and molded at the same temperature, so that a plurality of factors influencing the performance are large, a plurality of uncontrollable defects are generated, and the improvement of the optical performance of an optical fiber product is limited, which is one of the key factors restricting the development of night vision optics all the time. The leather material pipe 2 'is made of a transparent glass pipe made of a single material, and an absorption wire 4' and a filling wire 3 'are inserted between fibers, wherein the absorption wire 4' can realize the absorption of stray light 5 ', and the filling wire 3' can reduce the pore proportion. Such a structure composed of a plurality of different materials is more likely to cause defects such as dark spots, grids and the like.

Disclosure of Invention

In view of the above, the main objective of the present invention is to provide an optical fiber sheath tube and a method for manufacturing the same and an application thereof, wherein the outer surface layer of the sheath tube is reduced by a reduction treatment process to generate a dark absorption layer, and the absorption layer has stray light absorption capability; the structure of the optical fiber element is improved, the fiber composed of the original core material, the leather material and the absorption material is improved into the core material and the leather material, the optimization of the optical fiber structure is realized, the absorption effect of stray light is improved, and the optical performance of the optical fiber image transmission device is improved.

The purpose of the invention and the technical problem to be solved are realized by adopting the following technical scheme. According to the optical fiber leather material pipe provided by the invention, the optical fiber leather material pipe sequentially comprises a body layer, an absorption layer and an oxidation layer from inside to outside;

the bulk layer comprises a first oxide MO and M₂O₃Said first oxide MO is PbO; the first oxide M₂O₃Selected from Bi₂O₃、Cd₂O₃、Sn₂O₃、Sb₂O₃And As₂O₃At least one of;

the absorbing layer contains the same M element as the body layer, and at least one part of the M element exists in the absorbing layer in a simple substance form;

the oxide layer and the body layer have the same material composition.

The object of the present invention and the technical problem to be solved can be further achieved by the following technical solutions.

Preferably, in the optical fiber sheath tube, a ratio of thicknesses of the body layer, the absorption layer and the oxidation layer is (2.4-2.6): (0.2-0.4): (0.15-0.2).

Preferably, in the optical fiber ferrule tube, the body layer further includes a second oxide, and the second oxide includes SiO₂、B₂O₃、Al₂O₃、Na₂O、K₂O, BaO, CaO and ZrO₂(ii) a The body layer comprises the following components in percentage by mass:

SiO₂ 55-65%；

B₂O₃ 0-5%；

Al₂O₃ 0-5%；

Na₂O 5-8%；

K₂O 5-8%；

BaO 5-10%；

CaO 5-10%；

ZrO₂ 0-5%；

PbO、Bi₂O₃、Cd₂O₃、Sn₂O₃、Sb₂O₃and As₂O₃1-2% of the total amount of the components.

The purpose of the invention and the technical problem to be solved can be realized by adopting the following technical scheme. The preparation method of the optical fiber leather material pipe provided by the invention comprises the following steps:

a reduction step: carrying out reduction reaction on the raw leather pipe in a hydrogen environment; the raw material leather hose comprises a first oxide MO/M₂O₃Said first oxide MO is PbO; the first oxide M₂O₃Selected from Bi₂O₃、Cd₂O₃、Sn₂O₃、Sb₂O₃And As₂O₃At least one of; part of the first oxide in the outer surface of the raw material leather hose and the area below the outer surface is reduced into a simple substance M to form an absorption layer;

an oxidation step: in the air environment, the cladding pipe obtained in the step 1)

Heating from normal temperature to 500-600 ℃ for 3-4 hours, and preserving the heat for 2-3 hours,

then heating to 600-630 ℃ for 2-3 hours and preserving the heat for 2-3 hours,

heating to Tg +50 ℃ after 1-2 hours, preserving the heat for 2-3 hours,

cooling to 500-600 ℃ after 2-3 hours;

cooling to normal temperature after 10-15 hours;

so that the outer surface of the absorption layer and part of the simple substance M in the area below the outer surface are oxidized to form an oxidized layer.

Preferably, in the preparation method of the optical fiber sheath tube, before the reduction step, a pretreatment step is further included:

supporting the inner surface of the leather tube by a support;

vacuumizing the inner part of the leather hose until the vacuum degree is 5-20 pa; and

and sealing two ports of the leather hose by melting.

Preferably, in the preparation method of the optical fiber sheath tube, after the step 2), the method further includes: cooling the leather glass tube obtained in the step 2) to normal temperature, cutting off the seals at two ends, and dismantling and fixing.

The purpose of the invention and the technical problem to be solved can be realized by adopting the following technical scheme.

The optical fiber provided by the invention comprises a skin layer and a core layer, wherein the skin layer sequentially comprises a body layer, an absorption layer and an oxidation layer from inside to outside;

the oxide layer and the body layer have the same material composition.

Preferably, in the optical fiber, the thickness ratio of the bulk layer, the absorption layer and the oxide layer is (2.4-2.6): (0.2-0.4): (0.15-0.2).

According to the present invention, an optical fiber bundle is provided, which includes a plurality of optical fibers as described above.

The purpose of the invention and the technical problem to be solved can be realized by adopting the following technical scheme. According to the optical fiber image transmission element provided by the invention, the optical fiber image transmission element comprises a plurality of optical fibers.

Preferably, in the optical fiber image transmission element, the optical fiber image transmission element is an optical fiber panel or an optical fiber image inverter.

Preferably, in the aforementioned optical fiber image transmission element, the optical fiber image transmission element is a light cone.

The purpose and the problem to be solved by the invention can be realized by adopting the following technical scheme. According to the night vision goggles provided by the invention, the night vision goggles comprise the image intensifier, and the image intensifier comprises the optical fiber image transmission element.

The purpose and the problem to be solved by the invention can be realized by adopting the following technical scheme. The endoscope provided by the invention comprises the optical fiber image transmitting element.

The purpose and the problem to be solved by the invention can be realized by adopting the following technical scheme.

According to the invention, the electronic device comprises the optical fiber image transmitting element, and the electronic device is a particle detector or a signal detector.

The leather tube is subjected to reduction process treatment, so that the outer layer of the leather tube generates a gradual change absorption layer and an oxidation layer, and the defect that fusion is generated between two different materials of the leather and the absorption wire due to the fact that a single absorption wire is inserted between fibers is avoided.

Compared with the prior art, the invention has the following beneficial effects:

the optical fiber cladding tube prepared by the invention not only can simplify the integral structure of the optical fiber, but also greatly reduces the generation of light transmission defects caused by the defects of fusion interfaces of various materials in the preparation process of the optical fiber, improves the relative consistency and integrity of each optical fiber and improves the optical performance of an optical fiber image transmission device. The optical fiber leather tube not only has full-angle absorption capacity on stray light, but also has higher absorption performance. The optical fiber leather material tube has the full-angle stray light absorption capacity of 360 degrees in the circumferential direction, and the absorption angle is far higher than the absorption angle of 38.5 degrees which can be reached by the arrangement mode of single fiber peripheral absorption threads in the existing high-performance optical fiber product (the contrast of transmitted optical signals is less than 1 percent); and the light absorption layer is more uniform, so that the phenomenon of uneven surface transmittance of single fibers caused by the fact that the original absorption wire arrangement mode locally absorbs stray light is avoided. In addition, the optical fiber of the present invention can be applied to high-end equipment such as night vision instruments, medical imaging instruments, energy detection, etc., and leading edge fields.

The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.

Drawings

FIG. 1 is a schematic diagram of the internal structure of a prior art optical fiber fabrication;

FIG. 2 is a schematic view of the internal structure of the optical fiber of the present invention;

FIG. 3 is a schematic structural diagram of an optical fiber ferrule of the present invention;

FIG. 4 is a schematic structural view of a coil spring tooling of the present invention;

FIG. 5 is a schematic structural view of a fixture fixing plug according to the present invention;

FIG. 6 is a schematic structural view of the coil spring tooling of the present invention after installation;

FIG. 7 is a schematic diagram of stray light absorption of the fiber optic ferrule of the present invention;

FIG. 8 is a schematic view of a prior art arrangement of absorbent filaments in a fiber rod;

FIG. 9 is a schematic view of the absorption angle of a prior art fiber rod absorbent filament;

FIG. 10 is a graph showing a comparison of the transmittance before and after reduction in example 2 of the present invention;

FIG. 11 is a graph showing the effect of reduction duration on the transmittance of the prepared optical fiber sheath tube;

FIG. 12 is a graph showing the effect of the last incubation time on the transmittance of the prepared fiber optic sheath tube;

FIG. 13 is a graph showing a comparison of the transmittance before and after reduction of the sheath tube of optical fiber according to example 7 of the present invention;

FIG. 14 is a graph showing a comparison of the transmittance before and after reduction of the optical fiber sheath tube of example 8 of the present invention;

FIG. 15A is one of XPS plots after reduction in example 1 of the present invention;

FIG. 15B is a second XPS chart showing the reduction of example 1.

Detailed Description

To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description will be made on the fiber optic housing tube, its manufacturing method, its application, its specific implementation, its features and its effects according to the present invention with reference to the accompanying drawings and preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features or characteristics of one or more embodiments may be combined in any suitable manner.

The following materials or reagents, unless otherwise specified, are all commercially available.

As shown in fig. 3, the present invention provides an optical fiber leather hose, which includes a body layer 31, the body layer 31, an absorption layer 32 and an oxidation layer 33 sequentially arranged from inside to outside; said bulk layer 31 comprising a first oxide MO and M₂O₃Said first oxide MO is PbO; the first oxide M₂O₃Selected from Bi₂O₃、Cd₂O₃、Sn₂O₃、Sb₂O₃And As₂O₃Preferably PbO and Bi₂O₃Therefore, the hydrogen reduction effect can be better after optimization, and a dark and gradually changed absorption layer is generated on the surface of the glass; the absorbing layer 32 contains the same M element as the body layer 31, and at least a part of the M element exists in the absorbing layer 32 in a simple substance form, preferably, the absorbing layer 32 contains the absorbing layer 32 by the mass of the absorbing layer 320.3-0.9% of simple substance, so that the prepared optical fiber leather tube has better absorption capacity on stray light; preferably, the absorption layer 32 contains Pb and Bi, so that the absorption capability of the optical fiber leather tube to stray light is better and the absorption performance is higher; the oxide layer 33 and the bulk layer 31 have the same material composition; preferably, the absorption layer 32 contains PbO and Bi respectively₂O₃Therefore, the optical fiber leather material pipe can have better interfiber fusion effect after being optimized, and simultaneously effectively eliminates the internal stress of the glass pipe and effectively prevents the glass pipe from being burst.

In specific implementation, the thickness ratio of the body layer 31, the absorption layer 32 and the oxide layer 33 is (2.4-2.6): (0.2-0.4): (0.15-0.2). For example, the body layer 31 may be 0.24mm to 0.26mm thick; the thickness of the absorption layer can be 0.2mm-0.4 mm; the thickness of the oxide layer may be 0.15mm-0.2 mm. Preferably, the thickness of the absorption layer is 0.23mm to 0.32 mm; the thickness of the oxide layer is 0.2mm, so that the absorption capacity of stray light is improved after optimization, and a better interfiber fusion effect can be achieved. The absorption layer is gradually changed, and has 360-degree full-angle absorption capacity on stray light, namely the stray light can be absorbed by the absorption layer on the surface of the optical fiber leather pipe when the stray light enters from any angle around the optical fiber leather pipe. The wall thickness of the leather material pipe is 2.8 mm-3.2 mm, the inner diameter is 25 mm +/-0.1 mm, and the length is 400 mm-420 mm. The optical fiber leather tube has an absorption angle of 360 degrees in the circumferential direction, which is far higher than the absorption angle of 0 degree of the existing leather tube and the absorption angle of 38.5 degrees which can be reached by the arrangement mode of the single-fiber peripheral absorption yarns in the existing high-performance optical fiber product; the refractive index of the optical fiber leather material pipe is 1.45-1.55.

In specific implementation, the thickness of the absorption layer 32 is measured by a digital measurement projector, and the method specifically includes the following steps:

selecting a projection lens with proper multiplying power: determining the multiple of an objective lens according to the size of a sample of the measured optical fiber leather pipe;

placing the sample on a stage: according to the surface to be measured of the sample of the measured optical fiber leather tube, the sample is arranged on an objective table in the direction opposite to the lens;

turning on a power switch: turning on a power supply, and then turning on a transmission light source at the bottom of the contour projection;

adjusting the focal length: rotating a focus adjusting hand wheel to enable a clear image (a shadow part is an absorption layer) to be presented on the projection screen;

detecting and adjusting the moving direction of the workpiece: the measured part (shaded part) of the measured optical fiber leather pipe sample is positioned in the effective range of the main screen through the adjustment of the X-direction platform adjusting knob and the Y-direction platform adjusting knob;

and (3) size measurement: aligning one boundary of the measured part with the division line on the main screen by adjusting the X-direction platform adjusting button and the Y-direction platform adjusting button; and clearing the digital display positions in the X direction and the Y direction, moving the sample along the radial direction (the direction vertical to the absorption layer) of the measured optical fiber cladding pipe sample by adjusting an X or Y direction platform adjusting button, aligning the other boundary of the measured part with the division line on the main screen, and displaying the thickness value of the absorption layer on the digital display screen.

Similarly, the thicknesses of the bulk layer 31 and the oxide layer 33 can also be obtained by the above-mentioned method.

The "bulk layer", "absorber layer" and "oxide layer" are arbitrarily divided by the thickness measurement described above for ease of description, with no distinct interfaces between layers.

The above-mentioned "having an absorption angle of 360 ° in the circumferential direction" means that stray light incident from any angle around the circumference of the optical fiber cladding tube can be absorbed by the absorption layer on the surface of the optical fiber cladding tube.

In specific implementation, the body layer 31 further includes a second oxide, and the second oxide includes SiO₂、B₂O₃、Al₂O₃、Na₂O、K₂O, BaO, CaO and ZrO₂(ii) a The body layer 31 comprises the following components in percentage by mass:

SiO₂ 55-65%；

B₂O₃ 0-5%；

Al₂O₃ 0-5%；

Na₂O 5-8%；

K₂O 5-8%；

BaO 5-10%；

CaO 5-10%；

ZrO₂ 0-5%；

The invention also provides a preparation method of the optical fiber leather material pipe, which comprises the following steps:

a reduction step: carrying out reduction reaction on the raw leather pipe in a hydrogen environment; the raw material leather hose comprises a first oxide MO and M₂O₃Said first oxide MO is PbO; the first oxide M₂O₃Selected from Bi₂O₃、Cd₂O₃、Sn₂O₃、Sb₂O₃And As₂O₃At least one of the above components, so as to ensure that the glass surface generates a dark and gradually changed absorption layer after reduction; part of the first oxide in the outer surface of the raw material leather hose and the area below the outer surface is reduced into a simple substance M to form an absorption layer;

then heating to 600-650 ℃ for 2-3 hours and preserving the heat for 2-3 hours,

heating to Tg +20 ℃ after 1-2 hours, preserving the heat for 2-3 hours,

cooling to 500-600 ℃ after 2-3 hours;

cooling to normal temperature after 10-15 hours;

In specific implementation, before the reduction step, the method can also comprise a pretreatment step:

supporting the inner surface of the leather tube by a support;

and sealing two ports of the leather hose by melting.

In specific implementation, the pretreatment step specifically comprises:

placing the coil spring-shaped tool into a raw material leather hose to enable the inner wall of the leather hose to be tightly supported, and fixing two ends of the leather hose by fixing plugs; the inside of the leather tube is vacuumized to the vacuum degree of 5-20pa, and then port sealing is carried out at the temperature of Ts to Ts +50 ℃.

In specific implementation, the method further comprises the following steps after the step 2): cooling the leather glass tube obtained in the step 2) to normal temperature, cutting off the seals at two ends, and dismantling and fixing.

In specific implementation, the preparation method of the optical fiber leather tube specifically comprises the following steps:

1) ultrasonically cleaning a raw material leather hose with purified water for 20-30 minutes (removing pollutants such as dust particles and the like attached to the inner and outer surfaces) under the condition of more than thousand grades of purification degree (such as a purification workshop), cleaning with absolute ethyl alcohol for 1-2 times, and air-drying at normal temperature; placing the coil spring-shaped tool 10 shown in fig. 4 into the middle position inside a clean leather hose, and expanding the leather hose outwards until the leather hose is tightly attached to the inner wall to play a supporting role, wherein the reserved length of each of the two ends is 1-1.2 times of the outer diameter of the leather hose so as to facilitate port sealing, rotating anticlockwise to the direction of S1 shown in fig. 6 until the inner wall of the leather hose 30 is tightly expanded, fixing the two ends through the fixing plugs 20 shown in fig. 5 to prevent loosening, wherein the fixing plugs 20 are used for fixing the coil spring-shaped tool 10;

2) then placing the leather tube into a sealing furnace, vacuumizing the interior of the leather tube by using an oil-free vacuum pump until the vacuum degree is 5-20pa, sealing the end of the leather tube at the softening temperature Ts-Ts +50 ℃, and annealing for 6-10 hours until the temperature is reduced to normal temperature to obtain a vacuum leather tube; after sealing, the inside of the vacuum leather material pipe is isolated from hydrogen and does not react, so that the inside of the vacuum leather material pipe is in a non-reduction environment, and a reduction layer on the inner wall can be prevented from being generated in the reduction treatment process; cooling to normal temperature after 8-9 hours, and taking out;

3) reducing the vacuum leather pipe obtained in the step 2) for 10-15 hours at the glass transition temperature Tg-Tg +50 ℃ and under the hydrogen flow of 15-30ml/min, so that a uniform reduction layer of 0.5-0.6mm (preferably 0.5 mm) is formed on the surface of the vacuum leather pipe, the effective absorption of the pipe material to light after preparation can be ensured, the viscosity change caused by the overlarge thickness of the absorption layer can be reduced, the wire drawing difficulty is increased, and the temperature is reduced to the normal temperature after 6-10 hours;

4) placing the vacuum leather material pipe obtained in the step 3) in an annealing furnace, carrying out precision annealing to oxidize the surface layer of the vacuum leather material pipe to form an oxide layer of 0.2-0.3mm, and discharging waste gas through a discharge port of the reducing furnace; the specific conditions of the precision annealing are set as follows: after 3-4 hours, the furnace temperature is raised from the normal temperature to 500-plus-600 ℃, the temperature is preserved for 2-3 hours, then the temperature is raised to 600-plus-630 ℃ after 2-3 hours, the temperature is preserved for 2-3 hours, the temperature is raised to Tg +50 ℃ after 1-2 hours, the temperature is preserved for 2-3 hours, the temperature is lowered to 500-plus-600 ℃ after 2-3 hours, and then the temperature is lowered to the normal temperature after 12-15 hours; the prepared optical fiber leather pipe basically recovers the matching performance between leather materials by forming the oxidation layer with the thickness of 0.2-0.3mm, can play a better interfiber fusion effect, avoids the phenomenon that the straightening performance is reduced and more defects are caused due to the change of the component structure of the glass on the surface of the optical fiber leather pipe caused by the reduction process, effectively eliminates the internal stress of the glass pipe by the precision annealing process, and effectively prevents the explosion.

5) Cooling the vacuum leather material pipe obtained in the step 4) to normal temperature, taking out the vacuum leather material pipe, cutting two ends of the vacuum leather material pipe except the length of the coil spring-shaped tool by using a diamond cutting blade, taking down the fixing plug 20, rotating the coil spring-shaped tool reversely (in the direction of S2) as shown in figure 6 to separate the coil spring-shaped tool from the inner wall of the leather material pipe 30 ', then taking out the coil spring-shaped tool, ultrasonically cleaning the leather material pipe 30' by purified water at 50-60 ℃ for 20-30 minutes (with the frequency of 40-50 KHz), cleaning 1-2 times by absolute ethyl alcohol, and then naturally drying to obtain the optical fiber leather material pipe. As shown in fig. 7, after light is incident into the optical fiber cladding tube, if there is stray light 5 entering the optical fiber cladding tube, the stray light 5 will be absorbed by the absorption layer 40 of the optical fiber cladding tube, which gradually enhances the light absorption from inside to outside, before being emitted out of the outer wall of the cladding tube, and since the absorption layer 40 is completely covered on the outer surface, the stray light 5 at any angle can be effectively absorbed; therefore, interference caused by the fact that stray light which is emitted out propagates to the inside of adjacent and similar fibers can be effectively avoided, the light transmission efficiency of each fiber is improved, and the overall optical performance of the fiber element is improved; when stray light enters the existing leather tube, the light can be totally transmitted by the leather tube, namely the absorption angle of the light to the stray light is 0. The arrangement of the absorbing filaments of the existing optical fiber product is shown in fig. 8, and the outer part of each fiber 82 is provided with 1.5-2.5 absorbing filaments 81 on average; the stray light absorption angle of the single absorbing filament 81 with respect to the single fiber 82 is only 15.4 degrees (see fig. 9), so the peripheral stray light absorption angle of each fiber 82 is only 38.5 degrees at maximum. In practical production, in order to facilitate the insertion of the absorption filament into the single fiber gap, the total absorption angle of the stray light of the single fiber is only about 34 degrees, which is far lower than the absorption angle of the stray light of 360 degrees in the invention. Therefore, the optical fiber leather material pipe prepared by the invention not only has 360-degree full-angle absorption capacity on stray light, but also has higher absorption performance.

In the specific implementation, in the step 1), the coil spring-shaped tool 10 is a coil spring structure made of a titanium alloy material, has the characteristics of temperature resistance and no discoloration, and has 3 to 4 circles, wherein the thickness of each circle is 0.3 to 0.4mm, and the length of each circle is less than two pipe diameters of the length of the leather material pipe; the innermost side of the coil spring-shaped tool 10 is provided with a loading and unloading card 11 (see figure 4). The coil spring-shaped tool 10 can play a good role in supporting a fixed pipe shape during vacuum fusion sealing and high-temperature surface treatment.

In specific implementation, in step 1), as shown in fig. 5, the fixed plug 20 includes a cylindrical first plug 21 and a circular truncated cone-shaped second plug 22 integrally connected to the first plug 21; the diameter of the upper bottom surface of the second plug 22 is the same as that of the first plug 21, and the diameter of the lower bottom surface of the second plug 22 is larger than that of the upper bottom surface thereof. The side surface of the first plug body 21 is provided with a gap matched with the assembling and disassembling clamping piece 11 of the coil spring-shaped tool 10, and the assembling and disassembling clamping piece 11 is matched with the gap to realize the fixation of two ends of the leather material pipe.

In specific implementation, in the step 4), the specific conditions of the precision annealing are set as follows: the furnace temperature is raised from the normal temperature to 500 ℃ after 3 hours, the temperature is kept for 2 hours, the temperature is raised to 600 ℃ after 2 hours, the temperature is kept for 2 hours, the temperature is raised to the glass transition temperature Tg after 1 hour, the temperature is kept for 2 hours, the temperature is lowered to 500 ℃ after 2 hours, and the temperature is lowered to the normal temperature after 10 hours.

The invention also provides an optical fiber, which comprises a skin layer and a core layer, wherein the skin layer sequentially comprises a body layer 31, an absorption layer 32 and an oxidation layer 33 from inside to outside; said bulk layer 31 comprising a first oxide MO and M₂O₃Said first oxide MO is PbO; the first oxide M₂O₃Selected from Bi₂O₃、Cd₂O₃、Sn₂O₃、Sb₂O₃And As₂O₃At least one of; the absorbing layer 32 contains the same M element as that in the body layer 31, and at least a part of the M element exists in the absorbing layer 32 in a simple substance form; the oxide layer 33 has the same material composition as the bulk layer 31. The thicknesses of the bulk layer 31, the absorption layer 32 and the oxide layer 33 are described above and are not described herein.

In specific implementation, the skin layer is made of the optical fiber skin tube 2; the core layer is made of a core glass rod 1, a filling wire 3 is inserted between the core glass rod 1 and an optical fiber leather tube 2 to realize the absorption of stray light 5 (see fig. 2), and the core glass rod 1, the optical fiber leather tube 2 and the filling wire 3 are combined into a fiber structure through the prior art, and are not described again.

The invention also provides an optical fiber bundle which comprises a plurality of optical fibers.

The invention also provides an optical fiber image transmission device, and the optical fiber image transmission element comprises a plurality of optical fibers. The optical fiber image transmission device can be an optical fiber panel, an optical fiber image inverter or an optical cone.

The invention also provides night vision goggles which can comprise an image intensifier, wherein the image intensifier comprises the optical fiber image transmission element; the optical fiber image transmission element is an optical fiber panel or an optical fiber image inverter.

The invention also provides an endoscope, which can comprise the optical fiber image transmission element; the optical fiber image transmission element is an optical fiber panel or an optical fiber image inverter.

The invention also provides electronic equipment which can comprise the optical fiber image transmission element; the optical fiber image transmission device is an optical fiber panel, an optical fiber image inverter or an optical cone; the electronic device may be a particle detector or a signal detector.

The following is a further description with reference to specific examples.

Example 1

The embodiment provides a preparation method of an optical fiber leather material pipe, which comprises the following steps:

in a thousand-level purification workshop, putting a leather hose as a raw material into a 40KHz ultrasonic cleaning machine, cleaning the leather hose for 20 minutes by purified water at the temperature of 60 ℃, taking out the leather hose, putting the leather hose into an absolute ethyl alcohol tank again, cleaning the leather hose for 1 time by absolute ethyl alcohol, and vertically and naturally drying the leather hose; the raw material leather hose comprises the following components in percentage by mass: SiO 2₂ 63%；B₂O₃ 4.5%；Al₂O₃ 4%；Na₂O 6%；K₂O 5.3%；BaO 7.5%；CaO 6%；ZrO ₂2%；PbO 0.7%；Bi₂O₃1%。

And (3) placing the coil spring-shaped tool shown in the figure 4 into the air-dried leather hose, and placing the tool at the middle position to ensure that the lengths of the two ends are respectively reserved for 30 mm. And (3) rotating the coil spring-shaped tool anticlockwise, and plugging the fixing plug shown in the figure 5 into the coil spring-shaped tool for fixing after tightly supporting the inner wall of the leather hose. And then putting the leather material pipe into a melting sealing furnace, vacuumizing the interior of the leather material pipe by using an oil-free vacuum pump until the vacuum degree reaches 20Pa, manually operating sealing pliers at 650 ℃ to seal the two ends, and cooling to the normal temperature for 8 hours to finish the preparation of the vacuum leather material pipe.

And (2) putting the prepared vacuum leather pipe into a reduction furnace, introducing hydrogen for reduction treatment according to a reduction process, supplying hydrogen at a flow rate of 25ml/min in the reduction furnace, reducing for 12 hours at 625 ℃, and cooling to normal temperature after 8 hours to ensure that a uniform reduction layer with the thickness of about 0.5mm is formed on the surface of the vacuum leather pipe.

Then the vacuum leather material pipe is placed into an annealing furnace for precision annealing: after 3 hours, raising the furnace temperature from the normal temperature to 550 ℃, preserving heat for 2 hours, raising the temperature to 600 ℃ after 2 hours, preserving heat for 2 hours, raising the temperature to 625 ℃ after 1 hour, preserving heat for 2 hours, reducing the temperature to 500 ℃ after 2 hours, and then reducing the temperature to the normal temperature after 10 hours, so that the surface layer of the leather pipe is oxidized to form an oxide layer with the thickness of about 0.2mm, and discharging waste gas through a discharge port of a reduction furnace;

and cooling the vacuum leather tube to normal temperature, taking out the vacuum leather tube, cutting two ends of the vacuum leather tube except the length of the coil spring-shaped tool by using a diamond cutting blade, sealing, taking down the fixing plug, separating the fixing plug from the inner wall of the vacuum leather tube by reversely rotating the coil spring-shaped tool, taking out the coil spring-shaped tool, ultrasonically cleaning the vacuum leather tube for 20 minutes by using purified water, cleaning the vacuum leather tube for 1 time by using absolute ethyl alcohol, and naturally drying the vacuum leather tube to obtain the optical fiber leather tube. The thickness of the absorption layer on the surface of the optical fiber cladding tube was measured to be about 0.23mm, and the transmittance curve is shown in fig. 11. As can be seen from FIG. 11, the transmittance of the prepared fiber optic sheath tube under the irradiation of the collimated light with the wavelength of 400 and 1100nm is about 10%. The optical fiber cladding tube described in this embodiment sequentially comprises a body layer 31, an absorption layer 32 and an oxidation layer 33 from inside to outside; the bulk layer 31 comprises 0.7% of PbO and 1% of Bi by mass of the bulk layer₂O₃A thickness of about 2.57 mm; the absorber layer 32 contains 0.3% of Pb and 0.45% of Bi by mass of the absorber layer, and has a thickness of about 0.23 mm; the oxide layer 33 contains 0.7% of PbO and 1% of Bi by mass of the oxide layer₂O₃Its thickness is about 0.2 mm.

In addition, the sample of the hydrogen-reduced optical fiber sheath tube of the present example was subjected to X-ray photoelectron spectroscopy (XPS) characterization, as shown in FIGS. 15A-15B, and Pb was observed in FIGS. 15A-15B ²⁺ 4f_7/2Has a binding energy of 138.5eV and Pb² ⁺The binding energy of 4f7/2 is shifted to a lower binding peak, and that of 136.6eV corresponds to Pb⁰This indicates the presence of reduced Pb in the reduced sample of the fiber optic ferrule⁰；Bi ³⁺4f_7/2Has a binding energy of 160.6eV, Bi ³⁺4f_7/2The binding energy of (A) shifts to a lower binding peak, and the binding energy of 156.8eV corresponds to Bi⁰This indicates the presence of reduced Bi in the reduced sample of the fiber optic ferrule⁰. That is, when the hydrogen reduction time was 12 hours, both of Pb ions and Bi ions on the surface of the sample of the prepared optical fiber sheath tube were reduced to simple substances.

Drawing the optical fiber sheath tube, the core glass rod and the filling wire into a single optical fiber by the prior art, wherein the optical fiber comprises a sheath layer and a core layer, and the sheath layer sequentially comprises a body layer 31, an absorption layer 32 and an oxidation layer 33 from inside to outside; the transmittance of the optical fiber under the irradiation of diffused light with the wavelength of 430-; a plurality of optical fibers are manufactured into an optical fiber panel or an optical fiber image inverter by the prior art (such as arrangement into a rod, fusion molding, optical processing and the like), and the transmittance of the optical fiber panel or the optical fiber image inverter under the irradiation of diffused light with the wavelength of 430-900nm is 63%. The optical fiber panel or the optical fiber image inverter can be used in an image intensifier of night vision goggles and also can be used in a particle detector or a signal detector.

Example 2

The difference between this example and example 1 is that the hydrogen reduction time of this example is 15 hours, and the optical fiber leather tube with the thickness of the absorbing layer of about 0.32mm is finally prepared, and the transmittance test curve is shown in fig. 11, and it can be seen from fig. 11 that the transmittance of the prepared optical fiber leather tube when irradiated by the collimated light with the wavelength of 400 and 1100nm is about 2.4%.The optical fiber cladding tube described in this embodiment sequentially includes a body layer 31, an absorption layer 32, and an oxide layer 33 from inside to outside. The bulk layer 31 comprises 0.7% of PbO and 1% of Bi by mass of the bulk layer₂O₃A thickness of about 2.48 mm; the absorber layer 32 contains 0.33% of Pb and 0.49% of Bi by mass of the absorber layer, and has a thickness of about 0.32 mm; the oxide layer 33 contains 0.7% of PbO and 1% of Bi by mass of the oxide layer₂O₃Its thickness is about 0.2 mm.

As can be seen from fig. 10, when the collimated light with the wavelength of 400-. This indicates that the hydrogen reduction contributes to 0.7% of PbO and 1% of Bi₂O₃The transmittance of the optical fiber sheath tube is reduced.

Drawing the optical fiber sheath tube, the core glass rod and the filling wire into a single optical fiber by the prior art, wherein the optical fiber comprises a sheath layer and a core layer, and the sheath layer sequentially comprises a body layer 31, an absorption layer 32 and an oxidation layer 33 from inside to outside; the transmittance of the optical fiber under the irradiation of diffused light with the wavelength of 430-; a plurality of optical fibers are manufactured into an optical fiber panel or an optical fiber image inverter by the prior art (such as arrangement into a rod, fusion molding, optical processing and the like), and the transmittance of the optical fiber panel or the optical fiber image inverter under the irradiation of diffused light with the wavelength of 400-900nm is 57%. The optical fiber panel or the optical fiber image inverter can be used in an image intensifier of night vision goggles and also can be used in a particle detector or a signal detector.

Example 3

The difference between this example and example 1 is that the hydrogen reduction time is 8 hours, and the final cladding tube with the thickness of the absorbing layer of about 0.16mm is prepared, and the transmittance test curve is shown in fig. 11, and it can be seen from fig. 11 that the transmittance of the prepared optical fiber cladding tube when irradiated by the collimated light with the wavelength of 400-. The bulk layer 31 comprises 0.7% of PbO and 1% of Bi by mass of the bulk layer₂O₃A thickness of about 2.64 mm; the absorption layer 32 is an absorption layerContains 0.33% of Pb and 0.47% of Bi by mass, and has a thickness of about 0.16 mm; the oxide layer 33 contains 0.7% of PbO and 1% of Bi by mass of the oxide layer₂O₃Its thickness is about 0.2 mm.

Drawing the optical fiber sheath tube, the core glass rod and the filling wire into a single optical fiber by the prior art, wherein the optical fiber comprises a sheath layer and a core layer, and the sheath layer sequentially comprises a body layer 31, an absorption layer 32 and an oxidation layer 33 from inside to outside; the transmittance of the optical fiber under the irradiation of diffused light with the wavelength of 430-; a plurality of optical fibers are manufactured into an optical fiber panel or an optical fiber image inverter by the prior art (such as arrangement into a rod, fusion molding, optical processing and the like), and the transmittance of the optical fiber panel or the optical fiber image inverter under the irradiation of diffused light with the wavelength of 430-900nm is 69%. The fiber optic faceplate or fiber optic inverter may be used in an endoscope.

The above examples 1-3 were used to prepare fiber optic ferrules of different transmittances by varying the reduction duration. It can be seen from fig. 11 that, as the reduction time length increases, the transmittance of the prepared optical fiber leather tube also increases, and when the reduction time length is greater than or equal to 12 hours, the transmittance of the prepared optical fiber leather tube under the irradiation of collimated light with the wavelength of 400 and 1100nm is less than or equal to about 10%, which can meet the requirements of finally preparing an optical fiber panel or an optical fiber image inverter for night vision goggles, particle detectors or signal detectors; and when the reduction time is 15 hours, the transmittance of the prepared optical fiber leather tube is optimal when the prepared optical fiber leather tube is irradiated by the collimated light with the wavelength of 400-1100nm, and is about 2.4 percent.

Example 4

in a thousand-level purification workshop, putting a raw material leather hose into a 40KHz ultrasonic cleaning machine, cleaning the leather hose for 20 minutes by purified water at the temperature of 60 ℃, taking out the leather hose, putting the leather hose into an absolute ethyl alcohol tank again, cleaning the leather hose for 1 time by absolute ethyl alcohol, and vertically and naturally drying the leather hose; the raw material leather hose comprises the following components in percentage by mass: SiO 2₂ 63%；B₂O₃ 4.5%；Al₂O₃ 4%；Na₂O 6%；K₂O 5.3%；BaO 7.5%；CaO 6%；ZrO ₂2%；PbO0.7%；Bi₂O₃1%。

And (3) placing the coil spring-shaped tool shown in the figure 4 into the air-dried leather hose, and placing the tool at the middle position to ensure that the lengths of the two ends are respectively reserved for 30 mm. And (3) rotating the coil spring-shaped tool anticlockwise, and plugging the fixing plug shown in the figure 5 into the coil spring-shaped tool for fixing after tightly supporting the inner wall. And then putting the leather hose into a melting sealing furnace, vacuumizing the interior of the leather hose by using an oil-free vacuum pump until the vacuum degree reaches 20Pa, manually operating sealing pliers at 650 ℃ to seal the two ends, and cooling to normal temperature after 8 hours of annealing procedure to complete the preparation of the vacuum leather hose.

And (3) putting the prepared vacuum leather material pipe into a reduction furnace, and introducing hydrogen for reduction treatment according to a reduction process. In the reduction furnace, hydrogen is supplied at a flow rate of 20ml/min, the reduction time is 15 hours at a temperature of 625 ℃, and the temperature is reduced to the normal temperature after 8 hours. So that the surface of the vacuum cladding pipe forms a uniform reduction layer with the thickness of about 0.5 mm.

and cooling the vacuum leather tube to normal temperature, taking out the vacuum leather tube, cutting two ends of the vacuum leather tube except the length of the coil spring-shaped tool by using a diamond cutting blade, sealing, taking down the fixing plug, separating the fixing plug from the inner wall of the vacuum leather tube by reversely rotating the coil spring-shaped tool, taking out the coil spring-shaped tool, ultrasonically cleaning the vacuum leather tube for 20 minutes by using purified water, cleaning the vacuum leather tube for 1 time by using absolute ethyl alcohol, and naturally drying the vacuum leather tube to obtain the optical fiber leather tube. The thickness of the absorption layer on the surface of the optical fiber cladding tube was measured to be about 0.3mm, and the transmittance curve is shown in FIG. 12. As can be seen from FIG. 12, the prepared fiber optic fiber sheath tube has a transmission characteristic when irradiated by the collimated light with a wavelength of 400 and 1100nmThe rate was about 2.8%. The optical fiber cladding tube described in this embodiment sequentially includes a body layer 31, an absorption layer 32, and an oxide layer 33 from inside to outside. The bulk layer 31 comprises 0.7% of PbO and 1% of Bi by mass of the bulk layer₂O₃A thickness of about 2.5 mm; the absorber layer 32 contains 0.33% of Pb and 0.53% of Bi by mass of the absorber layer, and has a thickness of about 0.3 mm; the oxide layer 33 contains 0.7% by mass of bO and 1% by mass of Bi based on the mass of the oxide layer₂O₃Its thickness is about 0.2 mm.

Drawing the optical fiber sheath tube, the core glass rod and the filling wire into a single optical fiber by the prior art, wherein the optical fiber comprises a sheath layer and a core layer, and the sheath layer sequentially comprises a body layer 31, an absorption layer 32 and an oxidation layer 33 from inside to outside; the transmittance of the optical fiber under the irradiation of diffused light with the wavelength of 430-; a plurality of optical fibers are manufactured into an optical fiber panel or an optical fiber image inverter by the prior art (such as arrangement into a rod, fusion molding, optical processing and the like), and the transmittance of the optical fiber panel or the optical fiber image inverter under the irradiation of diffused light with the wavelength of 430-900nm is 58%. The optical fiber panel or the optical fiber image inverter can be used in an image intensifier of night vision goggles and also can be used in a particle detector or a signal detector.

Example 5

The difference between this embodiment and embodiment 4 is that the last heat preservation time in the precision annealing is 6 hours (the other steps and parameters are the same as those in embodiment 4), and the optical fiber leather tube with the thickness of the absorption layer of about 0.14mm is finally prepared, the transmittance curve is shown in fig. 12, and it can be seen from fig. 12 that the transmittance of the prepared optical fiber leather tube is about 30% when the prepared optical fiber leather tube is irradiated by the collimated light with the wavelength of 400-. The optical fiber cladding tube described in this embodiment sequentially includes a body layer 31, an absorption layer 32, and an oxide layer 33 from inside to outside. The bulk layer 31 comprises 0.7% of PbO and 1% of Bi by mass of the bulk layer₂O₃A thickness of about 2.66 mm; the absorber layer 32 contains 0.19% of Pb and 0.28% of Bi by mass of the absorber layer, and has a thickness of about 0.14 mm; the oxide layer 33 contains 0.7% of PbO and 1% of Bi by mass of the oxide layer₂O₃Thickness ofAbout 0.2 mm.

Drawing the optical fiber sheath tube, the core glass rod and the filling wire into a single optical fiber by the prior art, wherein the optical fiber comprises a sheath layer and a core layer, and the sheath layer sequentially comprises a body layer 31, an absorption layer 32 and an oxidation layer 33 from inside to outside; the transmittance of the optical fiber under the irradiation of diffused light with the wavelength of 430-; a plurality of optical fibers are manufactured into an optical fiber panel or an optical fiber image inverter by the prior art (such as arrangement into a rod, fusion molding, optical processing and the like), and the transmittance of the optical fiber panel or the optical fiber image inverter under the irradiation of diffused light with the wavelength of 430-900nm is 71%. The fiber optic faceplate or fiber optic inverter may be used in an endoscope.

Example 6

The difference between this embodiment and embodiment 4 is that the last heat preservation time in the precision annealing is 4 hours (the other steps and parameters are the same as those in embodiment 4), and the optical fiber leather tube with the thickness of the absorption layer of about 0.21mm is finally prepared, the transmittance test curve is shown in fig. 12, and it can be seen from fig. 12 that the transmittance of the prepared optical fiber leather tube is about 12% when the prepared optical fiber leather tube is irradiated by the collimated light with the wavelength of 400-. The optical fiber cladding tube described in this embodiment sequentially includes a body layer 31, an absorption layer 32, and an oxide layer 33 from inside to outside. The bulk layer 31 comprises 0.7% of PbO and 1% of Bi by mass of the bulk layer₂O₃A thickness of about 2.59 mm; the absorber layer 32 contains 0.29% of Pb and 0.39% of Bi by mass of the absorber layer, and has a thickness of about 0.21 mm; the oxide layer 33 contains 0.7% of PbO and 1% of Bi by mass of the oxide layer₂O₃Its thickness is about 0.2 mm.

Drawing the optical fiber sheath tube, the core glass rod and the filling wire into a single optical fiber by the prior art, wherein the optical fiber comprises a sheath layer and a core layer, and the sheath layer sequentially comprises a body layer 31, an absorption layer 32 and an oxidation layer 33 from inside to outside; the transmittance of the optical fiber under the irradiation of diffused light with the wavelength of 430-900nm is 84 percent; a plurality of optical fibers are manufactured into an optical fiber panel or an optical fiber image inverter by the prior art (such as arranging into a rod, performing melt-molding, performing optical processing and the like), and the transmittance of the optical fiber panel under the irradiation of diffused light with the wavelength of 430-900nm is 64%. The fiber optic faceplate or fiber optic inverter may be used in an endoscope.

Examples 4-6 above prepare fiber optic ferrules of different transmission rates by varying the length of the last incubation at the Tg temperature (625 deg.C). As can be seen from FIG. 12, the longer the holding time at 625 ℃, the more sufficient the oxidation of the surface of the reduction layer, the smaller the thickness of the absorption layer of the prepared optical fiber leather tube, the higher the transmittance of the optical fiber leather tube when irradiated by the collimated light with the wavelength of 400 and 1100nm, i.e. the lower the absorption rate of the optical fiber leather tube to the stray light; when the last heat preservation time is 2 hours, the transmittance of the prepared optical fiber leather tube under the irradiation of the collimated light with the wavelength of 400 and 1100nm is about 2.8 percent, and the requirement of finally preparing an optical fiber panel or an optical fiber image inverter for night vision goggles, particle detectors or signal detectors can be met.

Example 7

The difference between the present embodiment and embodiment 2 is that the raw material leather hose of the present embodiment comprises the following components by mass percent: SiO 2₂ 64%；B₂O₃ 5%；Al₂O₃ 4%；Na₂O 4.5%；K₂O 5.5%；BaO 6%；CaO 7.3%；ZrO ₂2%；PbO 0.8%；Sn₂O₃0.9 percent, and the rest steps and parameters are the same as those of the example 2, finally preparing the optical fiber leather tube with the thickness of the absorbing layer of about 0.3mm, wherein the transmittance of the prepared optical fiber leather tube is about 4 percent when the wavelength is 400-1100 nm. The optical fiber leather tube of the embodiment sequentially comprises a body layer 31, an absorption layer 32 and an oxidation layer 33 from inside to outside. The bulk layer 31 comprises 0.8% of PbO and 0.9% of Sn by mass of the bulk layer₂O₃A thickness of about 2.5 mm; the absorber layer 32 comprises 0.38% Pb and 0.44% Sn by mass of the absorber layer, and has a thickness of about 0.3 mm; the oxide layer 33 contains 0.8% of PbO and 0.9% of Sn by mass of the oxide layer₂O₃Its thickness is about 0.2 mm.

As can be seen from FIG. 13, when the collimated light with the wavelength of 400-The transmittance was about 92%, and after hydrogen reduction, the transmittance rapidly decreased to about 4%. This indicates that the hydrogen reduction contributes to 0.8% of PbO and 0.9% of Sn₂O₃The transmittance of the optical fiber sheath tube is reduced.

Drawing the optical fiber sheath tube, the core glass rod and the filling wire into a single optical fiber by the prior art, wherein the optical fiber comprises a sheath layer and a core layer, and the sheath layer sequentially comprises a body layer 31, an absorption layer 32 and an oxidation layer 33 from inside to outside; the transmittance of the optical fiber under the irradiation of diffused light with the wavelength of 430-900nm is 79 percent; a plurality of optical fibers are manufactured into an optical fiber panel or an optical fiber image inverter by the prior art (such as arranging into a rod, performing melt-molding, performing optical processing and the like), and the transmittance of the optical fiber panel under the irradiation of diffused light with the wavelength of 430-900nm is 59%. The optical fiber panel or the optical fiber image inverter can be used in an image intensifier of night vision goggles and also can be used in a particle detector or a signal detector.

Example 8

The difference between the present embodiment and embodiment 2 is that the raw material leather hose of the present embodiment comprises the following components by mass percent: SiO 2₂ 64%；B₂O₃ 5%；Al₂O₃ 4%；Na₂O 4.5%；K₂O 5.3%；BaO 6%；CaO 7.3%；ZrO ₂2%；As₂O₃1.0%；Bi₂O₃0.9 percent; the rest steps and parameters are the same as those of the example 2, and the optical fiber leather tube with the thickness of the absorbing layer of about 0.4mm is finally prepared, and the transmittance of the prepared optical fiber leather tube is about 7% when the prepared optical fiber leather tube is irradiated by the collimated light with the wavelength of 400 and 1100 nm. The optical fiber leather tube of the embodiment sequentially comprises a body layer 31, an absorption layer 32 and an oxidation layer 33 from inside to outside. The bulk layer 31 contains 1.0% by mass of As based on the mass of the bulk layer₂O₃And 0.9% of Bi₂O₃The thickness of the film is 2.4 mm; the absorber layer 32 comprises 0.46% Pb and 0.44% Sn by mass of the absorber layer, and has a thickness of about 0.4 mm; the oxidized layer 33 contains 1.0% by mass of As based on the mass of the oxidized layer₂O₃And 0.9% of Bi₂O₃Its thickness is about 0.2 mm.

As can be seen from fig. 14, when the collimated light with the wavelength of 400-. This indicates that the hydrogen reduction contributes to the 1.0% As content₂O₃And 0.9% Bi₂O₃The transmittance of the optical fiber sheath tube is reduced.

Drawing the optical fiber sheath tube, the core glass rod and the filling wire into a single optical fiber by the prior art, wherein the optical fiber comprises a sheath layer and a core layer, and the sheath layer sequentially comprises a body layer 31, an absorption layer 32 and an oxidation layer 33 from inside to outside; the transmittance of the optical fiber under the irradiation of diffused light with the wavelength of 430-900nm is 81 percent; a plurality of optical fibers are manufactured into an optical fiber panel or an optical fiber image inverter by the prior art (such as arrangement into a rod, fusion molding, optical processing and the like), and the transmittance of the optical fiber panel under the irradiation of diffused light with the wavelength of 430-900nm is 60%. The optical fiber panel or the optical fiber image inverter can be used in an image intensifier of night vision goggles and also can be used in a particle detector or a signal detector.

Example 9

The difference between the present embodiment and embodiment 2 is that the raw material leather hose of the present embodiment comprises the following components by mass percent: SiO 2₂ 63%；B₂O₃ 4.5%；Al₂O₃ 4%；Na₂O 6%；K₂O 5.3%；BaO 7.5%；CaO 6%；ZrO ₂2%；As₂O₃1.7 percent, and the rest steps and parameters are the same as those of the example 1, finally preparing the optical fiber leather tube with the thickness of the absorbing layer of about 0.24mm, wherein the transmittance of the prepared optical fiber leather tube is about 3 percent when the prepared optical fiber leather tube is irradiated by the collimated light with the wavelength of 400-1100 nm. The optical fiber leather tube of the embodiment sequentially comprises a body layer 31, an absorption layer 32 and an oxidation layer 33 from inside to outside. The bulk layer 31 contains 1.7% by mass of As based on the mass of the bulk layer₂O₃A thickness of about 2.58 mm; the absorbing layer 32 comprises 0.83% As by mass of the absorbing layer and has a thickness of about 0.34 mm; the oxidized layer 33 contains 1.7% by mass of As based on the mass of the oxidized layer₂O₃Which isThe thickness is about 0.18 mm.

Drawing the optical fiber sheath tube, the core glass rod and the filling wire into a single optical fiber by the prior art, wherein the optical fiber comprises a sheath layer and a core layer, and the sheath layer sequentially comprises a body layer 31, an absorption layer 32 and an oxidation layer 33 from inside to outside; the transmittance of the optical fiber under the irradiation of diffused light with the wavelength of 430-900nm is 78%; a plurality of the optical fibers are made into a light cone by the prior art (such as arranging into a rod, performing melt-molding, performing optical processing and the like), and the transmittance of the light cone under the irradiation of diffused light with the wavelength of 430-900nm is 59%. The light cone may be used for a signal detector.

Example 10

The difference between the present embodiment and embodiment 2 is that the raw material leather hose of the present embodiment comprises the following components by mass percent: SiO 2₂ 63%；B₂O₃ 4.5%；Al₂O₃ 4%；Na₂O 6%；K₂O 5.3%；BaO 7.5%；CaO 6%；ZrO ₂2%；Sn₂O₃0.7%；Sb₂O₃0.4%；Bi₂O₃0.6 percent, and the rest steps and parameters are the same as those of the example 2, finally preparing the optical fiber leather tube with the thickness of the absorbing layer of about 0.28mm, wherein the transmittance of the prepared optical fiber leather tube is about 2.3 percent when the prepared optical fiber leather tube is irradiated by the collimated light with the wavelength of 400 plus 1100 nm. The optical fiber leather tube of the embodiment sequentially comprises a body layer 31, an absorption layer 32 and an oxidation layer 33 from inside to outside. The bulk layer 31 contains 0.7% Sn by mass of the bulk layer₂O₃0.4% of Sb₂O₃And 0.6% of Bi₂O₃A thickness of about 2.57 mm; the absorber layer 32 comprises 0.34% Sn, 0.19% As and 0.28% Bi by mass of the absorber layer, and has a thickness of about 0.28 mm; the oxide layer 33 contains 0.7% Sn by mass of the absorber layer₂O₃0.4% of Sb₂O₃And 0.6% of Bi₂O₃Its thickness is about 0.15 mm.

Drawing the optical fiber sheath tube, the core glass rod and the filling wire into a single optical fiber by the prior art, wherein the optical fiber comprises a sheath layer and a core layer, and the sheath layer sequentially comprises a body layer 31, an absorption layer 32 and an oxidation layer 33 from inside to outside; the transmittance of the optical fiber under the irradiation of diffused light with the wavelength of 430-900nm is 75 percent; a plurality of the optical fibers are manufactured into an optical fiber panel or an optical fiber image inverter by the prior art (such as arrangement into a rod, fusion molding, optical processing and the like), and the transmittance of the optical fiber panel or the optical fiber image inverter under the irradiation of diffused light with the wavelength of 430-900nm is 57%. The optical fiber panel or the optical fiber image inverter can be used in an image intensifier of night vision goggles and also can be used in a particle detector or a signal detector.

Example 11

The difference between the present embodiment and embodiment 2 is that the raw material leather hose of the present embodiment comprises the following components by mass percent: SiO 2₂ 63%；B₂O₃ 4.5%；Al₂O₃ 4%；Na₂O 6%；K₂O 5.3%；BaO 7.5%；CaO 6%；ZrO ₂2%；Sn₂O₃0.4%；Cd₂O₃0.3%；Sb₂O₃0.4%；Bi₂O₃0.5%；As₂O₃0.1 percent, and the rest steps and parameters are the same as those of the example 2, finally preparing the optical fiber leather tube with the thickness of the absorbing layer of about 0.28mm, wherein the transmittance of the prepared optical fiber leather tube is about 2.2 percent when the prepared optical fiber leather tube is irradiated by the collimated light with the wavelength of 400 plus 1100 nm. The optical fiber leather tube of the embodiment sequentially comprises a body layer 31, an absorption layer 32 and an oxidation layer 33 from inside to outside. The bulk layer 31 comprises 0.4% Sn by mass of the bulk layer₂O₃0.3% of Cd₂O₃0.4% of Sb₂O₃0.5% of Bi₂O₃And 0.1% of As₂O₃A thickness of about 2.55 mm; the absorber layer 32 comprises 0.19% Sn, 0.15% Cd, 0.21% Sb by mass of the absorber layer_、0.26% Bi and 0.06% As, with a thickness of about 0.27 mm; the oxide layer 33 contains 0.4% by mass of Sn based on the mass of the oxide layer₂O₃0.3% of Cd₂O₃0.4% of Sb₂O₃0.5% of Bi₂O₃And 0.1% of As₂O₃Its thickness is about 0.18 mm.

Drawing the optical fiber sheath tube, the core glass rod and the filling wire into a single optical fiber by the prior art, wherein the optical fiber comprises a sheath layer and a core layer, and the sheath layer sequentially comprises a body layer 31, an absorption layer 32 and an oxidation layer 33 from inside to outside; the transmittance of the optical fiber under the irradiation of diffused light with the wavelength of 430-; a plurality of the optical fibers are manufactured into an optical fiber panel or an optical fiber image inverter by the prior art (such as arrangement into a rod, fusion molding, optical processing and the like), and the transmittance of the optical fiber panel or the optical fiber image inverter under the irradiation of diffused light with the wavelength of 430-900nm is 59%. The optical fiber panel or the optical fiber image inverter can be used in an image intensifier of night vision goggles and also can be used in a particle detector or a signal detector.

Example 12

The difference between the present embodiment and embodiment 2 is that the raw material leather hose of the present embodiment comprises the following components by mass percent: SiO 2₂ 63%；B₂O₃ 4.5%；Al₂O₃ 4%；Na₂O 6%；K₂O 5.3%；BaO 7.5%；CaO 6%；ZrO ₂2%；Sn₂O₃0.4%；Cd₂O₃0.2%；Sb₂O₃0.4%；Bi₂O₃0.5%；As₂O₃0.1 percent; PbO0.1%, and the rest steps and parameters are the same as those of example 2, so as to finally prepare the optical fiber leather tube with the thickness of the absorption layer of about 0.28mm, and the transmittance of the prepared optical fiber leather tube is about 2.0% when the prepared optical fiber leather tube is irradiated by the collimated light with the wavelength of 400 and 1100 nm. The optical fiber leather tube of the embodiment sequentially comprises a body layer 31, an absorption layer 32 and an oxidation layer 33 from inside to outside. The bulk layer 31 comprises 0.4% Sn by mass of the bulk layer₂O₃0.2% of Cd₂O₃0.4% of Sb₂O₃0.5% of Bi₂O₃0.1% of As₂O₃And 0.1% PbO having a thickness of about 2.47 mm; the absorber layer 32 comprises 0.19% Sn, 0.1% Cd, 0.21% Sb by mass of the absorber layer_、0.26% Bi, 0.06% As and 0.06% Pb, having a thickness of about 0.33 mm; the oxide layer 33 contains 0.4% by mass of Sn based on the mass of the oxide layer₂O₃0.2% of Cd₂O₃0.4% of Sb₂O₃0.5% of Bi₂O₃0.1% of As₂O₃And 0.1% PbO with a thickness of about 0.2 mm.

Drawing the optical fiber sheath tube, the core glass rod and the filling wire into a single optical fiber by the prior art, wherein the optical fiber comprises a sheath layer and a core layer, and the sheath layer sequentially comprises a body layer 31, an absorption layer 32 and an oxidation layer 33 from inside to outside; the transmittance of the optical fiber under the irradiation of diffused light with the wavelength of 430-; a plurality of the optical fibers are manufactured into an optical fiber panel or an optical fiber image inverter by the prior art (such as arrangement into a rod, fusion molding, optical processing and the like), and the transmittance of the optical fiber panel or the optical fiber image inverter under the irradiation of diffused light with the wavelength of 430-900nm is 56%. The optical fiber panel or the optical fiber image inverter can be used in an image intensifier of night vision goggles and also can be used in a particle detector or a signal detector.

The transmittance of the optical fiber sheath tube is measured according to the international standard (ISO 10110) of the technical requirements and the inspection requirements of optical elements, and the transmittance of the optical fiber sheath tube at the wavelength of 400-1100nm is measured.

The transmittance of the optical fiber is measured according to the GB/T11447 optical fiber panel test method, and the transmittance of the optical fiber at the wavelength of 430-900nm is measured.

The transmittance of the optical fiber panel or the optical fiber image inverter is measured according to the GB/T11447 optical fiber panel test method, and the transmittance of the optical fiber panel or the optical fiber image inverter at the wavelength of 430-900nm is measured.

In summary, when the other steps or parameters are the steps or parameters set in embodiment 1, when the hydrogen reduction time is longer than or equal to 12 hours, the transmittance of the prepared optical fiber cladding tube is about less than or equal to 10%, which can meet the requirements of finally preparing an optical fiber panel or an optical fiber image inverter for night vision goggles, particle detectors or signal detectors; under the condition that other steps or parameters are the steps or parameters set in the embodiment 1, when the hydrogen reduction time is 8 hours, the transmittance of the prepared optical fiber cladding tube is less than or equal to about 17 percent, and the requirements of finally preparing an optical fiber panel or an optical fiber image inverter for an endoscope can be met;

under the condition that other steps or parameters are the steps or parameters set in embodiment 4, when the last heat preservation time is less than or equal to 2 hours, the transmittance of the prepared optical fiber leather tube is less than or equal to 2.8 percent when the collimated light with the wavelength of 400-; under the condition that other steps or parameters are the steps or parameters set in the embodiment 4, when the last heat preservation time is longer than or equal to 4 hours, the transmittance of the prepared optical fiber leather tube under the irradiation of the collimated light with the wavelength of 400 and 1100nm is about longer than or equal to 12 percent, and the requirement of finally preparing an optical fiber panel or an optical fiber image inverter for the endoscope can be met;

in the case that the other steps or parameters are the steps or parameters set in example 2, when the composition of the raw material leather hose is as follows by mass percent: SiO 2₂ 64%；B₂O₃ 5%；Al₂O₃ 4%；Na₂O 4.5%；K₂O 5.5%；BaO 6%；CaO 7.3%；ZrO ₂2%；PbO 0.8%；Sn₂O₃When the transmittance of the prepared optical fiber leather material tube is 0.9 percent, the transmittance of the prepared optical fiber leather material tube is about 4 percent when the prepared optical fiber leather material tube is irradiated by collimated light with the wavelength of 400-1100nm, and the requirement of finally preparing an optical fiber panel or an optical fiber image inverter for night vision goggles, particle detectors or signal detectors can be met;

in the case that the other steps or parameters are the steps or parameters set in example 2, when the composition of the raw material leather hose is as follows by mass percent: SiO 2₂ 64%；B₂O₃ 5%；Al₂O₃ 4%；Na₂O 4.5%；K₂O 5.3%；BaO 6%；CaO 7.3%；ZrO ₂2%；As₂O₃1.0%；Bi₂O₃When the transmittance is 0.9 percent, the transmittance of the prepared optical fiber leather material pipe is about 7 percent when the prepared optical fiber leather material pipe is irradiated by collimated light with the wavelength of 400 and 1100nm, and the requirement of finally preparing an optical fiber panel or an optical fiber image inverter for night vision goggles, particle detectors or signal detectors can be met;

the case where the other steps or parameters were the set ones in example 2Under the condition, the raw material leather hose comprises the following components in percentage by mass: SiO 2₂ 63%；B₂O₃ 4.5%；Al₂O₃ 4%；Na₂O 6%；K₂O 5.3%；BaO 7.5%；CaO 6%；ZrO ₂2%；Sn₂O₃At 1.7%, the transmittance of the prepared optical fiber leather tube under the irradiation of collimated light with the wavelength of 400 and 1100nm is about 3%, so that the requirement of finally preparing a light cone for a signal detector can be met;

in the case that the other steps or parameters are the steps or parameters set in example 2, when the composition of the raw material leather hose is as follows by mass percent: SiO 2₂ 63%；B₂O₃ 4.5%；Al₂O₃ 4%；Na₂O 6%；K₂O 5.3%；BaO 7.5%；CaO 6%；ZrO ₂2%；Sn₂O₃0.7%；Sb₂O₃0.4%；Bi₂O₃When the transmittance is 0.6 percent, the transmittance of the prepared optical fiber leather material pipe is about 3 percent when the prepared optical fiber leather material pipe is irradiated by collimated light with the wavelength of 400 and 1100nm, and the requirement of finally preparing an optical fiber panel or an optical fiber image inverter for night vision goggles, particle detectors or signal detectors can be met;

in the case that the other steps or parameters are the steps or parameters set in example 2, when the composition of the raw material leather hose is as follows by mass percent: SiO 2₂ 63%；B₂O₃ 4.5%；Al₂O₃ 4%；Na₂O 6%；K₂O 5.3%；BaO 7.5%；CaO 6%；ZrO ₂2%；Sn₂O₃0.4%；Cd₂O₃0.3%；Sb₂O₃0.4%；Bi₂O₃0.5%；As₂O₃When the transmittance is 0.1 percent, the transmittance of the prepared optical fiber leather material pipe is about 2.2 percent when the prepared optical fiber leather material pipe is irradiated by collimated light with the wavelength of 400-1100nm, and the requirement of finally preparing an optical fiber panel or an optical fiber image inverter for night vision goggles, particle detectors or signal detectors can be met;

in the case that the other steps or parameters are the steps or parameters set in example 2, when the composition of the raw material leather hose is as follows by mass percent: SiO 2₂ 63%；B₂O₃ 4.5%；Al₂O₃ 4%；Na₂O 6%；K₂O 5.3%；BaO 7.5%；CaO 6%；ZrO ₂2%；Sn₂O₃0.4%；Cd₂O₃0.2%；Sb₂O₃0.4%；Bi₂O₃0.5%；As₂O₃0.1 percent; when PbO0.1%, the transmittance of the prepared optical fiber leather tube is about 2.0% when the wavelength is 400-1100nm collimated light, which can meet the requirement of preparing the optical fiber panel or the optical fiber image inverter for night vision goggles, particle detectors or signal detectors finally;

in the case that the other steps or parameters are the steps or parameters set in embodiment 2, when the hydrogen reduction time is longer than or equal to 10 hours, the transmittance of the prepared optical fiber leather tube under the irradiation of the collimated light with the wavelength of 400 and 1100nm is about 2.6%, which can meet the requirements of finally preparing the optical fiber panel or the optical fiber image inverter for night vision goggles, particle detectors or signal detectors.

In the description of the present invention, numerous specific details are set forth. It is understood, however, that embodiments of the invention may be practiced without these specific details. In some embodiments, well-known methods, structures and techniques have not been shown in detail in order not to obscure an understanding of this description.

It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.

In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. The optical fiber leather material pipe is characterized in that the optical fiber leather material pipe sequentially comprises a body layer, an absorption layer and an oxidation layer from inside to outside;

the oxide layer and the body layer have the same material composition;

the bulk layer further comprises a second oxide comprising SiO₂、B₂O₃、Al₂O₃、Na₂O、K₂O, BaO, CaO and ZrO₂(ii) a The body layer comprises the following components in percentage by mass:

SiO₂ 55-65%；

B₂O₃ 0-5%；

Al₂O₃ 0-5%；

Na₂O 5-8%；

K₂O 5-8%；

BaO 5-10%；

CaO 5-10%；

ZrO₂ 0-5%；

2. The fiber optic ferrule of claim 1, wherein the ratio of the thicknesses of the body layer, the absorption layer and the oxidation layer is (2.4-2.6): (0.2-0.4): (0.15-0.2).

3. The preparation method of the optical fiber leather material pipe is characterized by comprising the following steps:

a reduction step: carrying out reduction reaction on the raw material leather hose in a hydrogen environment; the raw material leather hose comprises a first oxide MO and M₂O₃Said first oxide MO is PbO; the first oxide M₂O₃Selected from Bi₂O₃、Cd₂O₃、Sn₂O₃、Sb₂O₃And As₂O₃At least one of; part of the first oxide in the outer surface of the raw material leather hose and the area below the outer surface is reduced into a simple substance M to form an absorption layer;

an oxidation step: in the air environment, the leather pipe obtained in the reduction step

heating to Tg +50 ℃ after 1-2 hours, preserving the heat for 2-3 hours,

cooling to 500-600 ℃ after 2-3 hours;

cooling to normal temperature after 10-15 hours;

4. The method of claim 3, further comprising a pre-treatment step prior to the reducing step of:

supporting the inner surface of the leather tube by a support;

and sealing two ports of the leather hose by melting.

5. The optical fiber comprises a skin layer and a core layer, and is characterized in that the skin layer sequentially comprises a body layer, an absorption layer and an oxidation layer from inside to outside;

the oxide layer and the body layer have the same material composition;

SiO₂ 55-65%；

B₂O₃ 0-5%；

Al₂O₃ 0-5%；

Na₂O 5-8%；

K₂O 5-8%；

BaO 5-10%；

CaO 5-10%；

ZrO₂ 0-5%；

6. The optical fiber of claim 5, wherein the ratio of the thicknesses of the bulk layer, the absorption layer and the oxide layer is (2.4-2.6): (0.2-0.4): (0.15-0.2).

7. An optical fiber bundle comprising a plurality of optical fibers according to claim 5 or 6.

8. An optical fiber image-transmitting member comprising a plurality of optical fibers according to claim 5 or 6.

9. The fiber optic image transfer element of claim 8, wherein the fiber optic image transfer element is a fiber optic faceplate or a fiber optic inverter.

10. The fiber optic image transfer element of claim 8, wherein the fiber optic image transfer element is a cone of light.

11. Night vision goggles, characterized in that they comprise an image intensifier comprising an optical fiber image-transmitting element according to claim 8 or 9.

12. An endoscope, characterized in that it comprises a fiber-optic image transmitting element according to claim 8 or 9.

13. An electronic device comprising the optical fiber image transmitting element according to any one of claims 8 to 10, wherein the electronic device is a particle detector or a signal detector.