CN110981192A - Microchannel plate cladding glass with high-stability temperature resistance characteristic for low temperature and preparation method and application thereof - Google Patents

Microchannel plate cladding glass with high-stability temperature resistance characteristic for low temperature and preparation method and application thereof Download PDF

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CN110981192A
CN110981192A CN201911267468.6A CN201911267468A CN110981192A CN 110981192 A CN110981192 A CN 110981192A CN 201911267468 A CN201911267468 A CN 201911267468A CN 110981192 A CN110981192 A CN 110981192A
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glass
microchannel plate
temperature
plate
low temperature
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CN110981192B (en
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蔡华
刘辉
周东站
贾金升
李庆
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China Building Materials Academy CBMA
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/102—Glass compositions containing silica with 40% to 90% silica, by weight containing lead
    • C03C3/105—Glass compositions containing silica with 40% to 90% silica, by weight containing lead containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B17/00—Forming molten glass by flowing-out, pushing-out, extruding or drawing downwardly or laterally from forming slits or by overflowing over lips
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B17/00—Forming molten glass by flowing-out, pushing-out, extruding or drawing downwardly or laterally from forming slits or by overflowing over lips
    • C03B17/04—Forming tubes or rods by drawing from stationary or rotating tools or from forming nozzles
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B23/00—Re-forming shaped glass
    • C03B23/20—Uniting glass pieces by fusing without substantial reshaping
    • C03B23/207—Uniting glass rods, glass tubes, or hollow glassware
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J43/00—Secondary-emission tubes; Electron-multiplier tubes
    • H01J43/04—Electron multipliers
    • H01J43/06—Electrode arrangements
    • H01J43/10—Dynodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J43/00—Secondary-emission tubes; Electron-multiplier tubes
    • H01J43/04—Electron multipliers
    • H01J43/06—Electrode arrangements
    • H01J43/18—Electrode arrangements using essentially more than one dynode
    • H01J43/24—Dynodes having potential gradient along their surfaces
    • H01J43/246—Microchannel plates [MCP]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/02—Manufacture of electrodes or electrode systems
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J31/00—Cathode ray tubes; Electron beam tubes
    • H01J31/08—Cathode ray tubes; Electron beam tubes having a screen on or from which an image or pattern is formed, picked up, converted, or stored
    • H01J31/50—Image-conversion or image-amplification tubes, i.e. having optical, X-ray, or analogous input, and optical output
    • H01J31/506—Image-conversion or image-amplification tubes, i.e. having optical, X-ray, or analogous input, and optical output tubes using secondary emission effect
    • H01J31/507—Image-conversion or image-amplification tubes, i.e. having optical, X-ray, or analogous input, and optical output tubes using secondary emission effect using a large number of channels, e.g. microchannel plates

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Abstract

The invention relates to a microchannel plate cladding glass with high stable temperature resistance characteristic for low temperature, a preparation method and application thereof. The microchannel plate cladding glass comprises the following components in percentage by mole: SiO 2250％～78％；Bi2O31.5％～8％；PbO 5.0％～15％；Na2O、K2O and Cs24.0 to 25 percent of at least one of O; 1.0 to 6 percent of at least one of MgO, BaO and CaO; al (Al)2O30.1％～2.5％；RuO21.5% -12% of the invention, from the viewpoint of the temperature resistance characteristic modification of the microchannel plate, special oxide is directly introduced into the glass material to realize the conductive layer structure of the microchannel plate regulated and controlled by the components of the glass material, thereby reducing the ultralow temperature bulk resistance of the microchannel plate and greatly improving the capacity of the ultralow temperature signal ultra-fast reading and response of the microchannel plate.

Description

Microchannel plate cladding glass with high-stability temperature resistance characteristic for low temperature and preparation method and application thereof
Technical Field
The invention belongs to the field of glass processing, particularly relates to microchannel plate leather glass and a preparation method and application thereof, and particularly relates to microchannel plate leather glass with high stable temperature resistance for low temperature and a preparation method and application thereof.
Background
The microchannel plate is a special glass material and a device for carrying out parallel multiplication on charged particle flow distributed in a two-dimensional space. Due to the advantages of high time resolution, high spatial resolution, extremely high signal amplification factor, compact structure and the like, the microchannel plate becomes an important device with the most potential for reading out low-temperature quantum analog computation signals. The low-temperature quantum simulation calculation requires that the signal reading device has the signal reading time of not more than 10 under the condition that the temperature is not more than 30K-5s to meet ultra-fast read requirements.
The signal reading time of the microchannel plate under the ultralow temperature condition is mainly determined by the body resistance of the microchannel plate and is in direct proportion to the body resistance. After being processed by a special process, the inner wall of the micro-channel plate forms a secondary electron emission layer and an electron conduction layer, is a semiconductor-like structure and has obvious negative resistance temperature coefficient characteristics. The microchannel plate is usually used at room temperature, the conventional bulk resistance is 100-200M omega, but under the ultralow temperature condition of 20-30K, the bulk resistance can be raised to about 10 of the bulk resistance at room temperature5～106The corresponding signal reading time is prolonged to 10-2s-1 s, and ultra-fast speed required by low-temperature quantum simulation calculationQuantum signal readout is far apart. Therefore, the high resistance under the ultralow temperature condition is a major bottleneck for the fast reading of quantum signals of the silicate glass microchannel plate.
For the ultra-low temperature low body resistance micro-channel plate, the body resistance of the micro-channel plate under the ultra-low temperature use condition is reduced by adjusting the composition of the micro-channel plate material and optimizing the physical and chemical treatment process according to the prior patents and documents at home and abroad. However, there is no related patent or literature report for reducing the resistance of the microchannel plate body under the ultra-low temperature condition directly from the viewpoint of the modification and stabilization of the temperature resistance characteristics of the glass material components of the microchannel plate.
Disclosure of Invention
In view of the above, the main objective of the present invention is to provide a microchannel plate skin material glass with high stable temperature resistance for low temperature, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides a microchannel plate skin glass with high stable temperature resistance for low temperature, which comprises, in mole percent:
Figure BDA0002313263950000021
preferably, the microchannel plate skin glass with high stable temperature resistance characteristic for low temperature further comprises 0.10 to 0.80 weight percent of Sb2O3And/or As2O3。
Preferably, the transition temperature of the microchannel plate cladding glass with high stable temperature resistance characteristic for low temperature is TgNot less than 450 ℃ and a softening temperature Tf≥545℃。
Preferably, the microchannel plate cladding glass with high stable temperature resistance characteristic for low temperature is used, wherein the thermal expansion coefficient of the microchannel plate cladding glass with high stable temperature resistance characteristic for low temperature at 100 ℃ to 300 ℃ is (60-105) x 10-7/℃。
Preferably, the microchannel plate skin glass with high stable temperature resistance characteristic for low temperature has no crystallization at 500-950 ℃, and has good crystallization resistance.
In order to achieve the above object, the present invention further provides a method for preparing a microchannel plate skin material glass with high stable temperature resistance characteristic for low temperature, comprising the following steps:
1) mixing quartz sand, lead oxide, bismuth oxide, barium salt, sodium carbonate, cesium carbonate, potassium salt, basic magnesium carbonate, calcium carbonate, aluminum hydroxide and ruthenium compound to obtain a batch mixture, and adding a clarifying agent accounting for 0.10-0.80 wt% of the total weight of the batch mixture;
2) adding the batch containing the clarifying agent into a crucible at 1300-1550 ℃ for one or more times for melting, wherein the time interval between each time of feeding is 15-90 minutes;
3) after the feeding is finished, heating to 1400-1550 ℃ for clarification for 2-12 hours;
4) cooling to 1200-;
5) drawing and forming the glass liquid into a glass tube material at 1200-1350 ℃ after homogenization;
6) and (3) preserving the heat of the formed glass tube material for 2-6 hours at the temperature of 550-650 ℃, then cutting off the power and annealing to room temperature and discharging to obtain the microchannel plate cladding material glass.
Preferably, the method for preparing the microchannel plate skin glass with high stable temperature resistance characteristic for low temperature comprises the following steps:
Figure BDA0002313263950000031
preferably, in the method for preparing the microchannel plate skin material glass with high stable temperature resistance characteristic for low temperature, the lead oxide is red lead or yellow lead; the barium salt is barium nitrate or barium carbonate; the potassium salt is potassium carbonate or potassium nitrate; the ruthenium compound is ruthenium trichloride, ruthenium trichloride hydrate, ruthenium dioxide or ruthenium dioxide hydrate.
Preferably, in the method for preparing the microchannel plate cladding glass with high stable temperature resistance characteristic for low temperature, the refining agent is Sb2O3And/or As2O3。
In order to achieve the above object, the present invention further provides a microchannel plate with high stable temperature resistance for low temperature, which comprises a substrate and electrodes disposed on the upper and lower surfaces of the substrate, wherein the substrate comprises a frit glass with independent hollow channels and a cladding glass covering the outside of a hollow channel array composed of the frit glass, and the frit glass is the frit glass of the microchannel plate according to any one of claims 1 to 3.
In order to achieve the above object, the present invention further provides a method for preparing a microchannel plate with high stable temperature resistance for low temperature, comprising the following steps:
s1, drawing and forming a leather glass tube, wherein the leather glass tube is made of the leather glass of the microchannel plate;
s2, preparing a core material glass rod;
s3, nesting the core material glass rod into the leather material glass tube and drawing the core material glass rod into a monofilament;
s4, combining a plurality of monofilaments and then drawing the monofilaments into multifilaments;
s5, regularly arranging multifilaments, and then melting and pressing the multifilaments into blank sections;
s6, slicing, chamfering, grinding and polishing the blank sections to obtain a blank plate;
and S7, corroding the blank plate with acid liquor to remove cores, reducing the blank plate with high-temperature hydrogen, and plating a metal electrode to obtain the micro-channel plate with high stable temperature resistance for low temperature.
Preferably, the method for preparing a microchannel plate having a high stable temperature resistance characteristic for low temperature as described above, wherein,
step S6 specifically includes: slicing, chamfering, grinding and polishing the blank sections to obtain a micro-channel plate blank plate with high stable temperature resistance for low temperature;
step S7 specifically includes: the method comprises the steps of corroding and coring a blank plate by acid liquor to obtain an independent hollow channel structure with millions of micron-sized apertures, reducing the structure by high-temperature hydrogen to grow a conducting layer and a silicon dioxide secondary electron emission layer with high stable temperature resistance characteristics in situ on the surface of the inner wall of the hollow channel, and then evaporating metal electrodes on the upper surface and the lower surface of the conducting layer and the silicon dioxide secondary electron emission layer to obtain the micro-channel plate with high stable temperature resistance characteristics for low temperature.
Preferably, the method for preparing a microchannel plate having a high stable temperature resistance characteristic for low temperature as described above, wherein,
in the step S1, the drawing forming temperature of the leather glass tube is 1200-1350 ℃;
in step S7, the acid solution is at least one of nitric acid and hydrochloric acid, the solubility of the acid solution is 0.1 mol% -30 mol%, the corrosion time of the acid solution is 10 min-600 min, and the corrosion temperature of the acid solution is 30-90 ℃;
in step S7, the temperature of the high-temperature hydrogen reduction is 350-520 ℃, the time of the high-temperature hydrogen reduction is 20-600 min, and the flow rate of the hydrogen is 0.005-10L/min;
in step S7, the metal electrode is a Ti, Cr, Au, or Ni/Cr surface electrode; the sheet resistance of the metal electrode is not higher than 300 Ω.
In order to achieve the above object, the present invention also provides an ALD (atomic layer deposition) modified microchannel plate, which comprises a substrate having a single or multiple layers of modified thin films deposited on an inner wall surface thereof.
Preferably, the ALD-modified microchannel plate is a microchannel plate having a high stable temperature resistance characteristic for low temperature as described above.
In order to achieve the above object, the present invention further provides a method for preparing an ALD modified microchannel plate, comprising the following steps:
and (3) taking the low-temperature high-stability temperature-resistance microchannel plate as a substrate, and preparing a single-layer or multi-layer modified film on the surface of the inner wall of the channel of the microchannel plate by using an atomic layer deposition method to obtain the ALD modified microchannel plate.
The invention starts from the aspect of modifying the temperature resistance characteristic of the microchannel plate, and directly introduces special oxide into the glass material to realize the conductive layer structure of the microchannel plate for regulating and controlling the components of the glass material, thereby reducing the ultralow temperature bulk resistance of the microchannel plate, greatly improving the capacity of the ultralow temperature signal of the microchannel plate for reading and responding at an ultralow speed, and promoting the further application of the microchannel plate in the fields of ultralow temperature quantum analog computation and the like.
By the technical scheme, the invention at least has the following advantages:
according to the invention, the ruthenium-containing oxide with resistance temperature characteristic modification is directly introduced into the microchannel plate cladding glass material, and a conducting layer structure with high stable temperature resistance characteristic is formed on the glass surface by in-situ growth after high-temperature hydrogen reduction, so that the obvious negative resistance temperature characteristic modification of the microchannel plate for low temperature can be realized, and the resistance temperature coefficient can be adjusted.
The invention can modify the intrinsic negative resistance temperature characteristic of the microchannel plate, reduce the change rate of exponential increase of the body resistance of the microchannel plate along with temperature reduction under the ultralow temperature condition, is beneficial to improving the temperature resistance coefficient stability of the microchannel plate under the ultralow temperature condition, and can reduce the ultralow temperature body resistance of the microchannel plate, thereby realizing the ultra-fast signal reading and response under the lower temperature condition.
Compared with the prior art which adopts various means and only reduces the resistivity of the conducting layer of the microchannel plate and the resistance of the normal temperature body, the invention utilizes the ruthenium-containing oxide directly introduced into the glass material to regulate and control the resistance temperature characteristic of the glass material of the microchannel plate, and slows down the trend that the resistance of the microchannel plate body increases rapidly along with the temperature under the ultralow temperature condition from the aspect of the modification of the resistance-temperature coefficient of the microchannel plate body, thereby realizing the high stable temperature resistance characteristic of the microchannel plate under the ultralow temperature condition, reducing the resistance of the microchannel plate under the ultralow temperature condition, aiming at the ultralow temperature section range applied by devices, the composition proportion of the ruthenium-containing oxide and the high-temperature hydrogen reduction treatment process can be adjusted and optimized to obtain the micro-channel plate suitable for the body resistance and the resistance temperature characteristic, so that the micro-channel plate has quicker signal reading and response in the required application ultralow temperature section.
Drawings
FIG. 1 is a schematic diagram of a micro-channel plate blank with high stable temperature resistance for low temperature use according to the present invention;
FIG. 2 is a schematic diagram of the structure of a microchannel plate blank with high stable temperature resistance for low temperature use according to the present invention;
FIG. 3 is a schematic structural view of a microchannel plate with high stable temperature resistance for low temperature use according to the present invention;
FIG. 4 is a schematic view showing the structure of the inner wall of the channel in embodiment 4 of the present invention;
FIG. 5 is a schematic view showing the structure of a microchannel plate and the inner wall of a channel in comparative example 4 of the present invention;
FIG. 6 is a schematic structural view of a microchannel plate and an inner wall of a channel in comparative example 3 of the present invention;
wherein: 1-skin glass, 2-core glass, 3-edge glass, 4-substrate, 5-channel inner wall, 6-electrode, 7-conducting layer and emission layer with high stable temperature resistance, 8-atom layer deposition microchannel plate film modification layer, 9-conventional substrate, 10-channel inner wall of conventional microchannel plate, and 11-conventional conducting layer and emission layer.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description of the embodiments, structures, characteristics and effects of the microchannel plate cladding glass with high stable temperature resistance for low temperature and the preparation method and application thereof according to the present invention are provided with 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, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
The invention provides a microchannel plate cladding glass with high stable temperature resistance characteristic for low temperature, which comprises the following components in percentage by mole:
Figure BDA0002313263950000061
wherein, SiO2Is a glass former oxide, is a basic skeleton of a glass structure, is a main component of the cladding glass, and when the content exceeds 78 mol%,the glass contains a large amount of SiO2]The planar structure is not beneficial to the chemical stability of the glass, the viscosity of the glass is also reduced, the thermal expansion coefficient is improved, and the compatibility with the micro-channel plate core glass with high stable temperature resistance for low temperature is deteriorated; when the content is less than 50 mol%, the glass stability may be deteriorated.
Bi2O3Is the oxide of the network outer body of the glass, is the fluxing agent of the glass, and proper Bi is added into the glass2O3The material property of glass forming can be improved, the thermal processing property of glass is improved, the high-temperature melting viscosity of the glass is reduced, and a conductive metal phase in a conductive layer can be formed after the high-temperature hydrogen reduction, but the content of the conductive metal phase exceeds 8 mol%, the phase splitting phenomenon is easy to occur, and the resistance property of the reduced glass is unstable; when the concentration is less than 1.5 mol%, the resistance of the prepared microchannel plate is unstable.
Na2O，K2O and Cs2O is a network exo-oxide of the glass, alkali metal ions are easy to move and diffuse in the glass body, the viscosity of the glass melted at high temperature can be reduced, the glass is easy to melt, the glass is a good fluxing agent, the thermal expansion coefficient of the glass can be increased, the chemical stability and the mechanical strength of the glass are reduced, and the introduction amount is not too large; na in micro-channel plate core material glass with high stable temperature resistance characteristic for low temperature2O，K2O and Cs2Adjusting the content of O, and introducing one or more of the O and the O to reduce the diffusion degree of the core skin in the fiber drawing and high-temperature hot pressing processes; if Na2O，K2O and Cs2When the total content of O is less than 4%, the glass forming property is poor; however, if the total content thereof is more than 25 mol%, the swelling is too high and the glass stability is poor.
MgO, BaO and CaO are network external oxides of the glass, are alkaline earth metal oxides, are beneficial to improving the anti-devitrification capability of the glass, adjusting the material property of the glass and improving the thermal processing performance of the glass, but the performance of the glass is unstable due to excessive addition, and the phase separation phenomenon occurs. If the total content of MgO, BaO and CaO is less than 1 mol%, the hot workability of the glass is poor; however, if the total content is more than 6 mol%, the phase of the glass tends to be easily separated.
Al2O3The content of the oxide is the glass structure adjusting oxide, and the thermal expansion coefficient and the chemical and thermal stability of the glass are influenced. However, when the content is more than 2.5 mol%, the refractive index and dispersion of the glass are increased; when the amount is less than 0.1 mol%, the thermal stability of the glass is poor.
RuO2The material is a glass conductive phase and a conductive phase precursor phase, is also a temperature resistance characteristic adjusting modified oxide of a conductive layer formed by in-situ growth of a microchannel plate, can form a novel ruthenium and ruthenium-based conductive metal phase after being reduced by high-temperature hydrogen, but is easy to generate crystallization and phase splitting phenomena after the content of the ruthenium and ruthenium-based conductive metal phase exceeds 12 mol%, and the stability of the resistance performance of the reduced glass is reduced; when the amount is less than 1.5 mol%, high resistance temperature stability cannot be satisfied.
The preparation methods of the micro-channel plate cladding glass with high stable temperature resistance characteristic for low temperature of the embodiment 1-4 and the cladding glass of the comparative example 1-2 comprise the following steps:
mixing quartz sand, lead oxide (red lead or yellow lead), bismuth oxide, barium salt (barium nitrate or barium carbonate), sodium carbonate, cesium carbonate, potassium salt (potassium carbonate or potassium nitrate), basic magnesium carbonate, calcium carbonate, aluminum hydroxide and ruthenium compound (ruthenium trichloride or ruthenium trichloride hydrate or ruthenium dioxide hydrate) to obtain a batch, and adding a clarifying agent Sb accounting for 0.10-0.80 wt% of the total weight of the batch2O3And/or As2O3；
Adding the batch mixture containing the clarifying agent into a crucible at 1300-1550 ℃ for one or more times for melting, wherein the time interval between each time of feeding is 15-90 minutes; after the feeding is finished, heating to 1400-1550 ℃ for clarification for 2-12 hours and 5-10 hours; cooling to 1200 and 1350 ℃ after the clarification is finished, and preserving the heat for 1-5 hours for homogenization; drawing and forming the glass liquid into a glass tube material at 1200-1350 ℃ after homogenization; and (3) preserving the heat of the formed glass tube material for 2-6 hours at the temperature of 550-650 ℃, then cutting off the power and annealing to room temperature and discharging to obtain the microchannel plate cladding material glass.
The method for preparing the conventional microchannel plate skin glass of comparative examples 3 to 4 of the present invention comprises the steps of:
mixing quartz sand, lead oxide (red lead or yellow lead), bismuth oxide, barium salt (barium nitrate or barium carbonate), sodium carbonate, cesium carbonate, potassium salt (potassium carbonate or potassium nitrate), basic magnesium carbonate, calcium carbonate and aluminum hydroxide to obtain a batch mixture, and adding a clarifying agent Sb accounting for 0.10-0.80 wt% of the total weight of the batch mixture2O3And/or As2O3；
Adding the batch mixture containing the clarifying agent into a crucible at 1300-1550 ℃ for one or more times for melting, wherein the time interval between each time of feeding is 15-90 minutes; after the feeding is finished, heating to 1400-1550 ℃ for clarification for 2-12 hours and 5-10 hours; cooling to 1200 and 1350 ℃ after the clarification is finished, and preserving the heat for 1-5 hours for homogenization; drawing and forming the glass liquid into a glass tube material at 1200-1350 ℃ after homogenization; the formed glass tube material is insulated for 2-6 hours at the temperature of 550-650 ℃, and then is cut off and annealed to room temperature to be discharged, thus obtaining the conventional microchannel plate cladding material glass described in the comparative examples 3-4.
The cladding glass of comparative example 1 of the present invention has poor glass forming characteristics and poor crystallization performance, and therefore, a microchannel plate with high stable temperature resistance characteristics for low temperature cannot be prepared, and the practicability of the cladding glass required for preparing the microchannel plate is not provided.
The preparation methods of the microchannel plate with high stable temperature resistance for low temperature in examples 1-3 and the microchannel plate in comparative example 2 of the invention adopt the cladding glass described in the above examples 1-3 and comparative example 2 as the cladding glass of the microchannel plate, and the preparation process mainly comprises the following steps:
pulling down at 1200-1350 ℃ to form a leather glass tube, wherein the leather glass tube is made of the leather glass of the microchannel plate; preparing a core glass rod, nesting the core glass rod into the cladding glass tube, drawing the core glass rod into a single filament, combining a plurality of single filaments, and drawing the combined single filaments into a multifilament; the multifilaments are arranged regularly and then are melted and pressed into blank sections; then, the blank plate is obtained through slicing, chamfering, grinding and polishing, and the structure of the blank plate is shown in figure 1 and comprises the following components: the glass comprises skin glass 1, core glass 2 arranged in the skin glass 1 and edge-covered glass 3 coated outside a hollow channel array formed by the skin glass 1 (a core material rod, a skin material pipe and the edge-covered glass all undergo multiple heat effects together, and the skin material pipe, the core material rod, the skin material pipe and the edge-covered glass are fused and diffused with components). Removing core glass 2 from the blank plate by acid liquor corrosion (the acid liquor is at least one of nitric acid and hydrochloric acid, the solubility of the acid liquor is 0.1 mol% -30 mol%, the time of the acid liquor corrosion is 10 min-600 min, the temperature of the acid liquor corrosion is 30-90 ℃), and forming the microchannel blank plate, wherein the microchannel blank plate has a structure shown in figure 2 and comprises: the hollow glass plate comprises a skin glass 1 with independent hollow channels and a coated glass 3 coated outside a hollow channel array formed by the skin glass 1. And then, carrying out high-temperature hydrogen reduction (the temperature is 350-520 ℃ for 20-600 min, the hydrogen flow is 0.005-10L/min) on the microchannel plate blank plate, plating a metal electrode to obtain the microchannel plate with the characteristics of 5-20 mu m of aperture, 0.20-0.80 mm of thickness and 10-50 mm of outer diameter phi and high stable temperature resistance for low temperature, wherein the structure of the microchannel plate is shown in figure 3, the microchannel plate comprises a base body 4 and electrodes 6 arranged on the upper surface and the lower surface of the base body 4, the base body 4 comprises cladding glass 1 with independent hollow channels and cladding glass 3 cladding the outside of a hollow channel array consisting of the cladding glass 1, and the cladding glass 1 comprises a base material and a channel inner wall 5 connected with the base material. The inner wall 5 of the channel is a high-stability temperature resistance conductive layer and an emission layer 7 generated in situ or as shown in fig. 4, and the inner wall 5 of the channel comprises the high-stability temperature resistance conductive layer and the emission layer 7 generated in situ and an atomic layer deposition microchannel plate film modification layer 8 attached to the high-stability temperature resistance conductive layer and the emission layer 7.
The preparation method of the microchannel plate with the high-temperature resistance and stability for low temperature in embodiment 4 of the present invention adopts the cladding glass described in embodiment 4 as the cladding glass of the microchannel plate, and the preparation process mainly includes:
pulling down at 1200-1350 ℃ to form a leather glass tube, wherein the leather glass tube is made of the leather glass of the microchannel plate; preparing a core glass rod, nesting the core glass rod into the cladding glass tube, drawing the core glass rod into a single filament, combining a plurality of single filaments, and drawing the combined single filaments into a multifilament; the multifilaments are arranged regularly and then melted and pressed into blanksA segment; then, the blank plate is obtained through slicing, chamfering, grinding and polishing, and the structure of the blank plate is shown in figure 1 and comprises the following components: the glass comprises skin glass 1, core glass 2 arranged in the skin glass 1 and edge glass 3 coated outside a hollow channel array formed by the skin glass 1. Removing core glass 2 from the blank plate by acid liquor corrosion (the acid liquor is at least one of nitric acid and hydrochloric acid, the solubility of the acid liquor is 0.1 mol% -30 mol%, the time of the acid liquor corrosion is 10 min-600 min, the temperature of the acid liquor corrosion is 30-90 ℃), and forming the microchannel blank plate, wherein the microchannel blank plate has a structure shown in figure 2 and comprises: the hollow glass plate comprises a skin glass 1 with independent hollow channels and a coated glass 3 coated outside a hollow channel array formed by the skin glass 1. And then, carrying out high-temperature hydrogen reduction (the temperature is 350-520 ℃ for 20-600 min, the hydrogen flow is 0.005L/min-10L/min), plating a metal electrode, and carrying out atomic layer deposition to plate a resistance temperature characteristic modification layer to obtain the micro-channel plate with the aperture of 5-20 microns, the thickness of 0.20-0.80 mm and the outer diameter phi of 10-50 mm, which has the high-temperature-stability temperature resistance characteristic and comprises a base body 4 and electrodes 6 arranged on the upper surface and the lower surface of the base body 4, wherein the base body 4 comprises a piece of cladding glass 1 with an independent hollow channel and a piece of cladding glass 3 coated outside the hollow channel array formed by the piece of cladding glass 1, and the piece of cladding glass 1 comprises a base material and a channel inner wall 5 connected with the base material. The inner wall 5 of the channel of the microchannel plate comprises a conducting layer and an emitting layer 7 with high stable temperature resistance characteristics generated in situ and an atomic layer deposition microchannel plate film modification layer 8 attached to the conducting layer and the emitting layer 7 with the high stable temperature resistance characteristics, wherein the atomic layer deposition microchannel plate film modification layer 8 is a barium strontium titanate composite film, the thickness of the film is 201-203 nm, and barium oxide (BaO) and titanium dioxide (TiO) which form a barium strontium titanate single-layer composite film material2) And strontium oxide (SrO) with the molar ratio of 11:25:10, and the barium strontium titanate multilayer composite film with the thickness of 201-203 nm is formed through 25 times of preparation and superposition of the barium strontium titanate single-layer composite film.
The preparation method of the conventional microchannel plate of comparative example 4 of the present invention adopts the conventional cladding glass of comparative example 4 as the cladding glass of the microchannel plate, and the preparation process mainly comprises:
pulling down at 1200-1350 ℃ to form a leather glass tube, wherein the leather glass tube is made of the leather glass of the microchannel plate; preparing a core glass rod, nesting the core glass rod into the cladding glass tube, drawing the core glass rod into a single filament, combining a plurality of single filaments, and drawing the combined single filaments into a multifilament; the multifilaments are arranged regularly and then are melted and pressed into blank sections; then, the blank plate is obtained through slicing, chamfering, grinding and polishing, and the structure of the blank plate is shown in figure 1 and comprises the following components: the glass comprises skin glass 1, core glass 2 arranged in the skin glass 1 and edge glass 3 coated outside a hollow channel array formed by the skin glass 1. Removing core glass 2 from the blank plate by acid liquor corrosion (the acid liquor is at least one of nitric acid and hydrochloric acid, the solubility of the acid liquor is 0.1 mol% -30 mol%, the time of the acid liquor corrosion is 10 min-600 min, the temperature of the acid liquor corrosion is 30-90 ℃), and forming the microchannel blank plate, wherein the microchannel blank plate has a structure shown in figure 2 and comprises: the hollow glass plate comprises a skin glass 1 with independent hollow channels and a coated glass 3 coated outside a hollow channel array formed by the skin glass 1. And then, carrying out high-temperature hydrogen reduction (the temperature is 350-520 ℃ for 20-600 min, the hydrogen flow is 0.005L/min-10L/min), plating a metal electrode, and carrying out atomic layer deposition to plate a resistance temperature characteristic modified layer to obtain the micro-channel plate with the aperture of 5-20 microns, the thickness of 0.20-0.80 mm and the outer diameter phi of 10-50 mm, which has the high-temperature-stability temperature resistance characteristic and comprises a conventional base body 9 and electrodes 6 arranged on the upper surface and the lower surface of the base body 9, wherein the base body 9 comprises a leather glass 1 with an independent hollow channel and a piece of edge-covering glass 3 covering the outside of the hollow channel array formed by the leather glass 1, and the leather glass 1 comprises a base material and a channel inner wall 10 connected with the base material. The inner wall 10 of the channel of the microchannel plate comprises a conventional conducting layer and an emitting layer 11 which are generated in situ and an atomic layer deposition microchannel plate film modification layer 8 attached to the conventional conducting layer and the emitting layer 11, wherein the atomic layer deposition microchannel plate film modification layer 8 is a barium strontium titanate composite film, the thickness of the film is 180nm, and barium oxide (BaO) and titanium dioxide (TiO) which form a barium strontium titanate single-layer composite film material2) And oxidation ofThe mol ratio of strontium (SrO) is 10:25:6, and the barium strontium titanate multilayer composite film with the thickness of 180nm is formed by preparing and overlapping the barium strontium titanate single-layer composite film for 25 times.
The preparation method of the microchannel plate of comparative example 3 of the present invention adopts the cladding glass of comparative example 3 as the cladding glass of the microchannel plate, and the preparation process mainly comprises:
pulling down at 1200-1350 ℃ to form a leather glass tube, wherein the leather glass tube is made of the leather glass of the microchannel plate; preparing a core glass rod, nesting the core glass rod into the cladding glass tube, drawing the core glass rod into a single filament, combining a plurality of single filaments, and drawing the combined single filaments into a multifilament; the multifilaments are arranged regularly and then are melted and pressed into blank sections; then, the blank plate is obtained through slicing, chamfering, grinding and polishing, and the structure of the blank plate is shown in figure 1 and comprises the following components: the glass comprises skin glass 1, core glass 2 arranged in the skin glass 1 and edge glass 3 coated outside a hollow channel array formed by the skin glass 1. Removing core glass 2 from the blank plate by acid liquor corrosion (the acid liquor is at least one of nitric acid and hydrochloric acid, the solubility of the acid liquor is 0.1 mol% -30 mol%, the time of the acid liquor corrosion is 10 min-600 min, the temperature of the acid liquor corrosion is 30-90 ℃), and forming the microchannel blank plate, wherein the microchannel blank plate has a structure shown in figure 2 and comprises: the hollow glass plate comprises a skin glass 1 with independent hollow channels and a coated glass 3 coated outside a hollow channel array formed by the skin glass 1. And then, carrying out high-temperature hydrogen reduction (the temperature is 350-520 ℃ for 20-600 min, the hydrogen flow is 0.005-10L/min) on the microchannel plate blank plate, plating a metal electrode to obtain the microchannel plate with the aperture of 5-20 microns, the thickness of 0.20-0.80 mm and the outer diameter phi of 10-50 mm, wherein the microchannel plate has the structure shown in figure 6 and comprises a conventional base body 9 and electrodes 6 arranged on the upper surface and the lower surface of the base body 9, the base body 9 comprises cladding glass 1 with independent hollow channels and cladding glass 3 cladding the outside of a hollow channel array formed by the cladding glass 1, and the cladding glass 1 comprises a base material and a channel inner wall 10 connected with the base material. Wherein, the inner wall 10 of the channel is a conventional conductive layer and an emitting layer 11 generated in situ.
In the microchannel plate and the preparation method thereof, except that the cladding glass is the high-temperature-resistance-property high-stability cladding glass for the microchannel plate for low temperature obtained by the invention, other raw materials and preparation processes adopt corresponding means in the prior art, so the details are not repeated herein.
The inner wall structures of the channels of the microchannel plates described in embodiments 1 to 3 are all as shown in fig. 3, that is, the inner wall structures of the channels of the microchannel plates are the in-situ generated conductive layer and the emission layer 7 with high stable temperature resistance.
The structure of the inner wall of the microchannel plate in embodiment 4 is as shown in fig. 4, that is, the inner wall of the microchannel plate includes a conductive layer and an emission layer 7 with a high stable temperature resistance generated in situ, and an atomic layer deposition microchannel plate thin film modification layer 8 attached to the conductive layer and the emission layer 7 with the high stable temperature resistance, where the atomic layer deposition microchannel plate thin film modification layer 8 is a barium strontium titanate composite thin film, and in embodiment 4, the thickness of the thin film is 201 to 203nm, and barium oxide (BaO) and titanium dioxide (TiO) constituting a barium strontium titanate single-layer composite thin film material are barium strontium titanate single-layer composite thin films2) And strontium oxide (SrO) in a molar ratio of 11:25:10, preparing and laminating the single-layer barium strontium titanate composite film for 25 times to form a barium strontium titanate multilayer composite film with the thickness of 201-203 nm, wherein in comparative example 4, the barium strontium titanate composite film has the thickness of 180nm, and barium oxide (BaO) and titanium dioxide (TiO) forming the barium strontium titanate single-layer composite film material2) And the mol ratio of strontium oxide (SrO) is 10:25:6, and the barium strontium titanate multilayer film with the thickness of 180nm is formed through 25 times of barium strontium titanate single-layer film preparation and superposition.
The clad glasses used in comparative examples 3 to 4 of the present invention are those of conventional microchannel plates, and the main difference between the glasses and examples 1 to 4 of the present invention is that the former clad glasses do not contain ruthenium oxide having a positive temperature resistance characteristic. The microchannel plate and the channel inner wall structure thereof described in comparative example 4 are structures as shown in fig. 5, the microchannel plate comprises a conventional substrate 9 of the microchannel plate made of a conventional glass material and electrodes 6 provided on the upper and lower surfaces of the conventional substrate 9, the conventional substrate 9 comprises the channel inner wall 10 of the conventional microchannel plate, and the channel inner wall 10 of the conventional microchannel plate comprises an in-situ generated conventional inner wall 10 of the conventional microchannel plateThe conductive layer and the emitting layer 11 and the atomic layer deposition microchannel plate thin film modification layer 8 attached on the conventional conductive layer and the emitting layer 11, wherein the atomic layer deposition microchannel plate thin film modification layer 11 is a barium strontium titanate composite thin film, and in the comparative example 4, the thickness of the barium strontium titanate composite thin film is 180nm, and barium oxide (BaO) and titanium dioxide (TiO) which form the barium strontium titanate single-layer composite thin film material2) And the mol ratio of strontium oxide (SrO) is 10:25:6, and the barium strontium titanate multilayer film with the thickness of 180nm is formed through 25 times of barium strontium titanate single-layer film preparation and superposition.
As shown in Table 1 below, the clad glass material used in comparative example 4 was RuO removed from the clad glass material used in comparative example 22Preparing a micro-channel plate substrate from similar glass materials as in comparative example 2, and performing Atomic Layer Deposition (ALD) on a micro-channel plate thin film modification layer 8, wherein the thickness of the barium strontium titanate composite thin film is 180nm, and the molar ratio of the barium strontium titanate single-layer composite thin film material is BaO to TiO2SrO is 10:25:6, and the barium strontium titanate multilayer thin film with the thickness of 180nm is formed through 25 times of barium strontium titanate single-layer thin film preparation. Comparative example 4 has a resistance of not more than 5G Ω at a temperature of 30K while substantially satisfying high resistance temperature stability at an ultra-low temperature, but the latter is significantly more excellent in resistance temperature stability than example 4.
TABLE 1 compositions and Performance tests of the skin glasses for microchannel plates having high stable temperature resistance characteristics for low temperature according to examples 1 to 4 of the present invention and comparative examples 1 to 4, and Performance tests of microchannel plates respectively prepared using the skin glasses of examples 1 to 4 and comparative examples 2 to 4 described above
Figure BDA0002313263950000131
Figure BDA0002313263950000141
As can be seen from Table 1, the smaller the absolute value of the temperature coefficient of resistance of example 4, the higher the temperature stability of resistance of the clad glass prepared in example 4, i.e., by coating the glass with the coatingThe material is introduced with positive temperature resistance oxide, and the ALD modified thin film layer with positive temperature resistance is introduced on the surface of the inner wall of the channel, so that the micro-channel plate with high stable temperature resistance under the ultralow temperature condition can be realized; the absolute value of the resistance temperature coefficient of the embodiments 2, 1 and 3 is the second order, namely, the micro-channel plate with high stable temperature resistance characteristic under the ultralow temperature condition can be realized by introducing the positive temperature resistance characteristic oxide into the glass material, and the bulk resistances of the embodiments 2, 1 and 3 under the 30K low temperature condition are all less than 5G omega, so that the ultra-fast reading response requirements under the ultralow temperature detection conditions such as ultralow temperature quantum simulation calculation and the like can be met; the absolute value of the resistance temperature coefficient of the comparative example 3 is small, but the volume resistance of the resistance temperature coefficient exceeds 5G omega under the low-temperature conditions of 35K and 30K, and the ultra-fast reading response requirement under the low-temperature detection conditions of ultralow-temperature quantum simulation calculation and the like cannot be met; RuO having Positive temperature resistance characteristic due to temperature resistance characteristic modification in comparative example 12Too much glass forming property of the cladding glass is greatly reduced, the anti-crystallization performance is too poor, the anti-crystallization property required by the preparation of the microchannel plate cannot be met, the microchannel plate cannot be prepared, and the practicability of the cladding glass required by the preparation of the microchannel plate is not realized.
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 (14)

1. The microchannel plate cladding glass with high stable temperature resistance characteristic for low temperature is characterized by comprising the following components in percentage by mole:
Figure FDA0002313263940000011
2. the microchannel plate frit glass according to claim 1, wherein the microchannel plate frit glass with high stable temperature resistance for low temperature further comprises 0.10 to 0.80% by weight of Sb2O3And/or As2O3。
3. The microchannel plate frit glass according to claim 1, wherein the microchannel plate frit glass having high temperature resistance for low temperature use has a transition temperature Tg of 450 ℃ or more, a softening temperature Tf of 545 ℃ or more, and a thermal expansion coefficient of (60 to 105) × 10 at 100 ℃ to 300 ℃ of (60 to 105) × 10-7No crystallization at 500-950 deg.C.
4. A method for preparing the microchannel plate skin glass with high stable temperature resistance characteristic for low temperature according to any one of claims 1 to 3, which comprises the following steps:
1) mixing quartz sand, lead oxide, bismuth oxide, barium salt, sodium carbonate, cesium carbonate, potassium salt, basic magnesium carbonate, calcium carbonate, aluminum hydroxide and ruthenium compound to obtain a batch mixture, and adding a clarifying agent accounting for 0.10-0.80 wt% of the total weight of the batch mixture;
2) adding the batch containing the clarifying agent into a crucible at 1300-1550 ℃ for one or more times for melting, wherein the time interval between each time of feeding is 15-90 minutes;
3) after the feeding is finished, heating to 1400-1550 ℃ for clarification for 2-12 hours;
4) cooling to 1200-;
5) drawing and forming the glass liquid into a glass tube material at 1200-1350 ℃ after homogenization;
6) and (3) preserving the heat of the formed glass tube material for 2-6 hours at the temperature of 550-650 ℃, then cutting off the power and annealing to room temperature and discharging to obtain the microchannel plate cladding material glass.
5. The method of claim 1, wherein a weakly oxidizing atmosphere is maintained in the crucible during the melting, the weakly oxidizing atmosphere having an oxygen partial pressure greater than 20 kPa.
6. The method of claim 1, wherein the batch comprises, in mole percent:
Figure FDA0002313263940000021
7. the method of claim 6, wherein the lead oxide is red lead or yellow lead; the barium salt is barium nitrate or barium carbonate; the potassium salt is potassium carbonate or potassium nitrate; the ruthenium compound is ruthenium trichloride, ruthenium trichloride hydrate, ruthenium dioxide or ruthenium dioxide hydrate; the clarifying agent is Sb2O3And/or As2O3。
8. A microchannel plate with high-stability temperature resistance for low temperature, which is characterized by comprising a substrate and electrodes arranged on the upper surface and the lower surface of the substrate, wherein the substrate comprises cladding glass with independent hollow channels and edge-coated glass coated on the outer surface of the cladding glass, and the cladding glass is the cladding glass of the microchannel plate as claimed in any one of claims 1 to 3.
9. A preparation method of a microchannel plate with high stable temperature resistance characteristic for low temperature is characterized by comprising the following steps:
s1, drawing and forming a leather glass tube, wherein the leather glass tube is made of the leather glass of the microchannel plate according to any one of claims 1-3;
s2, preparing a core material glass rod;
s3, nesting the core material glass rod into the leather material glass tube and drawing the core material glass rod into a monofilament;
s4, combining a plurality of monofilaments and then drawing the monofilaments into multifilaments;
s5, regularly arranging multifilaments, and then melting and pressing the multifilaments into blank sections;
s6, slicing, chamfering, grinding and polishing the blank sections to obtain a blank plate;
and S7, corroding the blank plate with acid liquor to remove cores, reducing the blank plate with high-temperature hydrogen, and plating a metal electrode to obtain the micro-channel plate with high stable temperature resistance for low temperature.
10. The method according to claim 9,
step S6 specifically includes: slicing, chamfering, grinding and polishing the blank sections to obtain a micro-channel plate blank plate with high stable temperature resistance for low temperature;
step S7 specifically includes: the method comprises the steps of corroding and coring a blank plate by acid liquor to obtain an independent hollow channel structure with millions of micron-sized apertures, reducing the structure by high-temperature hydrogen to grow a conducting layer and a silicon dioxide secondary electron emission layer with high stable temperature resistance characteristics in situ on the surface of the inner wall of the hollow channel, and then evaporating metal electrodes on the upper surface and the lower surface of the conducting layer and the silicon dioxide secondary electron emission layer to obtain the micro-channel plate with high stable temperature resistance characteristics for low temperature.
11. The method according to claim 10,
in the step S1, the drawing forming temperature of the leather glass tube is 1200-1350 ℃;
in step S7, the acid solution is at least one of nitric acid and hydrochloric acid, the solubility of the acid solution is 0.1 mol% -30 mol%, the corrosion time of the acid solution is 10 min-600 min, and the corrosion temperature of the acid solution is 30-90 ℃;
in step S7, the temperature of the high-temperature hydrogen reduction is 350-520 ℃, the time of the high-temperature hydrogen reduction is 20-600 min, and the flow rate of the hydrogen is 0.005-10L/min;
in step S7, the metal electrode is a Ti, Cr, Au, or Ni/Cr surface electrode; the sheet resistance of the metal electrode is not higher than 300 Ω.
12. An ALD modified microchannel plate, comprising a substrate having a single-layer or multi-layer modified thin film deposited on an inner wall surface thereof.
13. The ALD-modified microchannel plate of claim 12, wherein the substrate is the microchannel plate for low temperature high stability temperature resistance characteristics of any one of claims 1 to 3.
14. A method of preparing the ALD modified microchannel plate of claim 12 or 13, comprising the steps of:
the ALD modified microchannel plate is obtained by using the microchannel plate with the low-temperature and high-stability temperature resistance characteristic as claimed in claim 8 as a substrate and preparing a single-layer or multi-layer modified thin film on the surface of the inner wall of the channel of the microchannel plate by using an atomic layer deposition method.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111463102A (en) * 2020-05-09 2020-07-28 北方夜视技术股份有限公司 Microchannel plate
CN112979160A (en) * 2021-03-03 2021-06-18 中国建筑材料科学研究总院有限公司 Ion bombardment-resistant glass composition, microchannel plate cladding glass, microchannel plate and preparation method
CN113916910A (en) * 2021-10-19 2022-01-11 中国建筑材料科学研究总院有限公司 X-ray detection lens and preparation method and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10182185A (en) * 1996-11-07 1998-07-07 Toray Ind Inc Photosensitive glass paste
CN106630596A (en) * 2016-12-29 2017-05-10 中国建筑材料科学研究总院 Silicate skin glass, micro-pore optics and preparation method thereof
JP2018092730A (en) * 2016-11-30 2018-06-14 住友金属鉱山株式会社 Composition for resistor and resistor paste containing the same furthermore thick film resistor therewith
CN108493083A (en) * 2018-04-13 2018-09-04 中国建筑材料科学研究总院有限公司 Ultralow temperature stablizes the microchannel plate and preparation method thereof of temperature resistance characteristic
CN109321892A (en) * 2018-10-10 2019-02-12 西安近代化学研究所 A kind of resistive layer and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10182185A (en) * 1996-11-07 1998-07-07 Toray Ind Inc Photosensitive glass paste
JP2018092730A (en) * 2016-11-30 2018-06-14 住友金属鉱山株式会社 Composition for resistor and resistor paste containing the same furthermore thick film resistor therewith
CN106630596A (en) * 2016-12-29 2017-05-10 中国建筑材料科学研究总院 Silicate skin glass, micro-pore optics and preparation method thereof
CN108493083A (en) * 2018-04-13 2018-09-04 中国建筑材料科学研究总院有限公司 Ultralow temperature stablizes the microchannel plate and preparation method thereof of temperature resistance characteristic
CN109321892A (en) * 2018-10-10 2019-02-12 西安近代化学研究所 A kind of resistive layer and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111463102A (en) * 2020-05-09 2020-07-28 北方夜视技术股份有限公司 Microchannel plate
CN111463102B (en) * 2020-05-09 2023-03-31 北方夜视技术股份有限公司 Microchannel plate
CN112979160A (en) * 2021-03-03 2021-06-18 中国建筑材料科学研究总院有限公司 Ion bombardment-resistant glass composition, microchannel plate cladding glass, microchannel plate and preparation method
CN113916910A (en) * 2021-10-19 2022-01-11 中国建筑材料科学研究总院有限公司 X-ray detection lens and preparation method and application thereof
CN113916910B (en) * 2021-10-19 2023-07-28 中国建筑材料科学研究总院有限公司 X-ray detection lens and preparation method and application thereof

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