CN109734334A - It is a kind of with fire-retardant, Low emissivity wear-resisting property vacuum energy-saving glass and preparation method thereof - Google Patents

Abstract

The present invention provides a kind of hollow energy-saving glass fiber with fire-retardant Low emissivity wear-resisting property; the hollow energy-saving glass fiber is made of two panels original sheet glass, and the specific structure of the vacuum energy-saving glass is the first original sheet glass, the successively UV-absorbing layer coated on the first original sheet glass surface, heat-barrier coating, the first wearing layer, the second original sheet glass and the flame retardant coating, the second wearing layer, the porous optical thin films layer that are successively coated on the second original sheet glass surface；It further include adhesive between the two panels original sheet glass, adhesive is located at around two panels original sheet glass, forms closed cavity between two panels original sheet glass.The invention also discloses the preparation methods of the hollow energy-saving glass fiber, specifically: original sheet glass is activated first, functional coating solution is then made respectively, and it is successively coated on to original sheet glass surface, it is sintered under certain condition after drying, fine and close functional coating is made.The hollow energy-saving glass fiber heat-proof quality is excellent, and flame retardant property is good.

Description

It is a kind of with fire-retardant, Low emissivity wear-resisting property vacuum energy-saving glass and its preparation Method

Technical field:

The present invention relates to glass preparation fields, are specifically related to a kind of with fire-retardant, Low emissivity wear-resisting property vacuum section It can glass.

Background technique:

With advances in technology with the development of society, glass has been not only traditional common building materials, but Be widely used in information show, the critical material of the multiple fields such as new energy, biologic medical and aerospace, while these fields Application increasingly higher demands are proposed to the performance of modern glass material, function, component and manufacturing technology, new technology and new The research and development difficulty of product is increasing.

In modern society, renewable energy consumption is quicklyd increase, and the energy in short supply and is faced as the whole world important One of problem is excessively got worse using caused a series of environmental problems by the energy, in energy consumption, passes through building The energy, which scatters and disappears, occupies very big a part, and glass is insulation most weak part in energy saving building energy consumption.Due to building The optical transparence and higher heat-conductivity that glass has, the inlet of indoor infrared radiation energy determine by it, therefore, transparent glass Heat-proof quality have become measure the whether energy-efficient important indicator of building glass.Therefore, how to be made and to have excellent performance Energy-saving glass is an important measures for solving energy consumption problem.In the prior art, there are two types of methods to be made functional heat-insulated The building energy conservation glass of heat preservation.First is that reducing the heat transfer coefficient of glass using hollow, vacuum, filled layer glass etc. to reach heat-insulated The energy saving purpose of heat preservation；Second is that reducing the sheltering coefficient of glass using the technology including heat reflection, pad pasting and plated film etc.. Wherein, coated glass is a kind of more common method.Coating film on glass can be divided into two major classes according to membrane formation mechanism.The first kind is Plated film refers to that chemical reaction, which has occurred, in substrate surface by raw material in coating process forms film, including colloidal sol Gel method, chemical vapour deposition technique, electric float glass process, hot spray process etc.；Low two class is physical coating, is that film is passed through physical method On the glass substrate by particle deposition, the generation that whole process does not chemically react, such as vacuum vapor deposition method, sputtering method, ion beam Sedimentation etc..

The method that Chinese patent 200880013331.1 discloses energy-saving glass and manufactures energy-saving glass, the energy-saving glass packet The first surface and second surface being substantially parallel to one another are included, contain solar radiant energy absorbent, solar radiant energy in glass substance Absorbent is present in close to towards in the layer of the glass substance of the first surface outside building, when from described first When surface is deep into the glass substance, the concentration of the radiation energy absorber is substantially reduced in said layer, thus from When the first surface measurement of the glass, the absorbent is present at least 0.1 micron and is not more than 100 microns of depth Degree, for solar radiant energy to be absorbed into the layer of the glass, the layer of the glass is close to the first surface.The energy conservation glass The opposite on the solar radiative absorption surface of glass can be coated with coated conductive oxide layer, and sun sorbent surface can further completely Or it is partly coated with nano-sized titanium dioxide particle.

Chinese patent 201510793325.4 discloses a kind of low-voltage vacuum energy-saving glass and preparation method thereof comprising One transparent glass and the second transparent glass, the low-voltage vacuum energy-saving glass further include separation pad and sealing flux, which is located at Between first transparent glass and second transparent glass, which is located at first transparent glass and second transparent glass Periphery and the low-voltage vacuum energy-saving glass further include first transparent glass and second transparent glass under vacuum conditions Between a closed vacuum chamber being surrounded by the sealing flux.

Chinese patent 201710245172.9 disclose it is a kind of it is novel can the double silver low radiation energy-saving glass of tempering, the energy conservation glass Glass includes original sheet glass and film plating layer；The film plating layer from original sheet glass outward successively include: first medium layer, first medium It protects and seed layer, the first functional layer, second dielectric layer, third dielectric layer, second medium protects simultaneous seed layer, the second function Layer, the second coat of metal, the 4th dielectric layer, third protective layer；First coat of metal be ceramic alumina zinc-aluminium layer or Nicr layer, the first medium layer and second dielectric layer are silicon nitride layer, and the first medium is protected and seed layer is zinc oxide Layer, the first functional layer and the second functional layer are silver layer, and third dielectric layer is zinc oxide tin layers, and the 4th dielectric layer is silicon nitride layer, Third protective layer is graphite linings.The energy-saving glass not only has misalignment before and after tempering small, and it is high, positive that there is also film surface intensity The small advantage with Side Color colour cast promotes application of the LOW-E glass in each field.

It is generally used single method in the prior art to be modified glass, although for pair of vacuum glass heat It spreads heat and conduction heat transfer and is fallen too low, so that gas heat-transfer can be ignored, but its production method is more multiple Miscellaneous, equipment cost is higher, and product quality yield rate cannot be stablized.And the problem of single coating method, essentially consists between film layer Binding force it is poor, be easy to happen falling off between film layer, under extreme environmental conditions so as to cause strength of glass and thermal insulation The decline of energy.

Summary of the invention:

In view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of with fire-retardant, Low emissivity wear-resisting property true Empty energy-saving glass and preparation method thereof is respectively coated functional coating to original sheet glass, then will be coated with functional coating Original sheet glass prepares vacuum energy-saving glass, solves existing simplex method and prepares energy-saving glass and is difficult to reach heat-proof quality, mechanical property The all good requirement of energy, endurance quality.

To achieve the above object, the invention adopts the following technical scheme:

It is a kind of with fire-retardant, Low emissivity wear-resisting property vacuum energy-saving glass, the vacuum energy-saving glass is by two panels glass Glass original piece composition, the specific structure of the energy-saving glass are followed successively by the first original sheet glass, are successively coated on the first original sheet glass table The UV-absorbing layer in face, heat-barrier coating, the first wearing layer, the second original sheet glass and to be successively coated on the second glass former The flame retardant coating on piece surface, the second wearing layer, porous optical thin films layer；It further include adhesive between the two panels original sheet glass, Adhesive is located at around two panels original sheet glass, and airtight vacuum chamber is formed between two panels original sheet glass.

As a preferred embodiment of the above technical solution, the material of the UV-absorbing layer is the titanium deoxid film layer for mixing yttrium, It is with a thickness of 15nm.

As a preferred embodiment of the above technical solution, the material of the heat-barrier coating is aerosil/polystyrene Tiny balloon composite layer, with a thickness of 5nm.

As a preferred embodiment of the above technical solution, the material of first wearing layer is silicon nitride layer, with a thickness of 10nm.

As a preferred embodiment of the above technical solution, the material of the flame retardant coating is the polyurethane material of Modified by Expandable Graphite Material, with a thickness of 10nm.

As a preferred embodiment of the above technical solution, the material of second wearing layer is that nano-sheet nitrogenizes poly- the four of boron modification Fluoride material, with a thickness of 20nm.

As a preferred embodiment of the above technical solution, the material of the porous optical thin films layer is that magnesium fluoride/silica is compound Coating, magnesium fluoride, silica mass ratio be 1:(3-6), with a thickness of 20nm.

As a preferred embodiment of the above technical solution, the material of the adhesive is silicone sealant.

The preparation method of the energy-saving glass, comprising the following steps:

(1) yttrium nitrate aqueous solution for preparing 1.5-4mol/L prepares the ethanol solution of titanium tetrachloride, with titanium, yttrium molar ratio The ethanol solution of yttrium nitrate aqueous solution and titanium tetrachloride is mixed for the ratio of 1:(0.32-0.45), it is molten that 10wt% hydrochloric acid is added dropwise Liquid, is stirred 3h under 3000rpm by 40 DEG C, then aging 10h at room temperature, and plural gel is made；

(2) ethyl orthosilicate is dissolved in ethyl alcohol, deionized water is added, at room temperature stir process under the revolving speed of 1500rpm 1h is subsequently placed in reaction kettle, and the sodium hydroxide solution of 10wt% is added, sealing, at 90 DEG C, reacts 2-4h, after reaction It is cooled to room temperature, silica solution is made；

(3) 30 parts of styrene monomers, 0.01-0.03 parts of emulsifiers and 8 parts of deionized waters are mixed, 0.02 part of over cure is added Polystyrene seed emulsion is made in sour potassium, the polymerization reaction 1h at 60 DEG C；Deionized water is added into polystyrene seed emulsion Being diluted to solid content is 5%, and 10 parts of benzene divinyls are then added, are stirred 30min, is filtered, by the solid after filter 0.001 It is scattered in deionized water under the action of part neopelex and 0.02 part of potassium peroxydisulfate is added, the reaction was continued at 60 DEG C 50min, filtering, the solid after filter are placed in ethyl alcohol and the mixed solution of DMF, stir 1-5h at room temperature, filter, solid is done It is dry, polystyrene hollow microballoon is made；By 20 parts of silica solution and 1-4 parts of polystyrene microspheres be scattered in deionized water be made every Thermal-protective coating solution；

(4) the first original sheet glass is placed in the hydrochloric acid solution of 10wt% using deionized water, acetone cleaning, drying, 25wt% hydrogen peroxide is added dropwise, water-bath immersion treatment 30min at 60 DEG C is dry after taking-up, and plural gel made from step (1) is applied It is overlying on the first original sheet glass surface, is dried 20min at 80 DEG C；Heat-barrier coating solution made from coating step (3) later, Continue dry 30min at 80 DEG C, the first original sheet glass after drying is placed in sintering furnace, and constant temperature is handled first at 300 DEG C 30min is warming up at 600 DEG C with the heating rate of 10 DEG C/min later, constant temperature handle 1h, after cool to room temperature with the furnace； Finally use magnetron sputtering method spraying silicon nitride coating；

(5) 10 parts of expansible graphites, 0.01 part of cetyl trimethylammonium bromide, 50 parts of deionized waters are mixed and is placed in row Ball-milling treatment 3-5h in planetary ball mill is filtered, dry, finally that 0.3-1 parts of treated expansible graphites and 22 parts are aqueous Polyurethane, 0.1 part of p-hydroxybenzenyl sulfonate, 30 parts of deionized waters are mixed to prepare dispersion liquid；

(6) 0.1-0.4 parts of nano-sheet boron nitride, 18 parts of ptfe emulsions, 0.1 part of silane coupling agent, 1 part are consolidated Polytetrafluoroethylene (PTFE) composite solution A is made in agent；The Fluorinse that mass concentration is 10% is prepared, it is molten that magnesium chloride is then added Liquid reacts 2-6h at 110 DEG C in reaction kettle, after filter, solid is dissolved in nitric acid, the isopropanol that silicon ethyl alcohol is added is molten Liquid is stirred obtained composite solution B；

(7) the second original sheet glass cleaning-drying is placed in the sodium hydroxide solution of 10wt%, 25wt% dioxygen is added dropwise Water, immersion treatment 30min at 50 DEG C, take out it is dry after, the successively dispersion liquid made from its surface coating step (5), at 50 DEG C Composite solution A is coated after drying, continues to coat composite solution B after dry, constant temperature is handled at 500 DEG C in sintering furnace after drying 2h；

(8) 12 parts of silicon rubber, 3 parts of dimethicones, 0.03 part of talcum powder are placed in after blender fills and be stirred, are added 0.005 part of silane coupling agent, 1 part of carbon black continue to be stirred, and adhesive is made；By adhesive be coated on the first original sheet glass and Around second original sheet glass, heat 30min at 300 DEG C, then by the first original sheet glass and the second original sheet glass in vacuum Under the conditions of be combined obtained hollow energy-saving glass fiber.

Compared with prior art, the invention has the following advantages that

The present invention be coated with functional coating the first original sheet glass and the second original sheet glass under conditions of vacuum into Row combination, and be sealed using adhesive, not only heat-proof quality is excellent and wear-resisting, fire-retardant for vacuum energy-saving glass obtained Excellent performance, mechanical property are good；Wherein, the silicon nitride coating on the first original sheet glass surface can effectively reduce down to a certain degree it is visible The transmitance in light area, can fuel factor caused by the visible light-transmissive sheet glass of stop portions, and silicon nitride can also have It imitates stop portions near infrared light and penetrates glass, the heat radiation of near infrared region can also be reduced and bring fuel factor, also to remote Infrared to have stronger reflectivity, so that glass obtained has good low radiance, and silicon nitride also has well Wear-resisting property.The present invention also uses the titanium deoxid film layer for mixing yttrium as UV-absorbing layer, and the doping of yttrium effectively improves Absorption of the titanium dioxide to ultraviolet light, improves the heat-proof quality of glass；Aerosil/polystyrene hollow microballoon As heat-barrier coating, aerosil hole is big, and Si-O key is mutually wound fine and close three-dimensional net structure, has Nanoscale hole can effectively obstruct heat transfer caused by cross-ventilation, the hollow knot of the structure and polystyrene hollow microballoon Structure can be effectively improved the heat-proof quality of energy-saving glass.

Expansible graphite and aqueous polyurethane form flame retardant coating, and expansible graphite can form heat insulation layer in burning, have Imitate it is heat-insulated, oxygen barrier, to inhibit the propagation of fire；It is former that the polytetrafluoroethylene material that nano-sheet nitrogenizes boron modification is coated on glass Piece surface forms good coating, and wearability is good, and optical thin film coating produced by the present invention is mixed by magnesium fluoride and silica solution It closes and is coated on original sheet glass surface, porous reticular structure can be formed under certain heat treatment, not only there is good light Performance is learned, and heat-proof quality is good.During preparation, the present invention first pre-processes original sheet glass, to activate glass Former piece facilitates post-processing, and material feedstock is directly coated on to original sheet glass surface, and the particle in stoste is uniformly dispersed, can be effective Be attached to original sheet glass surface, under certain conditions dry when, can original sheet glass surface formed fine and close colloidal solid and Cross-linked structure；Later using the heat treatment of certain condition, more fine and close reticular structure is formed, glass is effectively improved Performance.

Specific embodiment:

In order to better understand the present invention, below by embodiment, the present invention is further described, and embodiment is served only for solving The present invention is released, any restriction will not be constituted to the present invention.

Embodiment 1

(1) yttrium nitrate aqueous solution for preparing 1.5mol/L prepares the ethanol solution of titanium tetrachloride, is with titanium, yttrium molar ratio The ratio of 1:0.32 mixes the ethanol solution of yttrium nitrate aqueous solution and titanium tetrachloride, dropwise addition 10wt% hydrochloric acid solution, and 40 DEG C, It is stirred 3h under 3000rpm, then aging 10h at room temperature, plural gel is made；

(2) ethyl orthosilicate is dissolved in ethyl alcohol, deionized water is added, at room temperature stir process under the revolving speed of 1500rpm 1h is subsequently placed in reaction kettle, and the sodium hydroxide solution of 10wt% is added, sealing, at 90 DEG C, reacts 2h, cold after reaction But to room temperature, silica solution is made；

(3) 30 parts of styrene monomers, 0.01 part of emulsifier and 8 parts of deionized waters are mixed, 0.02 part of potassium peroxydisulfate are added, Polystyrene seed emulsion is made in the polymerization reaction 1h at 60 DEG C；Deionized water dilution is added into polystyrene seed emulsion It is 5% to solid content, 10 parts of benzene divinyls is then added, are stirred 30min, filters, by the solid after filter at 0.001 part ten It is scattered in deionized water 0.02 part of potassium peroxydisulfate of addition under the action of dialkyl benzene sulfonic acids sodium, the reaction was continued at 60 DEG C 50min, Filtering, the solid after filter are placed in ethyl alcohol and the mixed solution of DMF, stir 1h at room temperature, are filtered, and solid is dry, are made poly- Styrene tiny balloon；It is molten that obtained heat-barrier coating is dispersed in deionized water by 20 parts of silica solution and 1 part of polystyrene microsphere Liquid；

(4) the first original sheet glass is placed in the hydrochloric acid solution of 10wt% using deionized water, acetone cleaning, drying, 25wt% hydrogen peroxide is added dropwise, water-bath immersion treatment 30min at 60 DEG C is dry after taking-up, and plural gel made from step (1) is applied It is overlying on the first original sheet glass surface, is dried 20min at 80 DEG C；Heat-barrier coating solution made from coating step (3) later, Continue dry 30min at 80 DEG C, the first original sheet glass after drying is placed in sintering furnace, and constant temperature is handled first at 300 DEG C 30min is warming up at 600 DEG C with the heating rate of 10 DEG C/min later, constant temperature handle 1h, after cool to room temperature with the furnace； Finally use magnetron sputtering method spraying silicon nitride coating；

(5) 10 parts of expansible graphites, 0.01 part of cetyl trimethylammonium bromide, 50 parts of deionized waters are mixed and is placed in row Ball-milling treatment 3h in planetary ball mill is filtered, dry, finally by 0.3 part of treated expansible graphite and 22 parts of aqueous poly- ammonia Ester, 0.1 part of p-hydroxybenzenyl sulfonate, 30 parts of deionized waters are mixed to prepare dispersion liquid；

(6) by 0.1 part of nano-sheet boron nitride, 18 parts of ptfe emulsions, 0.1 part of silane coupling agent, 1 part of curing agent Polytetrafluoroethylene (PTFE) composite solution A is made；The Fluorinse that mass concentration is 10% is prepared, magnesium chloride solution is then added, instead Answer in kettle and react 2h at 110 DEG C, after filter, solid is dissolved in nitric acid, the aqueous isopropanol of silicon ethyl alcohol is added, stirring is mixed It closes and composite solution B is made；

(7) the second original sheet glass cleaning-drying is placed in the sodium hydroxide solution of 10wt%, 25wt% dioxygen is added dropwise Water, immersion treatment 30min at 50 DEG C, take out it is dry after, the successively dispersion liquid made from its surface coating step (5), at 50 DEG C Composite solution A is coated after drying, continues to coat composite solution B after dry, constant temperature is handled at 500 DEG C in sintering furnace after drying 2h；

(8) 12 parts of silicon rubber, 3 parts of dimethicones, 0.03 part of talcum powder are placed in after blender fills and be stirred, are added 0.005 part of silane coupling agent, 1 part of carbon black continue to be stirred, and adhesive is made；By adhesive be coated on the first original sheet glass and Around second original sheet glass, heat 30min at 300 DEG C, then by the first original sheet glass and the second original sheet glass in vacuum Under the conditions of be combined obtained hollow energy-saving glass fiber.

Embodiment 2

(1) yttrium nitrate aqueous solution for preparing 4mol/L prepares the ethanol solution of titanium tetrachloride, with titanium, yttrium molar ratio for 1: 0.45 ratio mixes the ethanol solution of yttrium nitrate aqueous solution and titanium tetrachloride, dropwise addition 10wt% hydrochloric acid solution, and 40 DEG C, It is stirred 3h under 3000rpm, then aging 10h at room temperature, plural gel is made；

(2) ethyl orthosilicate is dissolved in ethyl alcohol, deionized water is added, at room temperature stir process under the revolving speed of 1500rpm 1h is subsequently placed in reaction kettle, and the sodium hydroxide solution of 10wt% is added, sealing, at 90 DEG C, reacts 4h, cold after reaction But to room temperature, silica solution is made；

(3) 30 parts of styrene monomers, 0.03 part of emulsifier and 8 parts of deionized waters are mixed, 0.02 part of potassium peroxydisulfate are added, Polystyrene seed emulsion is made in the polymerization reaction 1h at 60 DEG C；Deionized water dilution is added into polystyrene seed emulsion It is 5% to solid content, 10 parts of benzene divinyls is then added, are stirred 30min, filters, by the solid after filter at 0.001 part ten It is scattered in deionized water 0.02 part of potassium peroxydisulfate of addition under the action of dialkyl benzene sulfonic acids sodium, the reaction was continued at 60 DEG C 50min, Filtering, the solid after filter are placed in ethyl alcohol and the mixed solution of DMF, stir 5h at room temperature, are filtered, and solid is dry, are made poly- Styrene tiny balloon；It is molten that obtained heat-barrier coating is dispersed in deionized water by 20 parts of silica solution and 4 parts of polystyrene microspheres Liquid；

(4) the first original sheet glass is placed in the hydrochloric acid solution of 10wt% using deionized water, acetone cleaning, drying, 25wt% hydrogen peroxide is added dropwise, water-bath immersion treatment 30min at 60 DEG C is dry after taking-up, and plural gel made from step (1) is applied It is overlying on the first original sheet glass surface, is dried 20min at 80 DEG C；Heat-barrier coating solution made from coating step (3) later, Continue dry 30min at 80 DEG C, the first original sheet glass after drying is placed in sintering furnace, and constant temperature is handled first at 300 DEG C 30min is warming up at 600 DEG C with the heating rate of 10 DEG C/min later, constant temperature handle 1h, after cool to room temperature with the furnace； Finally use magnetron sputtering method spraying silicon nitride coating；

(5) 10 parts of expansible graphites, 0.01 part of cetyl trimethylammonium bromide, 50 parts of deionized waters are mixed and is placed in row Ball-milling treatment 5h in planetary ball mill is filtered, dry, finally by 1 part of treated expansible graphite and 22 parts of aqueous polyurethanes, 0.1 part of p-hydroxybenzenyl sulfonate, 30 parts of deionized waters are mixed to prepare dispersion liquid；

(6) by 0.4 part of nano-sheet boron nitride, 18 parts of ptfe emulsions, 0.1 part of silane coupling agent, 1 part of curing agent Polytetrafluoroethylene (PTFE) composite solution A is made；The Fluorinse that mass concentration is 10% is prepared, magnesium chloride solution is then added, instead Answer in kettle and react 6h at 110 DEG C, after filter, solid is dissolved in nitric acid, the aqueous isopropanol of silicon ethyl alcohol is added, stirring is mixed It closes and composite solution B is made；

(7) the second original sheet glass cleaning-drying is placed in the sodium hydroxide solution of 10wt%, 25wt% dioxygen is added dropwise Water, immersion treatment 30min at 50 DEG C, take out it is dry after, the successively dispersion liquid made from its surface coating step (5), at 50 DEG C Composite solution A is coated after drying, continues to coat composite solution B after dry, constant temperature is handled at 500 DEG C in sintering furnace after drying 2h；

(8) 12 parts of silicon rubber, 3 parts of dimethicones, 0.03 part of talcum powder are placed in after blender fills and be stirred, are added 0.005 part of silane coupling agent, 1 part of carbon black continue to be stirred, and adhesive is made；By adhesive be coated on the first original sheet glass and Around second original sheet glass, heat 30min at 300 DEG C, then by the first original sheet glass and the second original sheet glass in vacuum Under the conditions of be combined obtained hollow energy-saving glass fiber.

Embodiment 3

(1) yttrium nitrate aqueous solution for preparing 2mol/L prepares the ethanol solution of titanium tetrachloride, with titanium, yttrium molar ratio for 1: 0.35 ratio mixes the ethanol solution of yttrium nitrate aqueous solution and titanium tetrachloride, dropwise addition 10wt% hydrochloric acid solution, and 40 DEG C, It is stirred 3h under 3000rpm, then aging 10h at room temperature, plural gel is made；

(2) ethyl orthosilicate is dissolved in ethyl alcohol, deionized water is added, at room temperature stir process under the revolving speed of 1500rpm 1h is subsequently placed in reaction kettle, and the sodium hydroxide solution of 10wt% is added, sealing, at 90 DEG C, reacts 3h, cold after reaction But to room temperature, silica solution is made；

(3) 30 parts of styrene monomers, 0.02 part of emulsifier and 8 parts of deionized waters are mixed, 0.02 part of potassium peroxydisulfate are added, Polystyrene seed emulsion is made in the polymerization reaction 1h at 60 DEG C；Deionized water dilution is added into polystyrene seed emulsion It is 5% to solid content, 10 parts of benzene divinyls is then added, are stirred 30min, filters, by the solid after filter at 0.001 part ten It is scattered in deionized water 0.02 part of potassium peroxydisulfate of addition under the action of dialkyl benzene sulfonic acids sodium, the reaction was continued at 60 DEG C 50min, Filtering, the solid after filter are placed in ethyl alcohol and the mixed solution of DMF, stir 2h at room temperature, are filtered, and solid is dry, are made poly- Styrene tiny balloon；It is molten that obtained heat-barrier coating is dispersed in deionized water by 20 parts of silica solution and 2 parts of polystyrene microspheres Liquid；

(4) the first original sheet glass is placed in the hydrochloric acid solution of 10wt% using deionized water, acetone cleaning, drying, 25wt% hydrogen peroxide is added dropwise, water-bath immersion treatment 30min at 60 DEG C is dry after taking-up, and plural gel made from step (1) is applied It is overlying on the first original sheet glass surface, is dried 20min at 80 DEG C；Heat-barrier coating solution made from coating step (3) later, Continue dry 30min at 80 DEG C, the first original sheet glass after drying is placed in sintering furnace, and constant temperature is handled first at 300 DEG C 30min is warming up at 600 DEG C with the heating rate of 10 DEG C/min later, constant temperature handle 1h, after cool to room temperature with the furnace； Finally use magnetron sputtering method spraying silicon nitride coating；

(5) 10 parts of expansible graphites, 0.01 part of cetyl trimethylammonium bromide, 50 parts of deionized waters are mixed and is placed in row Ball-milling treatment 3.5h in planetary ball mill is filtered, dry, finally that 0.5 part of treated expansible graphite and 22 parts is aqueous poly- Urethane, 0.1 part of p-hydroxybenzenyl sulfonate, 30 parts of deionized waters are mixed to prepare dispersion liquid；

(6) by 0.2 part of nano-sheet boron nitride, 18 parts of ptfe emulsions, 0.1 part of silane coupling agent, 1 part of curing agent Polytetrafluoroethylene (PTFE) composite solution A is made；The Fluorinse that mass concentration is 10% is prepared, magnesium chloride solution is then added, instead Answer in kettle and react 4h at 110 DEG C, after filter, solid is dissolved in nitric acid, the aqueous isopropanol of silicon ethyl alcohol is added, stirring is mixed It closes and composite solution B is made；

(7) the second original sheet glass cleaning-drying is placed in the sodium hydroxide solution of 10wt%, 25wt% dioxygen is added dropwise Water, immersion treatment 30min at 50 DEG C, take out it is dry after, the successively dispersion liquid made from its surface coating step (5), at 50 DEG C Composite solution A is coated after drying, continues to coat composite solution B after dry, constant temperature is handled at 500 DEG C in sintering furnace after drying 2h；

(8) 12 parts of silicon rubber, 3 parts of dimethicones, 0.03 part of talcum powder are placed in after blender fills and be stirred, are added 0.005 part of silane coupling agent, 1 part of carbon black continue to be stirred, and adhesive is made；By adhesive be coated on the first original sheet glass and Around second original sheet glass, heat 30min at 300 DEG C, then by the first original sheet glass and the second original sheet glass in vacuum Under the conditions of be combined obtained hollow energy-saving glass fiber.

Embodiment 4

(1) yttrium nitrate aqueous solution for preparing 3mol/L prepares the ethanol solution of titanium tetrachloride, with titanium, yttrium molar ratio for 1: 0.4 ratio mixes the ethanol solution of yttrium nitrate aqueous solution and titanium tetrachloride, dropwise addition 10wt% hydrochloric acid solution, and 40 DEG C, It is stirred 3h under 3000rpm, then aging 10h at room temperature, plural gel is made；

(2) ethyl orthosilicate is dissolved in ethyl alcohol, deionized water is added, at room temperature stir process under the revolving speed of 1500rpm 1h is subsequently placed in reaction kettle, and the sodium hydroxide solution of 10wt% is added, sealing, at 90 DEG C, reacts 3.5h, after reaction It is cooled to room temperature, silica solution is made；

(3) 30 parts of styrene monomers, 0.025 part of emulsifier and 8 parts of deionized waters are mixed, 0.02 part of persulfuric acid is added Polystyrene seed emulsion is made in potassium, the polymerization reaction 1h at 60 DEG C；It is dilute that deionized water is added into polystyrene seed emulsion Releasing to solid content is 5%, and 10 parts of benzene divinyls are then added, are stirred 30min, filter, by the solid after filter at 0.001 part It is scattered under the action of neopelex in deionized water and 0.02 part of potassium peroxydisulfate is added, the reaction was continued at 60 DEG C 50min, filtering, the solid after filter are placed in ethyl alcohol and the mixed solution of DMF, stir 4h at room temperature, are filtered, and solid is dry, Polystyrene hollow microballoon is made；It disperses 20 parts of silica solution and 3 parts of polystyrene microspheres in deionized water and heat-insulated guarantor is made Sheath solution；

(4) the first original sheet glass is placed in the hydrochloric acid solution of 10wt% using deionized water, acetone cleaning, drying, 25wt% hydrogen peroxide is added dropwise, water-bath immersion treatment 30min at 60 DEG C is dry after taking-up, and plural gel made from step (1) is applied It is overlying on the first original sheet glass surface, is dried 20min at 80 DEG C；Heat-barrier coating solution made from coating step (3) later, Continue dry 30min at 80 DEG C, the first original sheet glass after drying is placed in sintering furnace, and constant temperature is handled first at 300 DEG C 30min is warming up at 600 DEG C with the heating rate of 10 DEG C/min later, constant temperature handle 1h, after cool to room temperature with the furnace； Finally use magnetron sputtering method spraying silicon nitride coating；

(5) 10 parts of expansible graphites, 0.01 part of cetyl trimethylammonium bromide, 50 parts of deionized waters are mixed and is placed in row Ball-milling treatment 4.5h in planetary ball mill is filtered, dry, finally that 0.8 part of treated expansible graphite and 22 parts is aqueous poly- Urethane, 0.1 part of p-hydroxybenzenyl sulfonate, 30 parts of deionized waters are mixed to prepare dispersion liquid；

(6) by 0.3 part of nano-sheet boron nitride, 18 parts of ptfe emulsions, 0.1 part of silane coupling agent, 1 part of curing agent Polytetrafluoroethylene (PTFE) composite solution A is made；The Fluorinse that mass concentration is 10% is prepared, magnesium chloride solution is then added, instead Answer in kettle and react 5h at 110 DEG C, after filter, solid is dissolved in nitric acid, the aqueous isopropanol of silicon ethyl alcohol is added, stirring is mixed It closes and composite solution B is made；

(7) the second original sheet glass cleaning-drying is placed in the sodium hydroxide solution of 10wt%, 25wt% dioxygen is added dropwise Water, immersion treatment 30min at 50 DEG C, take out it is dry after, the successively dispersion liquid made from its surface coating step (5), at 50 DEG C Composite solution A is coated after drying, continues to coat composite solution B after dry, constant temperature is handled at 500 DEG C in sintering furnace after drying 2h；

(8) 12 parts of silicon rubber, 3 parts of dimethicones, 0.03 part of talcum powder are placed in after blender fills and be stirred, are added 0.005 part of silane coupling agent, 1 part of carbon black continue to be stirred, and adhesive is made；By adhesive be coated on the first original sheet glass and Around second original sheet glass, heat 30min at 300 DEG C, then by the first original sheet glass and the second original sheet glass in vacuum Under the conditions of be combined obtained hollow energy-saving glass fiber.

Through detecting, the limit oxygen index of hollow energy-saving glass fiber produced by the present invention is 49.5% or more, it is seen that light transmission rate For 76.8-80.5%, places it in 10% hydrochloric acid solution and 10% sodium hydroxide solution and impregnate 30h respectively, glass table Layer is unchanged；Hollow energy-saving glass fiber, which is placed in, to be heated on magnetic stirring apparatus, then set the beaker equipped with 50mL deionized water In on hollow energy-saving glass fiber, setting magnetic stirring apparatus to 60 DEG C of heated condition, after 12h, the temperature of deionized water in beaker Variation is only 1-3 DEG C, and heat-proof quality is excellent.

Although specific embodiments of the present invention are described, many other forms of the invention and change Change will be apparent to those skilled in the art.It should be understood that appended claims and the present invention usually cover the present invention very All these apparent forms and change in real spirit and scope.

Claims (9)

1. a kind of hollow energy-saving glass fiber with fire-retardant Low emissivity wear-resisting property, it is characterised in that: the hollow energy-saving glass fiber is It is made of two panels original sheet glass, the specific structure of the vacuum energy-saving glass is the first original sheet glass, is successively coated on the first glass The UV-absorbing layer on glass original piece surface, heat-barrier coating, the first wearing layer, the second original sheet glass and successively it is coated on the Flame retardant coating, the second wearing layer, the porous optical thin films layer on two original sheet glass surfaces；Further include between the two panels original sheet glass Adhesive, adhesive are located at around two panels original sheet glass, form closed cavity between two panels original sheet glass.

2. a kind of hollow energy-saving glass fiber with fire-retardant Low emissivity wear-resisting property according to claim 1, feature exist In: the material of the UV-absorbing layer is the titanium deoxid film layer for mixing yttrium, with a thickness of 15nm.

3. a kind of hollow energy-saving glass fiber with fire-retardant Low emissivity wear-resisting property according to claim 1, feature exist In: the material of the heat-barrier coating is aerosil/polystyrene hollow microballoon composite layer, with a thickness of 5nm.

4. a kind of hollow energy-saving glass fiber with fire-retardant Low emissivity wear-resisting property according to claim 1, feature exist In: the material of first wearing layer is silicon nitride layer, with a thickness of 10nm.

5. a kind of hollow energy-saving glass fiber with fire-retardant Low emissivity wear-resisting property according to claim 1, feature exist In: the material of the flame retardant coating is the polyurethane material of Modified by Expandable Graphite, with a thickness of 10nm.

6. a kind of hollow energy-saving glass fiber with fire-retardant Low emissivity wear-resisting property according to claim 1, feature exist In: the material of second wearing layer is the polytetrafluoroethylene material that nano-sheet nitrogenizes boron modification, with a thickness of 20nm.

7. a kind of hollow energy-saving glass fiber with fire-retardant Low emissivity wear-resisting property according to claim 1, feature exist In: the material of the porous optical thin films layer is magnesium fluoride/silica composite coating, the mass ratio of magnesium fluoride, silica For 1:(3-6), with a thickness of 20nm.

8. a kind of hollow energy-saving glass fiber with fire-retardant Low emissivity wear-resisting property according to claim 1, feature exist In: the material of the adhesive is silicone sealant.

9. a kind of system with fire-retardant, Low emissivity wear-resisting property hollow energy-saving glass fiber according to any one of claims 1 to 8 Preparation Method, which comprises the following steps:

(1) yttrium nitrate aqueous solution for preparing 1.5-4mol/L prepares the ethanol solution of titanium tetrachloride, with titanium, yttrium molar ratio for 1: The ratio of (0.32-0.45) mixes the ethanol solution of yttrium nitrate aqueous solution and titanium tetrachloride, dropwise addition 10wt% hydrochloric acid solution, and 40 DEG C, it is stirred 3h under 3000rpm, then aging 10h at room temperature, plural gel is made；

(2) ethyl orthosilicate is dissolved in ethyl alcohol, deionized water is added, at room temperature stir process 1h under the revolving speed of 1500rpm, so It is placed in reaction kettle, the sodium hydroxide solution of 10wt% is added, seal, at 90 DEG C, react 2-4h, be cooled to after reaction Silica solution is made in room temperature；

(3) 30 parts of styrene monomers, 0.01-0.03 parts of emulsifiers and 8 parts of deionized waters are mixed, 0.02 part of persulfuric acid is added Polystyrene seed emulsion is made in potassium, the polymerization reaction 1h at 60 DEG C；It is dilute that deionized water is added into polystyrene seed emulsion Releasing to solid content is 5%, and 10 parts of benzene divinyls are then added, are stirred 30min, filter, by the solid after filter at 0.001 part It is scattered under the action of neopelex in deionized water and 0.02 part of potassium peroxydisulfate is added, the reaction was continued at 60 DEG C 50min, filtering, the solid after filter are placed in ethyl alcohol and the mixed solution of DMF, stir 1-5h at room temperature, filter, solid is done It is dry, polystyrene hollow microballoon is made；By 20 parts of silica solution and 1-4 parts of polystyrene microspheres be scattered in deionized water be made every Thermal-protective coating solution；

(4) the first original sheet glass is placed in the hydrochloric acid solution of 10wt% using deionized water, acetone cleaning, drying, is added dropwise 25wt% hydrogen peroxide, water-bath immersion treatment 30min at 60 DEG C is dry after taking-up, and plural gel made from step (1) is coated on First original sheet glass surface is dried 20min at 80 DEG C；Heat-barrier coating solution made from coating step (3) later, 80 DEG C Under continue dry 30min, it is dry after the first original sheet glass be placed in sintering furnace, constant temperature handles 30min first at 300 DEG C, Be warming up at 600 DEG C with the heating rate of 10 DEG C/min later, constant temperature handle 1h, after cool to room temperature with the furnace；Finally adopt With magnetron sputtering method spraying silicon nitride coating；

(5) 10 parts of expansible graphites, 0.01 part of cetyl trimethylammonium bromide, 50 parts of deionized waters mixing are placed in planetary Ball-milling treatment 3-5h in ball mill is filtered, dry, finally by 0.3-1 parts of treated expansible graphite and 22 parts of aqueous poly- ammonia Ester, 0.1 part of p-hydroxybenzenyl sulfonate, 30 parts of deionized waters are mixed to prepare dispersion liquid；

(6) by 0.1-0.4 parts of nano-sheet boron nitride, 18 parts of ptfe emulsions, 0.1 part of silane coupling agent, 1 part of curing agent Polytetrafluoroethylene (PTFE) composite solution A is made；The Fluorinse that mass concentration is 10% is prepared, magnesium chloride solution is then added, instead Answer in kettle and react 2-6h at 110 DEG C, after filter, solid is dissolved in nitric acid, be added silicon ethyl alcohol aqueous isopropanol, stirring It is mixed to prepare composite solution B；

(7) the second original sheet glass cleaning-drying is placed in the sodium hydroxide solution of 10wt%, dropwise addition 25wt% hydrogen peroxide, 50 Immersion treatment 30min at DEG C takes out after drying, successively the dispersion liquid made from its surface coating step (5), after dry at 50 DEG C Composite solution A is coated, continues to coat composite solution B after dry, constant temperature handles 2h at 500 DEG C in sintering furnace after drying；

(8) 12 parts of silicon rubber, 3 parts of dimethicones, 0.03 part of talcum powder are placed in after blender fills and be stirred, are added 0.005 part of silane coupling agent, 1 part of carbon black continue to be stirred, and adhesive is made；By adhesive be coated on the first original sheet glass and Around second original sheet glass, heat 30min at 300 DEG C, then by the first original sheet glass and the second original sheet glass in vacuum Under the conditions of be combined obtained hollow energy-saving glass fiber.