CN107012591B - Dry laminating vacuum insulation core material and preparation method thereof - Google Patents

Dry laminating vacuum insulation core material and preparation method thereof Download PDF

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Publication number
CN107012591B
CN107012591B CN201710224522.3A CN201710224522A CN107012591B CN 107012591 B CN107012591 B CN 107012591B CN 201710224522 A CN201710224522 A CN 201710224522A CN 107012591 B CN107012591 B CN 107012591B
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core material
vacuum insulation
dry laminating
ultra
insulation core
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CN107012591A (en
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翟富强
郭茂
秦大江
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XUANHAN ZHENGYUAN MICRO GLASS FIBER Co Ltd
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XUANHAN ZHENGYUAN MICRO GLASS FIBER Co Ltd
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    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/002Inorganic yarns or filaments
    • D04H3/004Glass yarns or filaments
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C13/00Fibre or filament compositions
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Thermal Insulation (AREA)

Abstract

The present invention relates to dry laminating vacuum insulation core materials, by mass percentage, including 1~5wt% of ultra-fine fibre glass 70~80wt% of cotton, 15~25wt% of nanometer grade silica powder and processing aid;The nanometer grade silica diameier is 50~100nm;Na in the ultra-fine fibre glass cotton2O and K2The total content of O is controlled in 11~17wt%.The invention further relates to the preparation methods of dry laminating vacuum insulation core material, and ultra-fine fibre glass cotton and nanometer grade silica powder are combined together, and vacuum insulation core material is prepared using dry method hot pressing, and thermal coefficient is low, and intensity is high, and the service life increases.

Description

Dry laminating vacuum insulation core material and preparation method thereof
Technical field
The invention belongs to functional composite material technical fields, are related to dry laminating vacuum insulation core material and preparation method thereof.
Background technique
Vacuum heat-insulating plate (Vacuum Insulation Panel:VIP) is efficient thermal insulation material of new generation, thermal conductivity coefficient It can be that thermal coefficient is minimum in the world at present down to 2.0mW/ (mK) hereinafter, be equivalent to the 1/10 of traditional material thermal coefficient Heat preserving and insulating material.VIP is widely used in refrigerator, refrigerator-freezer, refrigerating box, freezer, construction wall heat preservation, naval vessels, ship, vapour The fields such as vehicle, electric heater.
The core material component most crucial as vacuum heat-insulating plate VIP, itself is made of porous material, limits residual aqueous vapor The free movement of molecule, and prevent convection current and the heat transfer of gas.Core material in vacuum encapsulation process, as support frame It is able to bear the pressure greater than 98KPa, guarantees barrier film and core material good fit without collapsing.For what is made with fibrous material Vacuum heat-insulating plate VIP core material, the aperture size of core material are collided with each other by molecule and are caused closer to gas molecule mean free path Gas heat transfer with regard to smaller, so the factors such as porosity, fibre diameter and aperture size have codetermined vacuum heat-insulating plate VIP Thermal coefficient.With the extension of use time, the gas adsorbed in core material can release, interior in vacuum heat-insulating plate VIP Pressure can increase to a certain extent, and interior pressure increases with thermal coefficient to have a great impact.For being made with silica Vacuum heat-insulating plate VIP core material can reduce the conduction heat transfer of gas because it is with nano-pore structure feature.
Publication No. CN104747862 has glass fibre sheet and gas phase SiO2It is open in the patent of the VIP core material of layer The intermediate core material that multilayer laminated glass fibre sheet is constituted, the upper surface and/or lower end surface of intermediate core material be covered with gas phase SiO2The periphery of plate or the intermediate core material is coated with gas phase SiO2Bisque.
In the patent of the method for Publication No. CN104628239 dry process core material of vacuum heat insulation plate, disclose a kind of dry The method that method prepares core material of vacuum heat insulation plate.Glass fibre is prepared and collected first, and glass fibre is heated to certain temperature, is applied Add pressure appropriate and maintain fiberglass surfacing after a period of time formed half melt class silica gel compound, this partly melts state Closing object makes glass fiber be cross-linked with each other to overlap and final cooling obtain VIP core material.
It is open in a kind of patent of glass core material of flyash doping of Publication No. CN104291772 and preparation method thereof Blanket of glass wool is made using wet processing, in its surface even application silane coupling agent in drying process, after its solidification, A vibration powder filling machine is placed above glass core material, and fly ash grain is placed wherein, fly ash grain is made to be evenly distributed on core In the hole of material fiber.
In above-mentioned three patent of invention, disclosed vacuum heat-insulating plate VIP core material be sheet fiberglass lamella core material with Powder lamella core material laying is combined, or individually fiberglass plies core material or independent powder lamella core material composition;Wherein institute The fiberglass plies core material stated is prepared in the way of wet process mashing, compared to dry method thermoforming way, wet process Pulping process can destroy fiber, complex forming technology, and energy consumption cost is higher;For powder lamella core material difficult forming, intensity compared with Difference, it is just more difficult especially for nano-scale particle powder compacting, it will cause core material in vacuum and deform, surface is recessed Convex not gentle thermal coefficient increases.Therefore, the composite core material of dry method hot pressing glass fibre and nanometer grade powder how is prepared, It is to prepare ultra-low thermal conductivity vacuum heat-insulating plate VIP urgent problem to be solved.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of surfacing, intensity height and thermal coefficient it is low dry method it is multiple Vacuum insulation core material is closed, the preparation method of the dry laminating vacuum insulation core material is also provided.
In order to achieve the above objectives, the invention provides the following technical scheme:
1, dry laminating vacuum insulation core material, by mass percentage, including following component: ultra-fine fibre glass cotton 70~ 1~5wt% of 80wt%, 15~25wt% of nanometer grade silica powder and processing aid;The ultra-fine fibre glass cotton presses matter Percentages are measured, it is composed of the following components: SiO2: 58.5~65wt%;Na2O:10.5~16wt%;K2O:0.5~3wt%; Al2O3: 2.4~7wt%;MgO:1~4.5wt%;CaO:3~7.5wt%;B2O3: 6~8wt%;Fe2O3: 0.05~ 0.2wt%;ZnO:0~2wt%;BaO:0.5~3.5wt%.
Further, the nanometer grade silica diameier is 50~100nm.
Further, Na in the ultra-fine fibre glass cotton2O and K2The total content of O is controlled in 11~17wt%.
Further, the nanometer grade silica powder selects fumed silica, precipitated silica or aeroge two One or more of silica.
Further, the processing aid selects KH792, KH550, KH560 silane coupling agent, NDZ-101 or NDZ-311 titanium One or more of acid esters coupling agent.
2, the preparation method of dry laminating vacuum insulation core material, includes the following steps:
(1) quartz sand, soda ash, potassium feldspar, albite, calcite, boron are chosen according to ultra-fine fibre glass cotton constituent Sand, dolomite, barium carbonate and zinc oxide uniformly mix and are smelted into the transparent glass metal of free from admixture;
(2) glass metal throws away ultra-fine fibre glass by high-speed rotating centrifugal pan;
(3) the nanometer grade silica powder uniform atomizing for being blended with processing aid is sprayed on ultra-fine fibre glass table Face is drawn onto formation dry laminating ultra-fine fibre glass cotton in cotton collecting machine by negative pressure induced wind;
(4) by dry laminating ultra-fine fibre glass cotton obtained through excess temperature be 550~650 DEG C curing oven hot pressing 3~ 10min obtains dry laminating vacuum insulation core material.
Further, 95% normal distribution of diameter of the ultra-fine fibre glass is at 2.5~4 μm, the ultra-fine fibre glass 90% normal distribution of length in 15~30mm.
Further, in 15~35mm, density domination exists the thickness control of step (4) the dry laminating vacuum insulation core material 150~300Kg/m3
Further, the injection pressure control that uniform atomizing is sprayed in step (3) is in 0.3~0.5Mpa, injection flow control In 150~250Kg/h.
The beneficial effects of the present invention are: ultra-fine fibre glass cotton chemical component neutral and alkali metal Na of the present invention2O+ K2O content control can effectively improve the comprehensive mechanical property of fiber in 11~17wt%, reduce thermal coefficient;Superfine glass is fine B in dimension2O3Content is 6~8wt%, can effectively reduce thermal coefficient;The all normal state of ultra-fine fibre glass diameter 95% prepared point At 2.5~4 μm, all normal distributions of fibre length 90% are controlled in 15~30mm, core thickness in 15~35mm, density domination cloth In 150~300Kg/m3, can effectively reduce the thermal coefficient for preparing dry laminating vacuum insulation core material.The present invention is by thermally conductive system The low-down ultra-fine fibre glass cottons of number and nanometer grade silica powder are effectively combined together, and using dry method hot pressing come Vacuum insulation core material is prepared, destruction of traditional wet process mashing to fiber, the dry laminating vacuum insulation core prepared have been broken Material service life greatly increases, compound using nanometer grade silica and ultra-fine fibre glass cotton, prepares by dry method hot pressing Composite evacuated insulation core material, the single material core material standby compared to other dry method hot pressings, thermal coefficient is lower, and intensity is high, Longer life expectancy;Compared to the core material of wet process mashing preparation, preparation process does not destroy fiber, and moulding process is simple, energy consumption cost It is low, while realizing effective addition of nano silica.The dry laminating vacuum insulation core material surface that the present invention prepares is flat Whole, intensity height and thermal coefficient are low, be highly suitable for refrigerator, refrigerator-freezer, refrigerating box, freezer, construction wall heat preservation, naval vessels, ship, The fields such as automobile, electric heater.
Specific embodiment
Below by a preferred embodiment of the present invention will be described in detail.
Embodiment 1
By weight choose 23.5 parts of quartz sands, 11 parts of soda ash, 4.5 parts of potassium feldspars, 5.5 albites, 2.5 parts of calcites, 8.5 boraxs, 6 dolomites, 1.5 parts of barium carbonates and 1 part of zinc oxide put into kiln calcining after evenly mixing, and it is uniform to melt ingredient out The transparent glass metal of free from admixture;Then glass metal throws away ultra-fine fibre glass by high-speed rotating centrifugal pan, and for preparing is super The all normal distributions of thin glass fiber diameter 95% are at 2.5~3 μm, and all normal distributions of fibre length 90% are in 20~30mm;It will mix Conjunction has the nano grade gas phase silicon dioxide powder uniform atomizing of content 1%KH560 silane coupling agent to be sprayed on ultra-fine fibre glass Surface, wherein injection pressure control is controlled in 0.4Mpa, injection flow in 200Kg/h;Then cotton collecting machine is drawn by negative pressure induced wind Interior formation dry laminating ultra-fine fibre glass cotton;It is finally 600 through excess temperature by dry laminating ultra-fine fibre glass cotton obtained DEG C solidification 8min;
Through detecting dry laminating vacuum insulation core material thickness 15mm, density 245Kg/m3, core material compression ratio 18% measures and leads For hot coefficient compared with other vacuum insulation core materials, concrete outcome is as follows:
It can be seen that the thermal coefficient for the dry laminating vacuum insulation core material prepared will be lower than single dry method glass Glass fiber core material and silica lamella fiberglass plies core material, while being also less than wet glass fibers core material.
Embodiment 2
By weight selection 26.5 parts of quartz sands, 12 parts of soda ash, 4 parts of potassium feldspars, 6 albites, 3 parts of calcites, 7.5 boron Sand, 6 dolomites, 2 parts of barium carbonates and 1.5 parts of zinc oxide put into kiln calcining after evenly mixing, and it is uniform without miscellaneous to melt ingredient out The transparent glass metal of matter;Then glass metal throws away ultra-fine fibre glass by high-speed rotating centrifugal pan, the ultra-fine glass prepared The all normal distributions of glass fibre diameter 95% are at 2.5~3 μm, and all normal distributions of fibre length 90% are in 15~25mm;It is blended with The nanometer grade silica aerogel powder uniform atomizing of content 3%KH792 silane coupling agent is sprayed on ultra-fine fibre glass table Face, wherein injection pressure control is controlled in 0.5Mpa, injection flow in 250Kg/h;Then it is drawn onto cotton collecting machine by negative pressure induced wind Form dry laminating ultra-fine fibre glass cotton;It is finally 630 DEG C through excess temperature by dry laminating ultra-fine fibre glass cotton obtained Solidification 5min;
Through detecting dry laminating vacuum insulation core material thickness 17mm, density 255Kg/m3, core material compression ratio 20% measures and leads For hot coefficient compared with other vacuum insulation core materials, concrete outcome is as follows:
It can be seen that the dry laminating vacuum insulation formed by nano silica and ultra-fine fibre glass cotton hot pressing The thermal coefficient of core material will be lower than single dry method glass fiber core material, while also be less than wet glass fibers core material.It proves The dry laminating vacuum insulation core material that the present invention prepares has the features such as at low cost, thermal coefficient is low.Therefore, in refrigerator, ice The fields such as cabinet, refrigerating box, freezer, construction wall heat preservation have a vast market foreground.
Finally, it is stated that preferred embodiment above is only used to illustrate the technical scheme of the present invention and not to limit it, although logical It crosses above preferred embodiment the present invention is described in detail, however, those skilled in the art should understand that, can be Various changes are made to it in form and in details, without departing from claims of the present invention limited range.

Claims (8)

1. dry laminating vacuum insulation core material, which is characterized in that by mass percentage, including following component: superfine glass is fine 1 ~ 5 wt% of 70 ~ 80 wt% of vinylon and cotton blend, 15 ~ 25 wt% of nanometer grade silica powder and processing aid;The ultra-fine fibre glass cotton By mass percentage, composed of the following components: SiO2: 58.5 ~ 65 wt%;Na2The wt% of O:10.5 ~ 16;K2O:0.5 ~ 3 wt%;Al2O3: 2.4 ~ 7 wt%;The wt% of MgO:1 ~ 4.5;The wt% of CaO:3 ~ 7.5;B2O3: 6 ~ 8 wt%;Fe2O3: 0.05 ~ 0.2 wt%;The wt% of ZnO:0 ~ 2;The wt% of BaO:0.5 ~ 3.5;The nanometer grade silica diameier is 50 ~ 100nm.
2. dry laminating vacuum insulation core material as described in claim 1, which is characterized in that in the ultra-fine fibre glass cotton Na2O and K2The total content of O is controlled in 11~17 wt %.
3. dry laminating vacuum insulation core material as described in claim 1, which is characterized in that the nanometer grade silica powder Select one or more of fumed silica, precipitated silica or aeroge silica.
4. dry laminating vacuum insulation core material as described in claim 1, which is characterized in that the processing aid selection KH792, One or more of KH550, KH560 silane coupling agent, NDZ-101 or NDZ-311 titanate coupling agent.
5. the preparation method of any dry laminating vacuum insulation core material of claim 1-4, which is characterized in that including as follows Step:
(1) quartz sand, soda ash, potassium feldspar, albite, calcite, borax, white is chosen according to ultra-fine fibre glass cotton constituent Marble, barium carbonate and zinc oxide uniformly mix and are smelted into the transparent glass metal of free from admixture;
(2) glass metal throws away ultra-fine fibre glass by high-speed rotating centrifugal pan;
(3) the nanometer grade silica powder uniform atomizing for being blended with processing aid is sprayed on ultra-fine fibre glass surface, leads to It crosses negative pressure induced wind and is drawn onto formation dry laminating ultra-fine fibre glass cotton in cotton collecting machine;
(4) the curing oven 3 ~ 10min of hot pressing for being 550 ~ 650 DEG C through excess temperature by dry laminating ultra-fine fibre glass cotton obtained, Obtain dry laminating vacuum insulation core material.
6. the preparation method of dry laminating vacuum insulation core material as claimed in claim 5, which is characterized in that the superfine glass 95% normal distribution of diameter of fiber is at 2.5~4 μm, and 90% normal distribution of length of the ultra-fine fibre glass is in 15~30mm.
7. the preparation method of dry laminating vacuum insulation core material as claimed in claim 5, which is characterized in that step (4) is described Dry laminating vacuum insulation core material thickness control is in 15 ~ 35mm, and density domination is in 150 ~ 300Kg/m3.
8. the preparation method of dry laminating vacuum insulation core material as claimed in claim 5, which is characterized in that in step (3) In 0.3 ~ 0.5Mpa, injection flow is controlled in 150 ~ 250Kg/h for the injection pressure control of even atomized spray.
CN201710224522.3A 2017-04-07 2017-04-07 Dry laminating vacuum insulation core material and preparation method thereof Active CN107012591B (en)

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CN107512851A (en) * 2017-08-31 2017-12-26 宣汉正原微玻纤有限公司 A kind of high-specific surface area AGM dividing plates modified superfine glass fibre cotton and preparation method thereof
CN107639920A (en) * 2017-09-20 2018-01-30 宣汉正原微玻纤有限公司 A kind of compound dry method hot pressing core material of vacuum heat insulation plate of low thermal conductivity and preparation method thereof
CN107558289B (en) * 2017-09-20 2019-01-11 宣汉正原微玻纤有限公司 A kind of high intensity low thermal conductivity ultra-fine fibre glass cotton dry method hot pressing core material and preparation method thereof
CN108101374A (en) * 2017-12-08 2018-06-01 重庆纤维研究设计院股份有限公司 A kind of environmentally friendly low thermal conductivity ultra-fine fibre glass spraying cotton particle for building and preparation method thereof
CN108468907A (en) * 2018-04-20 2018-08-31 宿迁南航新材料与装备制造研究院有限公司 A kind of vacuum heat-insulating plate and preparation method thereof of fiber reinforcement nano-powder material
CN109249507A (en) * 2018-09-27 2019-01-22 佛山齐安建筑科技有限公司 A kind of preparation method of core material of vacuum heat insulation plate
CN111893652A (en) * 2019-05-05 2020-11-06 南京和润隆环保科技有限公司 Preparation method of storage tank ceiling cold insulation glass cotton felt
CN110159873A (en) * 2019-06-06 2019-08-23 四川迈科隆真空新材料有限公司 A kind of vacuum heat-insulating plate and preparation method thereof
CN110845145A (en) * 2019-07-01 2020-02-28 重庆文理学院 Composite heat-resistant material for automobile engine heat shield and preparation method thereof
CN110846927A (en) * 2019-07-01 2020-02-28 重庆文理学院 Hydrophobic oleophylic modified superfine glass fiber cotton for oil product purification filter membrane and preparation method thereof
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CN111268995A (en) * 2019-11-19 2020-06-12 重庆文理学院 Honeycomb nano-pore structure composite heat insulation material and preparation method thereof
CN112032475A (en) * 2020-09-03 2020-12-04 盱眙润新材料技术服务中心 Core material for dry-process vacuum insulation panel and preparation method thereof

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