CN112979222B - Attapulgite composite glass fiber core material and preparation method thereof - Google Patents
Attapulgite composite glass fiber core material and preparation method thereof Download PDFInfo
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- CN112979222B CN112979222B CN201911425576.1A CN201911425576A CN112979222B CN 112979222 B CN112979222 B CN 112979222B CN 201911425576 A CN201911425576 A CN 201911425576A CN 112979222 B CN112979222 B CN 112979222B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/24—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
- C04B28/26—Silicates of the alkali metals
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/30—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values
- C04B2201/32—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values for the thermal conductivity, e.g. K-factors
Abstract
The invention discloses an attapulgite composite glass fiber core material and a preparation method thereof, wherein the core material adopts glass fiber as a matrix, and accounts for 60-78% by mass. Between the glass fiber pores, 15-25% of bird nest shaped nano rod crystal attapulgite, 5-10% of layer chain shaped attapulgite aerogel and 2-5% of binder are doped. The composite core material can effectively utilize the bird nest-shaped microstructure of the nano-rod crystal attapulgite and the layer chain-shaped nanofiber structure of the attapulgite aerogel, and optimize the micron-based microstructure of the glass fiber core material. Through the regulation and control of the microstructure pore grading and the pore size of the glass fiber core material, the structural stability and the heat insulation performance are improved, the air pressure sensitivity is reduced, and the service life of the vacuum heat insulation plate is prolonged. In addition, the excellent performances of corrosion resistance, high temperature resistance, environmental protection and the like of the nano-rod crystal attapulgite enable the composite core material to be used at a higher temperature.
Description
Technical Field
The invention relates to a glass fiber and a preparation method thereof, in particular to an attapulgite composite glass fiber core material and a preparation method thereof.
Background
Attapulgite, also known as palygorskite, is an aqueous magnesium-rich silicate mineral, the ideal chemical formula of which is: mg (magnesium)5Si8O20(HO)2(OH2)4·4H2And O. The attapulgite is a fibrous porous crystal, and is widely applied to the fields of chemical industry, textile, building materials, environmental protection and the like due to good adsorption, purification, bonding, decoloration and the like. The attapulgite in China has abundant mineral resources and excellent performance. With the improvement of the use requirement, natural attapulgite is gradually replaced by nano-rod crystal attapulgite due to the defects of more impurities, scattered structure and the like. The nano-rod crystal attapulgite has excellent performances in the aspects of corrosion resistance, high temperature resistance, insulation, heat insulation, environmental protection and the like. Most of the natural nano-rod crystal attapulgite is gathered in a nest shape or a hackle shape. The nest-shaped or hack-shaped attapulgite has the characteristics of high structural stability, low thermal conductivity and the like. In addition, the nano-rod crystal attapulgite is compounded with the high polymer uniformlyThe suspension is prepared into the aerogel material by a certain drying technology, the internal structure of the aerogel material is changed from the original rod-shaped nanocrystal into a layer chain shape containing a large number of loose pore canals and even a three-dimensional fiber network structure which are formed by mutually connecting nano skeletons, the heat transfer and the heat convection transfer are seriously hindered, the aerogel material has extremely low heat conductivity, shows excellent heat insulation and has wide application prospect.
Along with the proposal of the energy law in China, the importance of building energy conservation is increasingly highlighted. Vacuum insulation panels have attracted much attention as a new and efficient thermal insulation material. The traditional vacuum insulation panel generally adopts glass fiber as a core material, the core material has the advantages of good heat insulation performance, small thickness and the like, but the core material cannot block gas diffusion due to large pores among the glass fiber, and the vacuum insulation panel can lose effectiveness due to the rise of the heat conductivity coefficient as long as a small amount of gas is permeated.
The invention discloses an environment-friendly vacuum insulation panel, which is disclosed by the Chinese patent with the application number of 201710505291.3 and has the advantages that glass fibers with low thermal conductivity are selected as main materials of a core material, diatomite and attapulgite are added to increase the plasticity of the core material, and the core material is convenient to press and form. In addition, when the glass fiber cotton is mixed with powder such as diatomite, attapulgite and the like, the heat conduction in the material can be greatly reduced. However, the invention only optimizes the tiny pores on the surface layer of the glass fiber, and when a small amount of gas permeates into the glass fiber, the thermal conductivity coefficient caused by gas thermal diffusion is obviously increased, so that the vacuum insulation panel can be failed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an attapulgite composite glass fiber core material and a preparation method thereof.
The scheme adopted for achieving the purpose of the invention is as follows: an attapulgite composite glass fiber core material. Comprises 60 to 78 mass percent of glass fiber, 15 to 25 mass percent of nano-rod crystal attapulgite, 5 to 10 mass percent of attapulgite aerogel and 2 to 5 mass percent of binder. On one hand, the heat insulation effect of the core material can be greatly improved by utilizing the glass fiber with low heat conductivity; on the other hand, by utilizing the bird nest-shaped structure of the nano-rod crystal attapulgite, the core material can be stressed more uniformly when bearing external force, so that the core material is kept stable. In addition, the attapulgite aerogel with a layer chain-shaped nanofiber structure is added, so that the heat conduction resistance of the core material is improved. The core material realizes the regulation and control of microstructure pore grading and pore size, and if the core material is applied to a vacuum insulation panel, the structural stability and the heat insulation performance of the vacuum insulation panel can be obviously improved, meanwhile, the air pressure sensitivity of the vacuum insulation panel can be greatly reduced, and the service life of the vacuum insulation panel can be prolonged.
On the basis of the technical scheme, the invention can be further improved as follows.
The glass fiber in the attapulgite composite glass fiber core material is high-alkali glass fiber, the average diameter of the glass fiber is 8-12 mu m, and the length of the glass fiber is 10-20 mm.
The nanorod crystal attapulgite is natural particles of attapulgite gathered in a nest shape or a hackle shape, the particle diameter is 50-70 mu m, the nanorod crystal diameter is 20-70 nm, and the length is 1-5 mu m.
The attapulgite aerogel is nanofiber gathered in a layer chain shape, and the diameter of the nanofiber is 50-70 mu m.
The binder is silicon oxide or sodium silicate.
The invention also provides a technical scheme for solving the technical problems as follows: a preparation method of an attapulgite composite glass fiber core material comprises the following preparation steps:
(1) mixing the nano-rod crystal attapulgite with polyacrylamide by adding water, and preparing uniform attapulgite suspension after ultrasonic treatment and stirring;
(2) tetraethyl orthosilicate, aluminum chloride and boric acid are uniformly mixed in water to prepare Al-B-Si sol with the molar ratio of Al/B/Si being (2.0-2.2) to 5: 1;
(3) adding the Al-B-Si sol into the attapulgite suspension, uniformly stirring to obtain a dispersion, degassing the dispersion in a vacuum chamber, transferring the dispersion into a mold, and removing impurities by freezing and calcining to obtain attapulgite aerogel with a layer chain structure;
(4) dispersing and stirring the attapulgite aerogel obtained in the step (3), the nanorod crystal attapulgite, the glass fiber and the binder in an acidic aqueous solution environment to obtain uniformly mixed composite core material slurry;
(5) feeding the composite core material slurry into a front net box, and dehydrating and forming the slurry by using a forming net to form a composite cotton felt blank;
(6) and (3) after the negative pressure dewatering of the composite cotton felt, sending the composite cotton felt into a baking oven for drying and curing, and cooling and cutting to obtain the attapulgite composite glass fiber core material.
The invention has the beneficial effects that: (1) the nano-rod crystal attapulgite has excellent performances of corrosion resistance, high temperature resistance, insulation, heat insulation, environmental protection and the like, and the corrosion resistance, the high temperature resistance and the heat insulation performance of the glass fiber core material can be improved by compounding the nano-rod crystal attapulgite, so that the application range of the glass fiber core material is expanded, and the nano-rod crystal attapulgite has an environmental protection significance; (2) the nano-rod crystal attapulgite and the attapulgite aerogel are added into the glass fiber, so that the micro-structure pore grading (both micron-scale pores and nanometer-scale pores) and the micro-structure pore size regulation can be realized. The method fully utilizes the nest-shaped pore structure of the nano-rod crystal attapulgite, the layer chain-shaped structure of the attapulgite aerogel and the nano pores thereof, optimizes the pore distribution, reduces the heat conductivity, and simultaneously improves the air pressure sensitivity of the glass fiber, thereby improving the critical internal pressure and prolonging the service life of the vacuum heat-insulating plate; (3) the bird nest-shaped structure has the advantages of low structural stability and thermal conductivity and the like, and the bird nest-shaped nanorod crystal attapulgite is fully utilized by the method to prepare the composite core material with high structural stability and low rebound rate; (4) the method has the advantages of abundant attapulgite mineral resources, low price and high cost.
Drawings
FIG. 1 is a schematic view of an attapulgite composite fiberglass core;
in the figure, 1 is glass fiber, 2 is bird nest shaped nano rod crystal attapulgite, and 3 is layer chain shaped attapulgite aerogel.
Detailed Description
The present invention is further illustrated by the following examples, which are intended to be purely exemplary and are not intended to limit the scope of the invention, as various equivalent modifications of the invention will occur to those skilled in the art upon reading the present specification and which fall within the limits of the appended claims.
Example 1
Referring to fig. 1, be the fine core of compound glass of attapulgite, 1 is glass fiber, and 2 are bird's nest form nanorod crystal attapulgite, and 3 are layer chain form attapulgite aerogel, its characterized in that: the glass fiber reinforced plastic composite material comprises core material fibers, bonding agents, nanorod crystal attapulgite and attapulgite aerogel, wherein the spaces among the glass fiber are doped with the nanorod crystal attapulgite and the attapulgite aerogel, and the glass fiber reinforced plastic composite material comprises 70% of glass fibers, 25% of nanorod crystal attapulgite, 3% of attapulgite aerogel and 2% of sodium silicate according to mass percentage. The specific process in the preparation is as follows:
(1) mixing the nano-rod crystal attapulgite with polyacrylamide by adding water, and preparing uniform attapulgite suspension after ultrasonic treatment and stirring;
(2) tetraethyl orthosilicate, aluminum chloride and boric acid are uniformly mixed in water to prepare Al-B-Si sol with the molar ratio of Al/Si/B being 2: 5: 1;
(3) adding the Al-B-Si sol into the attapulgite suspension, uniformly stirring to obtain a dispersion, degassing the dispersion in a vacuum chamber, transferring the dispersion into a mold, and performing dry ice/acetone bath freezing treatment to obtain an attapulgite aerogel precursor. Calcining the aerogel precursor in flowing air at high temperature to remove polyacrylamide to generate attapulgite aerogel with a layer chain structure;
(4) putting the attapulgite aerogel prepared in the step (3), the nanorod crystal attapulgite, the glass fiber and the sodium silicate into a slurry mixing pool, adding concentrated sulfuric acid, and stirring to obtain uniform composite core material slurry;
(5) feeding the composite core material slurry into a front net box, and dehydrating and forming the slurry by using a forming net to form a composite cotton felt blank;
(6) removing water from the composite cotton felt blank under negative pressure to remove 70% of water in the blank; sending the composite cotton felt blank with the water removed into a baking oven for drying and curing, wherein the baking temperature is 350 ℃, and the baking time is 30 min; and after the glass fiber core material is cooled to normal temperature, cutting according to the use requirement to obtain the attapulgite composite glass fiber core material.
The air pressure sensitivity of the attapulgite composite glass fiber core material prepared by the embodiment is reduced to 300Pa from 100Pa, the heat conductivity coefficient is less than 0.003W/(m.K), the tolerance temperature is increased by 30 ℃, and the attapulgite composite glass fiber core material has important application value in the field of building energy conservation.
Example 2
Referring to fig. 1, be the fine core of compound glass of attapulgite, 1 is glass fiber, and 2 are bird's nest form nanorod crystal attapulgite, and 3 are layer chain form attapulgite aerogel, its characterized in that: the glass fiber reinforced plastic composite material comprises 65% of glass fiber, 25% of nano-rod crystal attapulgite, 5% of attapulgite aerogel and 5% of sodium silicate by mass percentage. The specific process in the preparation is as follows:
(1) mixing the nano-rod crystal attapulgite with polyacrylamide by adding water, and preparing uniform attapulgite suspension after ultrasonic treatment and stirring;
(2) tetraethyl orthosilicate, aluminum chloride and boric acid are uniformly mixed in water to prepare Al-B-Si sol with the molar ratio of Al/Si/B being 2: 5: 1;
(3) adding the Al-B-Si sol into the attapulgite suspension, uniformly stirring to obtain a dispersion, degassing the dispersion in a vacuum chamber, transferring the dispersion into a mold, and performing dry ice/acetone bath freezing treatment to obtain an attapulgite aerogel precursor. Calcining the aerogel precursor in flowing air at high temperature to remove polyacrylamide to generate attapulgite aerogel with a layer chain structure;
(4) putting the attapulgite aerogel prepared in the step (3), the nanorod crystal attapulgite, the glass fiber and the sodium silicate into a slurry mixing pool, adding concentrated sulfuric acid, and stirring to obtain uniform composite core material slurry;
(5) feeding the composite core material slurry into a front net box, and dehydrating and forming the slurry by using a forming net to form a composite cotton felt blank;
(6) removing water from the composite cotton felt blank under negative pressure to remove 70% of water in the blank; sending the composite cotton felt blank with the water removed into a baking oven for drying and curing, wherein the baking temperature is 350 ℃, and the baking time is 30 min; and after the glass fiber core material is cooled to normal temperature, cutting according to the use requirement to obtain the attapulgite composite glass fiber core material.
The air pressure sensitivity of the attapulgite composite glass fiber core material prepared by the embodiment is reduced from 100Pa to 350Pa, the heat conductivity coefficient is less than 0.003W/(m.K), the tolerance temperature is increased by 40 ℃, and the attapulgite composite glass fiber core material has important application value in the field of building energy conservation.
The above description is only an embodiment of the present invention, but the design concept of the present invention is not limited thereto, and any insubstantial modifications made by using the design concept should fall within the scope of infringing the protection of the present invention. However, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (1)
1. The utility model provides a fine core of compound glass of attapulgite which characterized in that: the core material fibers are provided with a binder, the glass fiber pores are doped with nano-rod crystal attapulgite and attapulgite aerogel, and the glass fiber pores comprise 60-78% of glass fibers, 15-25% of nano-rod crystal attapulgite, 5-10% of attapulgite aerogel and 2-5% of binder according to mass percentage; the glass fiber is high-alkali glass fiber, the diameter is 8-12 mu m, and the length is 10-20 mm; the nano-rod crystal attapulgite is natural particles of attapulgite aggregated in a nest shape or a hackle shape, the particle diameter is 50-70 mu m, the nano-rod crystal diameter is 20-70 nm, and the length is 1-5 mu m; the attapulgite aerogel is nanofiber gathered in a layer chain shape, and the diameter of the nanofiber is 50-70 mu m; the binder is silicon oxide or sodium silicate;
the preparation method of the attapulgite composite glass fiber core material comprises the following steps:
(1) mixing the nano-rod crystal attapulgite with polyacrylamide by adding water, and preparing uniform attapulgite suspension after ultrasonic treatment and stirring;
(2) tetraethyl orthosilicate, aluminum chloride and boric acid are uniformly mixed in water to prepare Al-B-Si sol with the molar ratio of Al/B/Si being (2.0-2.2) to 5: 1;
(3) adding the Al-B-Si sol into the attapulgite suspension, uniformly stirring to obtain a dispersion, degassing the dispersion in a vacuum chamber, transferring the dispersion into a mold, and removing impurities by freezing and calcining to obtain attapulgite aerogel with a layer chain structure;
(4) dispersing and stirring the attapulgite aerogel obtained in the step (3), the nanorod crystal attapulgite, the glass fiber and the binder in an acidic aqueous solution environment to obtain uniformly mixed composite core material slurry;
(5) feeding the composite core material slurry into a front net box, and dehydrating and forming the slurry by using a forming net to form a composite cotton felt blank;
(6) and (3) after the negative pressure dewatering of the composite cotton felt, sending the composite cotton felt into a baking oven for drying and curing, and cooling and cutting to obtain the attapulgite composite glass fiber core material.
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| CN101628804A (en) * | 2008-07-18 | 2010-01-20 | 山东鲁阳股份有限公司 | Aerogel heat insulation composite material and preparation method thereof |
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| CN107387944A (en) * | 2017-06-28 | 2017-11-24 | 高彦峰 | A kind of environment-friendly type vacuum insulation panel |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20190002356A1 (en) * | 2015-07-15 | 2019-01-03 | Neha Yeshwanta HEBALKAR | Improved process for producing silica aerogel thermal insulation product with increased efficiency |
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|---|---|---|---|---|
| CN101628804A (en) * | 2008-07-18 | 2010-01-20 | 山东鲁阳股份有限公司 | Aerogel heat insulation composite material and preparation method thereof |
| CN104370516A (en) * | 2013-08-12 | 2015-02-25 | 苏州维艾普新材料股份有限公司 | Core material prepared by mixing glass fibers and silicon dioxide aerogel and preparation method thereof |
| CN104291772A (en) * | 2014-08-12 | 2015-01-21 | 南京航空航天大学 | Fly ash doped glass fiber core material and preparation method thereof |
| CN107387944A (en) * | 2017-06-28 | 2017-11-24 | 高彦峰 | A kind of environment-friendly type vacuum insulation panel |
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