CN111910467B - Barium sulfate fiber inorganic refractory paper and preparation method and application thereof - Google Patents

Barium sulfate fiber inorganic refractory paper and preparation method and application thereof Download PDF

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CN111910467B
CN111910467B CN202010705522.7A CN202010705522A CN111910467B CN 111910467 B CN111910467 B CN 111910467B CN 202010705522 A CN202010705522 A CN 202010705522A CN 111910467 B CN111910467 B CN 111910467B
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barium sulfate
fiber
inorganic
paper
fibers
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CN111910467A (en
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朱英杰
吴进
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Shanghai Institute of Ceramics of CAS
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Shanghai Institute of Ceramics of CAS
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/36—Inorganic fibres or flakes
    • D21H13/38—Inorganic fibres or flakes siliceous
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/36—Inorganic fibres or flakes
    • D21H13/38—Inorganic fibres or flakes siliceous
    • D21H13/40—Inorganic fibres or flakes siliceous vitreous, e.g. mineral wool, glass fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/36—Inorganic fibres or flakes
    • D21H13/46—Non-siliceous fibres, e.g. from metal oxides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/36—Inorganic fibres or flakes
    • D21H13/46—Non-siliceous fibres, e.g. from metal oxides
    • D21H13/50—Carbon fibres

Abstract

The invention discloses barium sulfate fiber inorganic refractory paper and a preparation method and application thereof. The barium sulfate fiber inorganic refractory paper is a composite porous reticular structure formed by barium sulfate fibers with the length of more than 5 microns and the diameter of 0.1-5 microns and inorganic reinforcing fibers which are inserted in the barium sulfate fibers and have the diameter of 0.02-20 microns and the length of 0.1-12 millimeters, and inorganic adhesive is filled in pores of the composite porous reticular structure; the barium sulfate fiber is formed by assembling barium sulfate nano rods with the diameter of 5-100 nanometers and the length of 50-500 nanometers in parallel along the length direction.

Description

Barium sulfate fiber inorganic refractory paper and preparation method and application thereof
Technical Field
The invention belongs to the field of special inorganic refractory paper, and particularly relates to strong acid and strong alkali resistant inorganic refractory paper prepared by taking barium sulfate fiber as a raw material, and a preparation method and application thereof.
Background
Compared with traditional inorganic fiber products of cloth, felt, blanket and other types, the hydroxyapatite ultralong nanowire-based inorganic fireproof paper has the advantages that the surface is fine and compact, the hydroxyapatite ultralong nanowire-based inorganic fireproof paper has a nanometer porous structure, the thickness can be as thin as tens of micrometers, the hydroxyapatite ultralong nanowire-based inorganic fireproof paper can be used for writing and printing, high temperature resistance, fire resistance and heat insulation requirements can be met, and the hydroxyapatite ultralong nanowire-based inorganic fireproof paper has a good application prospect in the fields of high temperature resistant label paper, high temperature resistant battery diaphragms, light/cable fire-resistant heat insulation wrapping belts and the like for steel plants, nuclear power plants. However, there are applications where corrosion resistance of fire-resistant paper is required, such as high temperature resistant label paper which may involve an acid corrosive atmosphere, and high temperature resistant battery separator which may be used in an acidic environment. The traditional alumina silicate ceramic fiber paper has rough surface and low mechanical strength, and alumina silicate fiber is listed in a high attention substance list by the European Union chemical administration and is gradually limited to be used in the future. The patent number ZL201611095798.8 relates to a novel inorganic refractory paper prepared by taking hydroxyapatite super-long nanowires as raw materials, and a preparation method and application thereof. However, although the hydroxyapatite ultra-long nanowire-based refractory paper can resist strong alkali, the acid resistance of the hydroxyapatite ultra-long nanowire-based refractory paper is not ideal, so that the application of the hydroxyapatite ultra-long nanowire-based inorganic refractory paper in the field of acid corrosion resistance is limited.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide barium sulfate fiber inorganic refractory paper and a preparation method and application thereof. The barium sulfate fiber inorganic refractory paper has high mechanical strength, compact and flat surface, no toxicity and odor of barium sulfate as a main component, stable chemical property, insolubility in strong acid and strong alkali, and excellent high temperature resistance and fire resistance (the melting point is about 1580 ℃, and the decomposition temperature is about 1400 ℃).
In a first aspect, the invention provides a barium sulfate fiber inorganic fire-resistant paper, which is a composite porous reticular structure formed by barium sulfate fibers with the length of more than 5 microns and the diameter of 0.1-5 microns and inorganic reinforcing fibers with the diameter of 0.02-20 microns and the length of 0.1-12 mm, wherein inorganic adhesive is filled in pores of the composite porous reticular structure; the barium sulfate fiber is formed by assembling barium sulfate nano rods with the diameter of 5-100 nanometers and the length of 50-500 nanometers in parallel along the length direction.
The barium sulfate fiber inorganic refractory paper has a layered structure, and the inorganic reinforcing fibers are inserted into the layered structure to form a composite structure similar to 'steel bar-concrete', so that the barium sulfate fiber inorganic refractory paper has good mechanical strength. Different from the Chinese patent 'an inorganic refractory paper and the preparation method and application thereof' (patent number: ZL201611095798.8), the 'reinforced bar-concrete' layered composite structure is a porous reticular structure formed by interweaving barium sulfate fiber capable of resisting strong acid and inorganic reinforcing fiber. Therefore, the barium sulfate fiber inorganic refractory paper prepared by the method can resist strong acid, can be used in a strong acid environment, and can greatly expand the application field and range of the barium sulfate fiber inorganic refractory paper; the hydroxyapatite ultra-long nanowire inorganic refractory paper provided by the patent is not resistant to strong acid, can be quickly dissolved in the strong acid, and cannot be applied to a strong acid environment.
The invention firstly compounds the barium sulfate fiber and the inorganic reinforcing fiber internationally to obtain the barium sulfate fiber inorganic fire-resistant paper. The barium sulfate fiber is formed by assembling barium sulfate nanorods with the diameter of 5-100 nanometers and the length of 50-500 nanometers in parallel along the length direction, the length of the barium sulfate fiber is more than 5 micrometers, the diameter of the barium sulfate fiber is 0.1-5 micrometers, and the unique assembly structure of the barium sulfate fiber enables the barium sulfate fiber to have good flexibility and can be used for preparing flexible inorganic refractory paper capable of resisting strong acid.
In addition, the barium sulfate fiber refractory paper prepared from the single component of the barium sulfate fiber has low mechanical strength, and the application of the barium sulfate fiber refractory paper is limited. In order to improve the mechanical strength of the barium sulfate fiber fire-resistant paper, the invention adopts the barium sulfate fiber and the inorganic reinforcing fiber to compound and adds the inorganic adhesive to prepare the barium sulfate fiber inorganic fire-resistant paper, which can obviously improve the mechanical property of the fire-resistant paper and effectively solve the problem of low mechanical strength of the single-component barium sulfate fiber fire-resistant paper.
Preferably, the barium sulfate fiber inorganic refractory paper comprises 10-90% by mass of barium sulfate fiber and 1-60% by mass of inorganic reinforcing fiber; preferably, the mass content of the barium sulfate fiber is 0.5 to 25 times of that of the inorganic reinforcing fiber.
Preferably, the inorganic reinforcing fibers comprise at least one of hydroxyapatite fibers, glass fibers, carbon fibers, boron fibers, metal oxide fibers, silicate fibers, silicon carbide fibers, and metal fibers.
Preferably, the barium sulfate fiber inorganic refractory paper further comprises an inorganic adhesive with the mass percentage of 5% -80%. The mass percent of the inorganic binder is understood to be the mass percent of the inorganic binder and their reaction products remaining in the barium sulfate fiber inorganic fire-resistant paper, not the mass percent of the inorganic binder added to the aqueous dispersion of inorganic binder (the same example below), because a portion of the inorganic binder in the aqueous dispersion of inorganic binder does not remain in the paper during the papermaking process and remains in the filtrate as it flows through the paper.
Preferably, the inorganic adhesive includes at least one of a silicate adhesive, an aluminum salt adhesive, a phosphate adhesive, a borate adhesive, a silica sol adhesive, and an alumina sol adhesive. Such silicate-based adhesives include, but are not limited to, sodium metasilicate, potassium metasilicate, sodium silicate, potassium silicate, and the like. The aluminum salt adhesives include, but are not limited to, aluminum chloride, polyaluminum chloride, aluminum sulfate, aluminum nitrate, sodium aluminate, potassium aluminate, aluminum silicate, and the like. The phosphate-based adhesives include, but are not limited to, aluminum phosphate, aluminum dihydrogen phosphate, aluminum hydrogen phosphate, potassium pyrophosphate, sodium tripolyphosphate, potassium tripolyphosphate, sodium hexametaphosphate, potassium hexametaphosphate, ammonium polyphosphate, and the like. The borate-based adhesives include, but are not limited to, boric acid, sodium borate, potassium borate, ammonium borate, and the like.
Preferably, the thickness of the barium sulfate fiber inorganic refractory paper is more than 50 microns, preferably 80-2000 microns, and more preferably 100-800 microns.
The invention also provides a preparation method of the barium sulfate fiber inorganic refractory paper. The preparation method comprises the following steps: uniformly dispersing barium sulfate fiber, inorganic reinforcing fiber and inorganic adhesive in water to prepare fiber slurry; and filtering, forming, squeezing or rolling and drying the fiber slurry to prepare the barium sulfate fiber inorganic fire-resistant paper.
Preferably, the pressing pressure is 1-5MPa, and the pressing time is 1-30 minutes.
Preferably, the drying temperature is 60-105 ℃, and the drying time is 3-30 minutes.
Preferably, the preparation method further comprises the preparation method of the barium sulfate fiber: dissolving oleate, water-soluble barium salt and water-soluble sulfate in water to obtain a reaction precursor suspension, then placing the obtained reaction precursor suspension into a reaction kettle, sealing, carrying out hydrothermal treatment at the temperature of 120-240 ℃ for 6-72 hours, separating, and washing with ethanol and water to obtain the barium sulfate fiber.
Preferably, the preparation of the fiber slurry comprises: dispersing inorganic reinforcing fibers in water, and adding the inorganic reinforcing fibers into the barium sulfate fiber aqueous dispersion to form a composite fiber dispersion; dissolving an inorganic adhesive in water to form an inorganic adhesive dispersion; mixing the composite fiber dispersion liquid with an inorganic adhesive dispersion liquid to form a fiber slurry; or the preparation of the fiber slurry comprises: after dispersing the inorganic reinforcing fiber and the inorganic adhesive in water, mixing with an aqueous dispersion containing barium sulfate fiber to form the fiber slurry.
The preparation methods of the two fiber slurries can realize the uniform dispersion of the barium sulfate fiber and the inorganic reinforcing fiber.
The invention also provides application of the barium sulfate fiber inorganic refractory paper in the fields of special refractory paper, flame retardance, fire resistance, high temperature resistance, heat insulation, electric insulation, corrosion resistance, particularly strong acid and alkali resistance.
The barium sulfate fiber inorganic refractory paper prepared by the method has good flexibility, high temperature resistance, fire resistance, strong acid and strong alkali resistance and environmental friendliness, and can make up for the defect of strong acid resistance of the hydroxyapatite ultralong nanowire-based inorganic refractory paper. The barium sulfate fiber inorganic fireproof paper can be used as paper for writing, printing and printing, calligraphy drawing paper, high-temperature-resistant label paper, high-temperature-resistant fireproof paper, heat-insulating paper and the like, and has good application prospects in the fields of special fireproof paper, flame retardance, high temperature resistance, fire resistance, heat insulation, electric insulation, strong acid and alkali resistance and the like.
Drawings
FIG. 1 is a digital photograph of barium sulfate fiber inorganic refractory paper prepared in example 1 of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of the lower surface of the barium sulfate fiber inorganic refractory paper prepared in example 1 of the present invention; wherein the surface of the attaching substrate is a lower surface, the surface far away from the substrate is an upper surface, and the weaving pattern in the figure is an indentation of the weaving substrate in the paper making process;
FIG. 3 is a Scanning Electron Microscope (SEM) photograph of the lower surface of the barium sulfate fiber inorganic refractory paper prepared in example 1 of the present invention, wherein the surface attached to the substrate is the lower surface, the surface away from the substrate is the upper surface, and the protrusions in the drawing correspond to the indentations of the fibers in the woven cloth substrate;
FIG. 4 is a Scanning Electron Microscope (SEM) photograph of the side of the barium sulfate fiber inorganic refractory paper prepared in example 1 of the present invention;
FIG. 5 is a photograph of the barium sulfate fiber inorganic refractory paper prepared in example 1 of the present invention burned on the flame of an alcohol burner;
FIG. 6 is a comparison of the corrosion resistance of the barium sulfate fiber inorganic refractory paper prepared in example 2 of the present invention and the hydroxyapatite ultra-long nanowire refractory paper prepared in comparative example 1 in hydrochloric acid with a concentration of 1 mol/L;
FIG. 7 is a tensile strength curve of barium sulfate fiber inorganic refractory papers prepared in examples 1 and 2 of the present invention;
FIGS. 8, 9 and 10 are Scanning Electron Microscope (SEM) photographs on different scales of the barium sulfate fiber inorganic refractory paper prepared in example 3 of the present invention;
FIGS. 11 and 12 are Scanning Electron Microscope (SEM) photographs of the side surfaces of the barium sulfate fiber inorganic refractory paper prepared in example 3 of the present invention on different scales;
FIGS. 13, 14 and 15 are Scanning Electron Microscope (SEM) photographs on different scales of the barium sulfate fiber inorganic refractory paper prepared in example 5 of the present invention;
FIG. 16 is a back-scattered electron image of the barium sulfate fiber inorganic refractory paper prepared in example 5 of the present invention, in which the barium sulfate fiber has higher contrast and brighter color due to the high atomic number of barium element;
FIG. 17 is a graph showing the tensile strength curves of barium sulfate fiber inorganic refractory papers prepared in examples 3, 4 and 5 of the present invention;
fig. 18 and 19 are Scanning Electron Microscope (SEM) photographs of the barium sulfate fiber inorganic refractory paper prepared in comparative example 2 of the present invention at different magnifications.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative of, and not restrictive on, the present invention.
The main raw materials of the barium sulfate fiber inorganic refractory paper comprise barium sulfate fiber and inorganic reinforcing fiber. Or prepared by adopting barium sulfate fiber and inorganic reinforcing fiber and adding inorganic adhesive. The barium sulfate fiber is formed by assembling barium sulfate nanorods (with the diameter of 5-100 nanometers and the length of 50-500 nanometers) in parallel along the length direction, wherein the length of the barium sulfate fiber is more than 5 micrometers, and the diameter of the barium sulfate fiber is 0.1-5 micrometers. The barium sulfate nanorods are arranged in parallel to form barium sulfate fibers, and the unique assembly structure of the barium sulfate fibers enables the barium sulfate fibers to have good flexibility and can be used for preparing flexible inorganic refractory paper capable of resisting strong acid. On the other hand, when barium sulfate units are arranged in a random manner (for example, barium sulfate particles are formed), fibers cannot be formed, or the strength of the fibers is weak, and even when paper is formed, the performance is poor. Even though barium sulfate of other morphologies forms a one-dimensional structure, paper having a certain strength cannot be formed due to the excessively large or short length or diameter of barium sulfate.
As an example, the preparation method of the barium sulfate fiber is as follows: oleate is used as a reactant and an emulsifier, water-soluble barium salt is used as a barium source, water-soluble sulfate is used as a sulfur source, water is used as a solvent, and a precursor suspension is obtained after mixing, then the obtained precursor suspension is placed in a reaction kettle, sealed, subjected to hydrothermal treatment at the temperature of 120-240 ℃ for 6-72 hours, separated, and washed by ethanol and water to obtain the barium sulfate fiber. The water-soluble barium salt can be at least one of barium chloride and barium nitrate; the water-soluble sulfate can be at least one of sodium sulfate, potassium sulfate and ammonium sulfate; the oleate comprises at least one of sodium oleate, potassium oleate and ammonium oleate. In the precursor suspension, the concentration of oleate is 0.1-2 mol/L, the concentration of barium salt is 0.01-2 mol/L, and the concentration of sulfate is 0.01-6 mol/L. The barium sulfate fiber can also be prepared by other suitable methods as long as the barium sulfate fiber can be prepared.
The barium sulfate fiber inorganic fire-resistant paper comprises the following components: 10-90% of barium sulfate fiber, 1-60% of inorganic reinforcing fiber and 5-80% of inorganic adhesive. The preferable weight percentage of the barium sulfate fiber in the barium sulfate fiber inorganic refractory paper is 20-50%.
The inorganic reinforcing fiber comprises at least one of hydroxyapatite fiber, glass fiber, carbon fiber, boron fiber, metal oxide fiber, silicate fiber, silicon carbide fiber and metal fiber. The inorganic reinforcing fiber has a diameter of 0.02 to 20 μm and a length of 0.1 to 12 mm. Preferably, the inorganic reinforcing fibers have a diameter of 1 to 10 micrometers and a length of 1 to 5 millimeters. The weight percentage of the inorganic reinforcing fiber in the barium sulfate fiber inorganic fire-resistant paper can be 1-60%, preferably 10-40%.
In a preferred embodiment, the inorganic reinforcing fibers are glass fibers and hydroxyapatite fibers. The mass ratio of the glass fiber to the hydroxyapatite fiber is 1: 10-10: 1, preferably 1: 2-2: 1.
the composition of the inorganic adhesive comprises at least one of the following components: silicates (sodium metasilicate, potassium metasilicate, sodium silicate, potassium silicate, etc.), aluminum salts (aluminum chloride, polyaluminum chloride, aluminum sulfate, aluminum nitrate, sodium aluminate, potassium aluminate, aluminum silicate, etc.), phosphates (aluminum phosphate, aluminum dihydrogen phosphate, aluminum hydrogen phosphate, potassium pyrophosphate, sodium tripolyphosphate, potassium tripolyphosphate, sodium hexametaphosphate, potassium hexametaphosphate, ammonium polyphosphate, etc.), borates (boric acid, sodium borate, potassium borate, ammonium borate, etc.), silica sol, alumina sol, etc. The inorganic binder may or may not contain crystal water.
The barium sulfate fiber inorganic refractory paper prepared by the method can adopt a single-component inorganic adhesive, and also can adopt two or more than two components of inorganic adhesives. When the inorganic adhesive with two or more than two components is adopted, chemical reaction can occur between the inorganic adhesive components, and the generated product is coated on the barium sulfate fiber and the inorganic reinforcing fiber or filled in the gap of the fiber, so that the fibers can be interwoven and combined more tightly, and the mechanical strength of the barium sulfate fiber inorganic fire-resistant paper is improved. The weight percentage of the inorganic adhesive (including the adhesive itself, and the chemical reaction product between the adhesives) in the barium sulfate fiber inorganic refractory paper may be 5-80%, preferably 30-60%.
The barium sulfate fiber inorganic fire-resistant paper can be prepared by the traditional papermaking technology, and the specific papermaking technology comprises the following steps: and (3) filtering, forming, squeezing (pressure of 1-5MPa and time of 1-30 minutes) and drying (temperature of 60-105 ℃ and time of 3-30 minutes) the prepared fiber slurry to prepare the refractory paper. The fiber slurry can be obtained by stirring and mixing barium sulfate fiber, inorganic reinforcing fiber, inorganic adhesive and water. In the fiber slurry, the concentration of barium sulfate fibers is preferably 0.1-2 wt%.
The thickness of the barium sulfate fiber inorganic refractory paper is more than 50 microns, preferably 80-2000 microns, and more preferably 100-800 microns. The thickness of the barium sulfate fiber inorganic refractory paper can be adjusted according to needs, the barium sulfate fiber inorganic refractory paper can be used as a barium sulfate fiber-based inorganic refractory blanket when the thickness exceeds 3000 micrometers, and even the barium sulfate fiber-based inorganic refractory brick can be prepared when the thickness is larger. The tensile strength of the barium sulfate fiber inorganic refractory paper can be 2-50 MPa.
The barium sulfate fiber inorganic refractory paper has good flexibility and mechanical property, and good high-temperature flexibility, and can better maintain the flexibility in the flame burning process.
The present invention will be described in detail by way of examples. The present invention is further illustrated by the following specific examples, which are to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever. The invention is not limited to the embodiments described above, but rather, various modifications and changes may be made by those skilled in the art without departing from the scope of the invention. The specific process parameters and the like in the following examples are also only one example of suitable ranges, and the skilled person can make a selection within the suitable ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
Dispersing 0.44 g of glass fiber in 1.5L of water, adding 0.5L of water dispersion containing 10 g of barium sulfate fiber, and uniformly stirring to form composite fiber dispersion; dissolving 15.87 g of inorganic adhesive in 0.3L of water to form water dispersion, mixing the water dispersion with the composite fiber dispersion, and uniformly stirring to form fiber slurry; and then, carrying out water filtration forming on the fiber slurry on a Kaiser rapid paper sheet former, and squeezing (with woven cloth as a substrate, the pressure is 4MPa, the time is about 3 minutes), and drying (the temperature is 95 ℃, the time is about 10 minutes) the formed paper sheet to obtain the barium sulfate fiber inorganic fire-resistant paper.
The prepared barium sulfate inorganic refractory paper has a diameter of 20 cm (fig. 1) and a thickness of about 400 μm (fig. 4). In this example, the mass percentage of the inorganic adhesive in the barium sulfate fiber inorganic refractory paper is about 13%. The mass percent of the inorganic binder is understood to be the mass percent of the inorganic binder and their reaction products remaining in the barium sulfate fiber inorganic fire-resistant paper, not the amount of inorganic binder added to the aqueous dispersion of inorganic binder (the same example below), because a portion of the inorganic binder in the aqueous dispersion of inorganic binder does not remain in the paper during the papermaking process and remains in the filtrate as it flows through the paper. As shown in fig. 2 and fig. 3, in the prepared barium sulfate fiber inorganic refractory paper, the barium sulfate fibers are arranged very tightly, and the diameter of the barium sulfate fibers is much smaller than that of the fibers in the woven cloth substrate used in the paper making process (in the figure, the weaving-shaped impression is the outline of the fibers of the woven cloth). As shown in fig. 4, the barium sulfate fiber inorganic refractory paper has a layered structure, and the glass fiber is inserted into the layered structure to form a composite structure similar to "steel bar-concrete", thereby having a better mechanical strength (tensile strength of about 2.5MPa, see fig. 7). As shown in FIG. 5, the barium sulfate fiber inorganic refractory paper can resist burning of alcohol burner flame, and can perform more than 60 times of 'bending-stretching' reciprocating burning, which shows that the barium sulfate fiber inorganic refractory paper has good high-temperature flexibility.
Comparative example 1
Dispersing 0.44 g of glass fiber in 1.5L of water, adding 0.5L of water dispersion containing 10 g of hydroxyapatite fiber, and uniformly stirring to form composite fiber dispersion; dissolving 15.87 g of inorganic adhesive in 0.3L of water to form water dispersion, mixing the water dispersion with the composite fiber dispersion, and uniformly stirring to form fiber slurry; and then, carrying out water filtration forming on the fiber slurry on a Kaiser rapid paper sheet former, and squeezing (with woven cloth as a substrate, the pressure is 4MPa, the time is about 3 minutes) and drying (the temperature is 95 ℃ and the time is about 10 minutes) the formed paper sheet to obtain the hydroxyapatite fiber-based inorganic refractory paper.
The strong acid resistance of the hydroxyapatite fiber-based inorganic refractory paper is compared with that of the barium sulfate fiber inorganic refractory paper prepared in example 1 (fig. 6), and the result shows that the hydroxyapatite fiber-based inorganic refractory paper is quickly dispersed and dissolved in hydrochloric acid, while the barium sulfate fiber inorganic refractory paper is not dispersed and dissolved in hydrochloric acid and has better wet strength, which indicates that the barium sulfate fiber inorganic refractory paper prepared in the invention has excellent strong acid corrosion resistance.
Example 2
Mixing 0.05 g of glass fiber, 6.323 g of inorganic adhesive and 0.041 l of water, uniformly stirring, adding 0.02 l of aqueous dispersion containing 0.2 g of barium sulfate fiber, uniformly stirring to form fiber slurry, then carrying out water filtration forming on the fiber slurry on a vacuum filtration device, rolling the formed paper sheet (using filter paper as a substrate), and drying (the temperature is 70 ℃ for about 5 minutes) to obtain the barium sulfate fiber inorganic refractory paper.
The diameter of the prepared barium sulfate fiber inorganic refractory paper is 4 cm. As shown in FIG. 7, the prepared barium sulfate fiber inorganic refractory paper has a tensile strength of about 11.9MPa and a fracture deformation of about 3.9%.
Example 3
0.05 g of glass fiber, 6.323 g of inorganic adhesive and 0.051 l of water are mixed and stirred uniformly, 0.02 l of aqueous dispersion containing 0.1 g of barium sulfate fiber is added and stirred uniformly to form fiber slurry, then the fiber slurry is filtered and formed on a vacuum filtration device, and the formed fiber slurry is rolled (filter paper is used as a substrate) and dried (the temperature is 95 ℃ and the time is about 5 minutes) to obtain the barium sulfate fiber inorganic refractory paper.
The prepared barium sulfate fiber inorganic refractory paper has a diameter of 4 cm and a thickness of about 300 μm (fig. 11). The weight percentage of the inorganic adhesive in the prepared barium sulfate fiber inorganic refractory paper is about 51%, the tensile strength is about 6.3MPa, the fracture deformation is about 1.4%, and the barium sulfate fiber inorganic refractory paper still has certain tensile strength due to the connection effect of the glass fiber after fracture (figure 17). As shown in fig. 8, the glass fibers are relatively uniformly dispersed in the barium sulfate fiber matrix (the size of the barium sulfate fibers is much smaller than that of the glass fibers, and the barium sulfate fibers are assembled by barium sulfate nanorods in parallel along the length direction, see fig. 9), so as to form a composite structure similar to "steel bar-concrete". As shown in fig. 10, the surface of the barium sulfate fiber in the prepared barium sulfate fiber inorganic refractory paper is wrapped with a layer of inorganic adhesive, so that the bonding force between fibers can be improved, and the gaps between fibers can be filled, thereby being beneficial to improving the mechanical strength of the barium sulfate fiber inorganic refractory paper. As shown in fig. 11, the barium sulfate fiber inorganic refractory paper has a layered structure in which glass fibers are interpenetrated. As shown in fig. 12, the barium sulfate fiber can wrap the surface of the glass fiber under the action of the inorganic adhesive, so as to improve the bonding strength between the glass fiber and the barium sulfate fiber, which indicates that the inorganic adhesive is one of the important factors for improving the mechanical strength of the barium sulfate fiber inorganic fire-resistant paper.
Example 4
0.05 g of glass fiber, 6.323 g of inorganic adhesive and 0.051 l of water are mixed and stirred uniformly, 0.02 l of aqueous dispersion containing 0.075 g of barium sulfate fiber and 0.025 g of hydroxyapatite fiber is added and stirred uniformly to form fiber slurry, then the fiber slurry is filtered and formed on a vacuum filtration device, and the formed paper sheet is rolled (by using filter paper as a substrate) and dried (the temperature is 95 ℃ and the time is about 5 minutes) to obtain the barium sulfate fiber inorganic refractory paper.
The diameter of the prepared barium sulfate fiber inorganic refractory paper is 4 cm, and the weight percentage of the inorganic adhesive in the paper is about 44%. As shown in fig. 17, the tensile strength of the barium sulfate fiber inorganic refractory paper is about 14.4MPa, the fracture deformation is about 1.8%, and the barium sulfate fiber inorganic refractory paper still has a certain tensile strength due to the bonding effect of the glass fibers after fracture.
Example 5
0.05 g of glass fiber, 6.323 g of inorganic adhesive and 0.051 l of water are mixed and stirred uniformly, 0.02 l of aqueous dispersion containing 0.05 g of barium sulfate fiber and 0.05 g of hydroxyapatite fiber is added and stirred uniformly to form fiber slurry, then the fiber slurry is filtered and formed on a vacuum filtration device, and the formed paper sheet is rolled (by using filter paper as a substrate) and dried (the temperature is 95 ℃ and the time is about 5 minutes) to obtain the barium sulfate fiber inorganic refractory paper.
The diameter of the prepared barium sulfate fiber inorganic refractory paper is 4 cm, and the weight percentage of the inorganic adhesive in the paper is about 44%. As shown in fig. 17, the prepared barium sulfate fiber inorganic refractory paper has a tensile strength as high as 29MPa, a fracture deformation of about 3.5%, and a certain tensile strength after fracture due to the bonding effect of the glass fibers. As shown in fig. 13, the glass fibers are dispersed in the barium sulfate fibers and hydroxyapatite fibers (the barium sulfate fibers and hydroxyapatite fibers are much smaller in size than the glass fibers, see fig. 13 and 14), forming a composite structure similar to "steel-concrete". As shown in fig. 14 and 15, the inorganic adhesive particles are adhered to the fibers or filled in the pores between the fibers, which is beneficial to improving the mechanical strength of the barium sulfate fiber inorganic refractory paper. As shown in fig. 16, in the prepared barium sulfate fiber inorganic fire-resistant paper, the barium sulfate fiber (bright part) and the hydroxyapatite fiber (dark part) can be uniformly and densely interwoven, thereby being beneficial to improving the mechanical strength of the fire-resistant paper.
As can be seen from examples 3, 4 and 5, the strength of the prepared barium sulfate fiber inorganic refractory paper increases as the content of the hydroxyapatite fiber increases (fig. 17). Therefore, the hydroxyapatite fiber is an ideal reinforcing fiber of the barium sulfate fiber inorganic refractory paper.
Comparative example 2
Filtering and forming 0.06 liter of aqueous dispersion containing 0.2 g of barium sulfate fiber on a vacuum filtration device, rolling the formed paper (taking filter paper as a substrate), and drying (the temperature is 70 ℃ and the time is about 5 minutes) to obtain the barium sulfate fiber inorganic refractory paper.
The diameter of the prepared barium sulfate fiber inorganic refractory paper is 4 cm. The barium sulfate fiber inorganic refractory paper does not contain an inorganic adhesive and a reinforcing fiber, and although the barium sulfate fiber is arranged closely (fig. 18 and 19), the mechanical strength of the barium sulfate fiber inorganic refractory paper is poor, and the tensile strength of the barium sulfate fiber inorganic refractory paper is less than 0.1 MPa. Therefore, the inorganic adhesive and the inorganic reinforcing fiber are very important for improving the mechanical property of the barium sulfate fiber inorganic refractory paper.
Example 6
0.05 g of glass fiber, 6.392 g of inorganic adhesive and 0.051 l of water are mixed and stirred uniformly, 0.02 l of aqueous dispersion containing 0.1 g of barium sulfate fiber is added and stirred uniformly to form fiber slurry, then the fiber slurry is filtered and formed on a vacuum filtration device, and the formed paper sheet is rolled (by using filter paper as a substrate) and dried (the temperature is 95 ℃ for about 5 minutes) to obtain the barium sulfate fiber inorganic refractory paper.
Example 7
0.05 g of alumina fiber, 6.392 g of inorganic adhesive and 0.051 l of water are mixed and stirred uniformly, 0.02 l of aqueous dispersion containing 0.1 g of barium sulfate fiber is added and stirred uniformly to form fiber slurry, then the fiber slurry is filtered and formed on a vacuum filtration device, and the formed paper sheet is rolled (by using filter paper as a substrate) and dried (the temperature is 95 ℃ for about 5 minutes) to obtain the barium sulfate fiber inorganic refractory paper.
Example 8
0.05 g of aluminum silicate fiber, 4.566 g of inorganic adhesive and 0.051 l of water are mixed and stirred for forbidden transportation, 0.02 l of aqueous dispersion containing 0.1 g of barium sulfate fiber is added and stirred uniformly to form fiber slurry, then the fiber slurry is filtered and formed on a vacuum filtration device, and the formed paper sheet is rolled (by using filter paper as a substrate) and dried (the temperature is 95 ℃ and the time is about 5 minutes) to obtain the barium sulfate fiber inorganic refractory paper.
Example 9
0.05 g of magnesium silicate fiber, 3.678 g of inorganic adhesive and 0.051 l of water are mixed and stirred uniformly, 0.02 l of aqueous dispersion containing 0.1 g of barium sulfate fiber is added and stirred uniformly to form fiber slurry, then the fiber slurry is filtered and formed on a vacuum filtration device, and the formed paper sheet is rolled (by using filter paper as a substrate) and dried (the temperature is 95 ℃ for about 5 minutes) to obtain the barium sulfate fiber inorganic refractory paper.
Example 10
Mixing 0.05 g of carbon fiber, 5.086 g of inorganic adhesive and 0.06 liter of water, stirring for a period of time, adding 0.02 liter of aqueous dispersion containing 0.2 g of barium sulfate fiber, stirring uniformly to form fiber slurry, then carrying out water filtration forming on the fiber slurry on a vacuum filtration device, rolling the formed paper sheet (using filter paper as a substrate), and drying (the temperature is 95 ℃ for about 5 minutes) to obtain the barium sulfate fiber inorganic refractory paper.

Claims (10)

1. The barium sulfate fiber inorganic fire-resistant paper is characterized by being a composite porous net-shaped structure formed by barium sulfate fibers with the length of more than 5 micrometers and the diameter of 0.1-5 micrometers and inorganic reinforcing fibers with the diameter of 0.02-20 micrometers and the length of 0.1-12 millimeters, wherein inorganic adhesive is filled in pores of the composite porous net-shaped structure; the barium sulfate fiber is formed by assembling barium sulfate nano rods with the diameter of 5-100 nanometers and the length of 50-500 nanometers in parallel along the length direction.
2. The barium sulfate fiber inorganic refractory paper as claimed in claim 1, wherein the raw material composition of the barium sulfate fiber inorganic refractory paper comprises 10-90% by mass of barium sulfate fiber and 1-60% by mass of inorganic reinforcing fiber.
3. The barium sulfate fiber inorganic refractory paper as claimed in claim 2, wherein the mass of the barium sulfate fiber is 0.5-25 times of that of the inorganic reinforcing fiber.
4. The barium sulfate fiber inorganic refractory paper of claim 1, wherein the inorganic reinforcing fibers comprise at least one of hydroxyapatite fibers, glass fibers, carbon fibers, boron fibers, metal oxide fibers, silicate fibers, silicon carbide fibers, and metal fibers.
5. The barium sulfate fiber inorganic refractory paper according to claim 1, wherein the inorganic adhesive comprises at least one of a silicate-based adhesive, an aluminum salt-based adhesive, a phosphate-based adhesive, a borate-based adhesive, a silica sol adhesive, and an alumina sol adhesive.
6. The method for preparing the barium sulfate fiber inorganic refractory paper according to any one of claims 1 to 5, wherein the method comprises the following steps: uniformly dispersing barium sulfate fiber, inorganic reinforcing fiber and inorganic adhesive in water to prepare fiber slurry; and filtering, molding, squeezing or rolling and drying the fiber slurry to obtain the barium sulfate fiber inorganic fire-resistant paper.
7. The method for preparing the barium sulfate fiber inorganic refractory paper as claimed in claim 6, wherein the preparation of the fiber slurry comprises: dispersing inorganic reinforcing fibers in water, and adding the inorganic reinforcing fibers into the barium sulfate fiber aqueous dispersion to form a composite fiber dispersion; dissolving an inorganic adhesive in water to form an inorganic adhesive dispersion; mixing the composite fiber dispersion liquid with an inorganic adhesive dispersion liquid to form a fiber slurry; or
The preparation of the fiber slurry comprises the following steps: after dispersing the inorganic reinforcing fiber and the inorganic adhesive in water, mixing with an aqueous dispersion containing barium sulfate fiber to form the fiber slurry.
8. The method for preparing the barium sulfate fiber inorganic refractory paper as claimed in claim 6, wherein the pressing pressure is 1-5MPa and the pressing time is 1-30 minutes.
9. The method for preparing the barium sulfate fiber inorganic refractory paper according to claim 6, wherein the drying temperature is 60-105 ℃ and the drying time is 3-30 minutes.
10. Use of the barium sulfate fiber inorganic fire-resistant paper of any one of claims 1 to 5 in the fields of fire-resistance, high-temperature resistance, thermal insulation, electrical insulation, corrosion resistance.
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CN111892077B (en) * 2020-07-21 2021-06-15 中国科学院上海硅酸盐研究所 Barium sulfate fiber and preparation method thereof
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08283076A (en) * 1995-04-10 1996-10-29 Nichias Corp Porous granular compact
CN1740095A (en) * 2005-07-18 2006-03-01 同济大学 The method of structure with same quality and different profile with double formworks synchronously barium salt nano-superstructure
CN104709934A (en) * 2015-02-05 2015-06-17 成都新柯力化工科技有限公司 Preparation method of fibrous barium sulfate
CN106676947A (en) * 2016-12-02 2017-05-17 中国科学院上海硅酸盐研究所 Inorganic fire-resistant paper as well as preparation method and application thereof
CN109082942A (en) * 2018-08-01 2018-12-25 中国科学院上海硅酸盐研究所 " rice paper " is imitated in fire resisting

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08283076A (en) * 1995-04-10 1996-10-29 Nichias Corp Porous granular compact
CN1740095A (en) * 2005-07-18 2006-03-01 同济大学 The method of structure with same quality and different profile with double formworks synchronously barium salt nano-superstructure
CN104709934A (en) * 2015-02-05 2015-06-17 成都新柯力化工科技有限公司 Preparation method of fibrous barium sulfate
CN106676947A (en) * 2016-12-02 2017-05-17 中国科学院上海硅酸盐研究所 Inorganic fire-resistant paper as well as preparation method and application thereof
CN109082942A (en) * 2018-08-01 2018-12-25 中国科学院上海硅酸盐研究所 " rice paper " is imitated in fire resisting

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