阅读说明：本技术 一种纳米防火材料及其制备方法 (Nano fireproof material and preparation method thereof ) 是由 孙刚 于 2019-08-30 设计创作，主要内容包括：本发明涉及一种纳米防火材料及其制备方法,该纳米防火材料包括如下重量份的原料：超活性纳米二氧化钛15-25份；氧化石墨烯-碳纳米管分散液10-20份；玻化微珠5-10份；硅藻土12-22份；蛭石15-25份；无机胶黏剂20-30份；无机分散剂3-8份；水30-45份。本发明的纳米防火材料,通过氧化石墨烯与碳纳米管形成分散液与超活性纳米二氧化钛纳米形成三维框架结构,与组分中的其它阻燃或难燃材料配合作用时,能够提高各原料之间的相容性、分散性,最终增加防火材料的力学性能和阻燃性能。(The invention relates to a nanometer fireproof material and a preparation method thereof, wherein the nanometer fireproof material comprises the following raw materials in parts by weight: 15-25 parts of super-active nano titanium dioxide; 10-20 parts of graphene oxide-carbon nanotube dispersion liquid; 5-10 parts of vitrified micro bubbles; 12-22 parts of diatomite; 15-25 parts of vermiculite; 20-30 parts of an inorganic adhesive; 3-8 parts of an inorganic dispersant; 30-45 parts of water. According to the nanometer fireproof material, the graphene oxide and the carbon nano tube form dispersion liquid and the super-active nanometer titanium dioxide nanometer forms a three-dimensional frame structure, and when the nanometer fireproof material is matched with other flame-retardant or flame-retardant materials in the components, the compatibility and the dispersibility among the raw materials can be improved, and the mechanical property and the flame-retardant property of the fireproof material are finally improved.)

1. The nanometer fireproof material is characterized by comprising the following raw materials in parts by weight:

15-25 parts of super-active nano titanium dioxide; 10-20 parts of graphene oxide-carbon nanotube dispersion liquid; 5-10 parts of vitrified micro bubbles; 12-22 parts of diatomite; 15-25 parts of vermiculite; 20-30 parts of an inorganic adhesive; 3-8 parts of an inorganic dispersant; 30-45 parts of water.

2. The nano fireproof material of claim 1, wherein the diameter of the particles of the super active nano titanium dioxide is 1-5 nm.

3. The nano-fireproofing material of claim 1, wherein the particle diameter of the super-active nano-titanium dioxide is less than 2 nm.

4. The nano fireproof material of claim 1, wherein the graphene oxide-carbon nanotube dispersion liquid is a mixed dispersion solution formed by ultrasonic oscillation of graphene oxide and carbon nanotubes.

5. The nano fireproof material of claim 4, wherein the preparation method of the graphene oxide-carbon nanotube dispersion comprises the following steps:

1) preparing graphene oxide from graphene by using a Hummers method;

2) ultrasonically dispersing graphene oxide in water for 30-40min to form a graphene oxide dispersion liquid;

3) adding a carbon nano tube into the graphene oxide dispersion liquid, and continuing to perform ultrasonic oscillation for 1-2 hours to obtain the graphene oxide-carbon nano tube dispersion liquid.

6. The nano fireproof material according to claim 5, wherein the mass ratio of graphene oxide to carbon nanotubes in the graphene oxide-carbon nanotube dispersion liquid is (1-2): (2-3).

7. The nano fireproof material of claim 5, wherein the inorganic adhesive is an inorganic silicate adhesive with a solid content of 20-25% by weight, a viscosity of-4 cup for 60 seconds or more, and a stable physical property at 800-1400 ℃.

8. The nano fireproof material of claim 1, wherein the inorganic dispersant is a carbonate, phosphate or hydroxide of calcium, magnesium or barium.

9. A method for preparing a nano fire-proof material as claimed in any one of claims 1 to 8, comprising the steps of:

1) uniformly mixing the super-active nano titanium dioxide and the graphene oxide-carbon nanotube dispersion liquid to obtain a nano mixture;

2) ball-milling the vitrified micro bubbles, the diatomite and the vermiculite into powder by adopting a ball-milling technology to obtain ball-milled powder;

3) and adding an inorganic adhesive, an inorganic dispersant and water into the nano mixture and the ball milled powder, and uniformly stirring to obtain the nano fireproof material.

Technical Field

The invention belongs to the technical field of fireproof materials, and particularly relates to a nanometer fireproof material and a preparation method thereof.

Background

The use of a large amount of electronic appliances in modern life and the use of too many flammable materials in decoration materials are easy to trigger fire, thereby bringing potential safety hazards and even disasters to the life of people.

The existing fireproof plates, fireproof doors, fireproof glass and fireproof coatings generally achieve the effects of reducing fire load and reducing the fire spreading speed by coating or adding materials with flame-retardant or flame-retardant characteristics on the surfaces, but the existing fireproof materials have the problems of low fire resistance level, thick and heavy materials, harmful gas generation in fire or poor aging resistance and the like.

Disclosure of Invention

In order to solve the problems in the prior art, the invention provides a nano fireproof material and a preparation method thereof. The technical problem to be solved by the invention is realized by the following technical scheme:

a nanometer fireproof material comprises the following raw materials in parts by weight: 15-25 parts of super-active nano titanium dioxide; 10-20 parts of graphene oxide-carbon nanotube dispersion liquid; 5-10 parts of vitrified micro bubbles; 12-22 parts of diatomite; 15-25 parts of vermiculite; 20-30 parts of an inorganic adhesive; 3-8 parts of an inorganic dispersant; 30-45 parts of water.

Preferably, the particle diameter of the super-active nano titanium dioxide is 1-5 nm.

Preferably, the particle diameter of the super-active nano titanium dioxide is less than 2 nm.

Preferably, the graphene oxide-carbon nanotube dispersion liquid is a mixed dispersion solution formed by subjecting graphene oxide and carbon nanotubes to ultrasonic oscillation.

Preferably, the preparation method of the graphene oxide-carbon nanotube dispersion liquid comprises the following steps:

1) preparing graphene oxide from graphene by using a Hummers method;

2) ultrasonically dispersing graphene oxide in water for 30-40min to form a graphene oxide dispersion liquid;

3) adding a carbon nano tube into the graphene oxide dispersion liquid, and continuing to perform ultrasonic oscillation for 1-2 hours to obtain the graphene oxide-carbon nano tube dispersion liquid.

Preferably, the mass ratio of the graphene oxide to the carbon nanotubes in the graphene oxide-carbon nanotube dispersion liquid is (1-2): (2-3).

Preferably, the inorganic adhesive is an inorganic silicate adhesive with a solid content of 20-25% by weight, a viscosity of-4 cups for more than or equal to 60 seconds, and stable physical properties at a temperature of 800-1400 ℃.

Preferably, the inorganic dispersant is a carbonate, phosphate or hydroxide of calcium, magnesium, barium.

The preparation method of the nanometer fireproof material comprises the following steps:

1) uniformly mixing the super-active nano titanium dioxide and the graphene oxide-carbon nanotube dispersion liquid to obtain a nano mixture;

2) ball-milling the vitrified micro bubbles, the diatomite and the vermiculite into powder by adopting a ball-milling technology to obtain ball-milled powder;

3) and adding an inorganic adhesive, an inorganic dispersant and water into the nano mixture and the ball milled powder, and uniformly stirring to obtain the nano fireproof material.

Compared with the prior art, the invention has the beneficial effects that:

1. according to the nano fireproof material, the graphene oxide and the carbon nano tube form a dispersion liquid, the graphene oxide not only retains the original pi conjugated structure of the graphene, but also has a large number of oxygen-containing functional groups, so that the graphene oxide has good dispersibility; the carbon nano tube has excellent performances of heat, electricity, mechanics, hydrogen storage, catalysis and the like due to the unique structure, but has poor dispersibility; the dispersion liquid formed by the graphene oxide and the carbon nano tube can avoid the problem of dispersibility and has the advantages of the graphene oxide and the carbon nano tube; the material can form a three-dimensional frame structure with the super-active nano titanium dioxide, and when the material is matched with other materials in the components, the compatibility and the dispersibility among the raw materials can be improved, the occurrence of agglomeration phenomenon is effectively reduced, and finally the toughness, the strength and the flame retardant property of the fireproof material are improved.

2. The nanometer fireproof material has excellent dispersibility of the super-active nanometer titanium dioxide, and when the nanometer fireproof material is mixed with the graphene oxide-carbon nanotube dispersion liquid, the mixture of the two cannot generate an agglomeration phenomenon; and the excellent photocatalysis performance of the material can reflect ultraviolet light and infrared light irradiated on the surface of the fireproof material, so that heat energy is reflected, the effect of conducting heat effect from the external environment is eliminated, and the purpose of weather resistance of the fireproof material is achieved.

3. The vitrified micro bubbles of the nano fireproof material are a novel inorganic light heat-insulating material with high performance, the melting temperature resistance is very high, vermiculite has good flame retardant property, and the fire resistance of the fireproof material is further improved when the vitrified micro bubbles and other components act together.

4. According to the nanometer fireproof material, the used adhesive and the used dispersing agent are inorganic matters which are not easy to burn, and all the components are flame-retardant or flame-retardant substances, so that the fire resistance grade of the fireproof material can be effectively improved.

5. In the preparation method, the vitrified micro bubbles, the diatomite and the vermiculite are ball-milled into powder by adopting a ball milling technology, and are more easily and uniformly dispersed in the inorganic adhesive, the inorganic dispersing agent and water together with the nano mixture, so that the dispersibility among the raw materials is improved, and better flame-retardant and fireproof performances are achieved.

Detailed Description

The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.

Example one

The nanometer fireproof material comprises the following raw materials in parts by weight: 20 parts of super-active nano titanium dioxide; 16 parts of graphene oxide-carbon nanotube dispersion liquid; 7 parts of vitrified micro bubbles; 18 parts of diatomite; 20 parts of vermiculite; 25 parts of an inorganic adhesive; 6 parts of an inorganic dispersant; and 40 parts of water.

In the embodiment, the particle diameter of the super-active nano titanium dioxide is 1-5 nm; more preferably less than 2 nm.

The graphene oxide-carbon nanotube dispersion liquid is a mixed dispersion solution formed by ultrasonically oscillating graphene oxide and carbon nanotubes.

The preparation method of the graphene oxide-carbon nanotube dispersion liquid may include the steps of:

1) preparing graphene oxide from graphene by using a Hummers method;

2) ultrasonically dispersing graphene oxide in water for 30-40min to form a graphene oxide dispersion liquid;

3) adding a carbon nano tube into the graphene oxide dispersion liquid, and continuing to perform ultrasonic oscillation for 1-2 hours to obtain the graphene oxide-carbon nano tube dispersion liquid.

The mass ratio of the graphene oxide to the carbon nanotubes in the graphene oxide-carbon nanotube dispersion liquid is preferably 1: 2. the carbon nano tube comprises one or more of a surface carboxyl modified carbon nano tube, a surface amino modified carbon nano tube or a surface hydroxyl modified carbon nano tube. In this embodiment, the carbon nanotube is modified by carboxyl group.

The inorganic adhesive selected by the embodiment is an inorganic silicate adhesive with a solid content of 20-25% by weight, a viscosity of-4 cups for more than or equal to 60 seconds, and stable physical properties at a temperature of 800-1400 ℃. The inorganic dispersant is carbonate, phosphate or hydroxide of calcium, magnesium and barium, and may be calcium carbonate or calcium phosphate.

The preparation method of the nano fireproof material comprises the following steps:

1) uniformly mixing 20 parts of super-active nano titanium dioxide and 16 parts of graphene oxide-carbon nanotube dispersion liquid to obtain a nano mixture;

2) ball-milling 7 parts of vitrified microbeads, 18 parts of diatomite and 20 parts of vermiculite into powder by adopting a ball-milling technology to obtain ball-milled powder;

3) and adding 25 parts of inorganic adhesive, 6 parts of inorganic dispersant and 40 parts of water into the nano mixture and the ball milled powder, and uniformly stirring to obtain the nano fireproof material.

Example two

The nanometer fireproof material comprises the following raw materials in parts by weight: 15 parts of super-active nano titanium dioxide; 10 parts of graphene oxide-carbon nanotube dispersion liquid; 5 parts of vitrified micro bubbles; 12 parts of diatomite; 15 parts of vermiculite; 20 parts of inorganic adhesive; 3 parts of an inorganic dispersant; and 30 parts of water.

In this embodiment, the graphene oxide-carbon nanotube dispersion liquid is a mixed dispersion solution formed by subjecting graphene oxide and carbon nanotubes to ultrasonic oscillation. The mass ratio of graphene oxide to carbon nanotubes in the graphene oxide-carbon nanotube dispersion liquid is preferably 2: 3. the carbon nano tube comprises one or more of a surface carboxyl modified carbon nano tube, a surface amino modified carbon nano tube or a surface hydroxyl modified carbon nano tube. In this embodiment, the carbon nanotube is modified by hydroxyl on the surface.

The preparation method of the nano fireproof material comprises the following steps:

1) uniformly mixing 15 parts of super-active nano titanium dioxide and 10 parts of graphene oxide-carbon nanotube dispersion liquid to obtain a nano mixture;

2) ball-milling 5 parts of vitrified microbeads, 12 parts of diatomite and 15 parts of vermiculite into powder by adopting a ball-milling technology to obtain ball-milled powder;

3) and adding 20 parts of inorganic adhesive, 3 parts of inorganic dispersant and 30 parts of water into the nano mixture and the ball milled powder, and uniformly stirring to obtain the nano fireproof material.

EXAMPLE III

The nanometer fireproof material comprises the following raw materials in parts by weight: 25 parts of super-active nano titanium dioxide; 20 parts of graphene oxide-carbon nanotube dispersion liquid; 10 parts of vitrified micro bubbles; 22 parts of diatomite; 25 parts of vermiculite; 30 parts of inorganic adhesive; 8 parts of an inorganic dispersant; and 45 parts of water.

In this embodiment, the graphene oxide-carbon nanotube dispersion liquid is a mixed dispersion solution formed by subjecting graphene oxide and carbon nanotubes to ultrasonic oscillation. The mass ratio of graphene oxide to carbon nanotubes in the graphene oxide-carbon nanotube dispersion liquid is preferably 1: 1. the carbon nano tube comprises one or more of a surface carboxyl modified carbon nano tube, a surface amino modified carbon nano tube or a surface hydroxyl modified carbon nano tube. In this embodiment, the carbon nanotube with amino group modified surface is selected.

The vitrified micro bubbles used in the embodiment are acidic vitreous lava mineral (pitchstone sand), are processed by special technical treatment and production technology to form porous inner parts and vitrified closed surfaces, are spherical fine-diameter particles, and are novel inorganic light heat-insulating materials with high performance. The main chemical component is SiO₂﹑Al₂O₃CaO, with particle diameter of 0.1-2mm and volume weight of 50-100kg/m³The thermal conductivity was 0.028-0.048W/m.K, the flotation rate was greater than 95%, the vitrification rate for spheronization was greater than 95%, the water absorption was less than 50%, and the melting temperature was 1200 ℃.

The preparation method of the nano fireproof material comprises the following steps:

1) uniformly mixing 25 parts of super-active nano titanium dioxide and 20 parts of graphene oxide-carbon nanotube dispersion liquid to obtain a nano mixture;

2) ball-milling 10 parts of vitrified microbeads, 22 parts of diatomite and 25 parts of vermiculite into powder by adopting a ball-milling technology to obtain ball-milled powder;

3) and adding 30 parts of inorganic adhesive, 8 parts of inorganic dispersant and 45 parts of water into the nano mixture and the ball milled powder, and uniformly stirring to obtain the nano fireproof material.

Comparative example 1

The difference between the comparative example and the first example is that the raw materials do not contain the super-active nano titanium dioxide, and other components are the same; namely, the fireproof material of the comparative example comprises the following raw materials in parts by weight: 16 parts of graphene oxide-carbon nanotube dispersion liquid; 7 parts of vitrified micro bubbles; 18 parts of diatomite; 20 parts of vermiculite; 25 parts of an inorganic adhesive; 6 parts of an inorganic dispersant; and 40 parts of water.

Comparative example No. two

The comparative example is different from the first example in that the raw materials do not contain the graphene oxide-carbon nanotube dispersion liquid, and other components are the same; namely, the fireproof material of the comparative example comprises the following raw materials in parts by weight: 20 parts of super-active nano titanium dioxide; 7 parts of vitrified micro bubbles; 18 parts of diatomite; 20 parts of vermiculite; 25 parts of an inorganic adhesive; 6 parts of an inorganic dispersant; and 40 parts of water.

Comparative example No. three

The difference between the comparative example and the first example is that the raw materials contained in the comparative example are the same and have different contents; namely, the fireproof material of the comparative example comprises the following raw materials in parts by weight: 5 parts of super-active nano titanium dioxide; 5 parts of graphene oxide-carbon nanotube dispersion liquid; 3 parts of vitrified micro bubbles; 30 parts of diatomite; 30 parts of vermiculite; 35 parts of inorganic adhesive; 10 parts of an inorganic dispersant; 50 parts of water.

The fire-resistant performance of the fire-resistant material of each embodiment and each proportion of the invention is tested, and the test results are shown in the following table:

	fire resistance rating	Limiting oxygen index	Compressive strength (MPa)	Tensile strength (MPa)
					Example one	A1	35	7.1	5.3
Example two	A1	32	6.2	4.8
					EXAMPLE III	A1	33	6.5	5.0
Comparative example 1	B1	27	3.0	2.8
					Comparative example No. two	B1	27	2.5	2.3
Comparative example No. three	B1	28	3.2	3.0

As can be seen from the above table, the contents of the super-active nano titanium dioxide and the graphene oxide-carbon nanotube dispersion liquid in the components of the nano fireproof material of the present invention, and the mutual matching ratio of the raw materials have a great influence on the indexes such as the fire resistance and the mechanical properties of the finally formed fireproof material product.

According to the nano fireproof material, the graphene oxide and the carbon nano tube form a dispersion liquid, the graphene oxide not only retains the original pi conjugated structure of the graphene, but also has a large number of oxygen-containing functional groups, so that the graphene oxide has good dispersibility; the carbon nano tube has excellent performances of heat, electricity, mechanics, hydrogen storage, catalysis and the like due to the unique structure, but has poor dispersibility; the dispersion liquid formed by the graphene oxide and the carbon nano tube can avoid the problem of dispersibility and has the advantages of the graphene oxide and the carbon nano tube; the material can form a three-dimensional frame structure with the super-active nano titanium dioxide, and when the material is matched with other materials in the components, the compatibility and the dispersibility among the raw materials can be improved, the occurrence of agglomeration phenomenon is effectively reduced, and finally the toughness, the strength and the flame retardant property of the fireproof material are improved. The nanometer fireproof material has excellent dispersibility of the super-active nanometer titanium dioxide, and when the nanometer fireproof material is mixed with the graphene oxide-carbon nanotube dispersion liquid, the mixture of the two cannot generate an agglomeration phenomenon; and the excellent photocatalysis performance of the material can reflect ultraviolet light and infrared light irradiated on the surface of the fireproof material, so that heat energy is reflected, the effect of conducting heat effect from the external environment is eliminated, and the purpose of weather resistance of the fireproof material is achieved. The vitrified micro bubbles of the nano fireproof material are a novel inorganic light heat-insulating material with high performance, the melting temperature resistance is very high, vermiculite has good flame retardant property, and the fire resistance of the fireproof material is further improved when the vitrified micro bubbles and other components act together. According to the nanometer fireproof material, the used adhesive and the used dispersing agent are inorganic matters which are not easy to burn, and all the components are flame-retardant or flame-retardant substances, so that the fire resistance grade of the fireproof material can be effectively improved. In addition, in the preparation method, the vitrified micro bubbles, the diatomite and the vermiculite are ball-milled into powder by adopting a ball milling technology, and are easily and uniformly dispersed in the inorganic adhesive, the inorganic dispersing agent and water together with the nano mixture, so that the dispersibility among the raw materials is improved, and the better flame-retardant and fireproof performance is achieved.

The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.