CN109665781B

CN109665781B - Inorganic nano silicon ground material and preparation method thereof

Info

Publication number: CN109665781B
Application number: CN201910113800.7A
Authority: CN
Inventors: 郭绪平; 郭芋伶
Original assignee: Chengdu Shunjiameiheng New Material Co ltd
Current assignee: Chengdu shunjiameiheng New Material Co., Ltd
Priority date: 2019-02-14
Filing date: 2019-02-14
Publication date: 2021-03-26
Anticipated expiration: 2039-02-14
Also published as: CN109665781A

Abstract

The invention discloses an inorganic nano silicon ground material and a preparation method thereof, wherein the material comprises the following raw materials in parts by weight: 32-37 parts of ordinary portland cement with the strength grade of 42.5, 32-37 parts of composite portland cement with the strength grade of 32.5, 25-28 parts of heavy calcium carbonate, 6-10 parts of modified nano-silica, 3-6 parts of shells, 3-6 parts of mica, 3-6 parts of colored stone, 3-6 parts of colored sand, 3-6 parts of colored glass and a certain amount of cellulose ether, water reducing agent, latex powder, retarder and the like.

Description

Inorganic nano silicon ground material and preparation method thereof

Technical Field

The invention belongs to the field of building materials, and particularly relates to an inorganic nano-silicon floor material and a preparation method thereof.

Background

With the extension of the cementing material components to the nanometer scale, the application of the nanometer material in the cement-based material becomes the research focus of the current building material, for example, nanometer active silica, nanometer calcium carbonate, nanometer titanium dioxide, nanometer carbon black, carbon nanotube, nanometer kaolin and the like are all applied in the cement-based ground material, and the application examples prove that the mechanical properties, especially the compression resistance and the fracture resistance, of the cement mortar can be improved, and the durability can be obviously improved.

The data prove that the nano material (such as nano mineral powder) can fill fine gaps in the whole structure, so that the compactness is improved, and the impermeability of the cement-based material is obviously enhanced, so that the nano material is particularly suitable for engineering structures in coastal areas and can effectively resist long-term erosion of chloride. However, the cement-based material has extremely high requirements on the particle size of raw materials, needs a large amount of auxiliary gel materials with high fineness (1-5 μm) and silicate cement clinker with medium fineness (3-32 μm), has high production difficulty and extremely high cost, and cannot be prepared by directly adding water during use due to poor dispersibility of the nano materials, and needs a special dispersing method, so that a plurality of preparation steps are required, and the use is inconvenient.

Therefore, there is still a need to develop a cement-based ground material with low requirements for raw materials, especially particle size, good corrosion resistance and permeability resistance, which is easy to produce and practical, and has low cost, so as to prolong the service life, meet the requirements of special sites, and expand the application range.

Disclosure of Invention

The invention aims to solve the technical problems and provides a cement-based ground material with good corrosion resistance and permeability resistance, which has the advantages of compression resistance, fracture resistance, good durability, greatly improved corrosion resistance of the ground, low requirement on the particle size of raw materials, easily available raw materials, convenience in production and use and low cost.

In order to achieve the above purpose, the invention provides the following technical scheme:

the invention provides an inorganic nano-silicon floor material which is prepared from the following raw materials in parts by weight:

wherein the particle sizes of all raw materials are not more than 60 mu m, and the preparation method of the modified nano silicon dioxide comprises the following steps: dissolving stearic acid and hydroxypropyl methyl cellulose in 60-70% ethanol solution at 50-70 ℃, adding nano silicon dioxide, carrying out heat preservation and ultrasonic treatment for 2-3 hours, carrying out suction filtration, washing the obtained solid with absolute ethyl alcohol, then washing with water, and drying to obtain the compound.

In a preferred embodiment of the invention, the viscosity of the hydroxypropyl methylcellulose is 20000-30000 mPas, and the modified nano-silica prepared in the viscosity range has better stability and is not easy to be denatured by environment such as temperature and pH value change.

In a preferred embodiment of the invention, the weight ratio of the stearic acid to the hydroxypropyl methyl cellulose to the nano silicon dioxide is 0.15-0.2: 0.1-0.15: 1-1.2. The modified nano silicon dioxide prepared within the weight ratio range has better dispersity and is not easy to agglomerate.

In the preferred embodiment of the invention, the weight ratio of stearic acid, hydroxypropyl methylcellulose and nano silicon dioxide is 0.2:0.15:1, so that the nano silicon dioxide is more easily and uniformly dispersed in components such as cement concrete and the like in use and is not easy to generate discreteness with other materials after water is added.

In a preferred embodiment of the invention, the latex powder is acronal P5033, and compared with other latex powders, the acronal P5033 obviously increases the tensile strength and the elongation at break of the body of the floor material, and meanwhile, the self-leveling breaking strength is obviously improved, the elastic modulus of the self-leveling floor material is properly reduced, and the compression resistance and the fracture resistance are further improved.

In a preferred embodiment of the invention, the retarder is citric acid, and compared with retarders such as tartaric acid and sodium gluconate, the retarder has the lowest citric acid mixing amount, is not easy to lose fluidity and strength, and improves construction operability.

In a preferred embodiment of the present invention, the defoaming agent is a silicone-based defoaming agent, which can more rapidly eliminate bubbles caused by stirring or construction.

In a preferred embodiment of the invention, the ground material is prepared from the following raw materials in parts by weight:

the inorganic nano silicon ground material prepared by the components and the proportion has higher compression strength and rupture strength, smaller porosity of a cement body, more compact internal structure and strong material bonding force, thereby having higher impermeability and corrosion resistance.

The invention also provides a preferable preparation method of the ground material, which comprises the following steps: all the raw materials are mixed evenly, water accounting for 22 to 25 percent of the total weight of the mixture is added, and the mixture is stirred evenly.

In summary, compared with the prior art, the invention has the following beneficial effects:

(1) the research of the applicant of the invention finds that the nano silicon dioxide modified by stearic acid and hydroxypropyl methylcellulose has better filling performance on a porous structure of concrete, stronger sealing capability and better cohesiveness with a base material, and the prepared cement-based ground has obvious impermeability and corrosion resistance, has low requirement on the particle size of the raw material, is easy to obtain the raw material, and greatly reduces the production cost.

(2) Because of the requirement of construction environment, the ground material is often required to be added with mica, shell, color stone and other components, but when the cement mortar takes the shell, the mica and the like as one of the aggregate components, the flaky structure is easy to peel off, the fusion of the cement and other components can be influenced, and the cement and the nano material are prevented from forming a colloidal structure, so that the ground material with high strength and strong impermeability is still difficult to form by the raw material containing the mica even under the action of the nano material.

(3) When the traditional cement-based ground material containing the nano material is used, in order to better disperse the nano material in various raw materials, a special dispersing method is usually needed, so that the process steps are multiple, the condition requirement is higher, and the use is very inconvenient.

(4) The invention mixes ordinary portland cement with the strength grade of 42.5 and composite portland cement with the strength grade of 32.5 to prepare the ground material, breaks through the limitation of the traditional preparation of cement with the strength grade of 42.5 and above, can still obtain high compression strength and rupture strength even if prepared by using cement with lower strength under the comprehensive action of the modified nano-silica material, and the low-strength cement material has lower price compared with the high-strength cement material, thereby greatly reducing the production cost.

Detailed Description

The present invention will be described in further detail with reference to specific examples. It should be understood that the scope of the above-described subject matter is not limited to the following examples, and any techniques implemented based on the disclosure of the present invention are within the scope of the present invention.

Comparative example 1

An inorganic nano silicon floor material comprises the following raw materials in parts by weight:

components	Parts by weight
		Portland cement of strength grade 42.5 (15 μm)	37 portions of
Slag (60 μm)	20 portions of
		Silica fume (15 μm)	4.5 parts of
Fly ash (60 mu m)	30 portions of
		Gypsum (15 μm)	3.5 parts of

The components are mixed evenly, water accounting for 25 percent of the total weight of the mixture is added, and the mixture is stirred evenly.

Comparative example 2

Comparative example 3

components	Parts by weight
		Portland cement of strength grade 42.5 (15 μm)	37 portions of
Slag (3 μm)	20 portions of
		Silica fume (0.5 μm)	4.5 parts of
Fly ash (60 mu m)	30 portions of
		Gypsum (15 μm)	3.5 parts of
Mica (60 μm)	4 portions of
		Shell (60 μm)	2 portions of

Comparative example 4

components	Parts by weight
		Portland cement of strength grade 42.5	34 portions of
Composite portland cement with strength grade of 42.5	34 portions of
		Ground calcium carbonate	26 portions of
Nano silicon dioxide	8 portions of
		Shell	5 portions of
Mica	5 portions of
		Methyl cellulose ether (viscosity of 10000-15000 mPa)·s)	0.2 part
Lithium sulfate	0.5 portion
		Calcium aluminate	0.3 part
2651F	0.3 part
		AcronalP5033	2 portions of
Citric acid	0.2 part
		Fluorosiloxanes	0.3 part

Wherein the particle sizes of all the raw materials are within the range of 15-60 mu m, the components are uniformly mixed, water accounting for 25% of the total weight of the mixture is added, and the mixture is uniformly stirred.

Comparative example 5

A floor material was prepared according to the raw material composition and preparation method described in comparative example 4, except that modified nano-silica was used instead of nano-silica, and the preparation method of the modified nano-silica was: mixing 30 parts of polypropylene, 55 parts of nano-silicon dioxide and a proper amount of water, uniformly stirring, forming wet granules, extruding and granulating by an extruder, and then diluting and mixing the granules and 10 parts of polypropylene to obtain the polypropylene composite material.

Comparative example 6

A floor material was prepared according to the raw material composition and preparation method described in comparative example 4, except that instead of the nano-silica, a modified nano-silica was used, the modified nano-silica beingThe preparation method of the rice silica comprises the following steps: adding 0.5g acetic acid dropwise into 200g polyether solution, stirring in 40 deg.C water bath for 15min, and adding 5gH dropwise₂O₂And 4.5g of vinyltriethoxysilane, then 12.4g of acrylic acid, 0.81g of vitamin C, 0.84g of mercaptopropionic acid and 51g of water are dropwise added, the mixture is dropwise added for 85min, the temperature is kept for 15min in a 40 ℃ water bath, a 3.5mM sodium hydroxide solution is dropwise added to obtain a modifier PCE, the nano-silica sol and the modifier PCE are weighed according to the mass ratio of 4:1, the modifier is dropwise added into the nano-silica sol within 30min, the nano-silica sol is reacted for 4h in a 40 ℃ water bath, and then the mixture is dialyzed and purified to obtain the modified nano-silica.

Comparative example 7

the particle size of all the raw materials is 15-60 mu m, and the preparation method of the modified nano silicon dioxide comprises the following steps: dissolving stearic acid in 70% ethanol solution at 50 deg.C, adding nano-silica, maintaining temperature and ultrasonic treating for 3 hr, filtering, washing the obtained solid with anhydrous ethanol, washing with water, and drying. Weighing the raw material components in the table, uniformly mixing the components, adding water accounting for 22 percent of the total weight of the mixture, and uniformly stirring.

Example 1

components	Parts by weight
		Portland cement of strength grade 42.5	32 portions of
Composite portland cement with strength grade of 32.5	37 portions of
		Ground calcium carbonate	28 portions of
Modified nano silicon dioxide	10 portions of
		Shell	6 portions of
Mica	3 portions of
		Color stone	6 portions of
Color sand	6 portions of
		Color glass	3 portions of
Hydroxyethyl cellulose ether (viscosity of 30000-40000 mPa s)	0.3 part
		Lithium sulfate	0.4 portion of
Calcium aluminate	0.2 part
		SP-409	0.4 portion of
DA1410	2.2 parts of
		Tartaric acid	0.25 part
Polymethylcyclotetrasiloxane	0.35 part

The particle size of all the raw materials is 15-60 mu m, and the preparation method of the modified nano silicon dioxide comprises the following steps: dissolving stearic acid and hydroxypropyl methylcellulose (15000 mPas) in 60% ethanol solution at 70 ℃, adding nano silicon dioxide, wherein the weight ratio of stearic acid to hydroxypropyl methylcellulose to nano silicon dioxide is 0.15:0.1:1.2, carrying out heat preservation and ultrasonic treatment for 3 hours, carrying out suction filtration, washing the obtained solid with absolute ethyl alcohol, then washing with water, and drying to obtain the compound. Weighing the raw material components in the table, uniformly mixing the components, adding water accounting for 25 percent of the total weight of the mixture, and uniformly stirring.

Example 2

components	Parts by weight
		Portland cement of strength grade 42.5	37 portions of
Composite portland cement with strength grade of 32.5	32 portions of
		Ground calcium carbonate	25 portions of
Modified nano silicon dioxide	6 portions of
		Shell	3 portions of
Mica	6 portions of
		Color stone	3 portions of
Color sand	3 portions of
		Color glass	6 portions of
Methyl cellulose ether (viscosity 10000 to 15000 mPas)	0.2 part
		Lithium sulfate	0.5 portion
Calcium aluminate	0.3 part
		3701	0.3 part
TS605	2 portions of
		Citric acid	0.2 part
Fluorosiloxanes	0.3 part

The particle size of all the raw materials is 15-60 mu m, and the preparation method of the modified nano silicon dioxide comprises the following steps: the preparation method of the modified nano silicon dioxide comprises the following steps: dissolving stearic acid and hydroxypropyl methylcellulose (20000 mPas) in 70% ethanol solution at 50 ℃, adding nano silicon dioxide, wherein the weight ratio of stearic acid to hydroxypropyl methylcellulose to nano silicon dioxide is 0.2:0.15:1, keeping the temperature and performing ultrasonic treatment for 2 hours, performing suction filtration, washing the obtained solid with absolute ethyl alcohol, then washing with water, and drying to obtain the product. Weighing the raw material components in the table, uniformly mixing the components, adding water accounting for 22 percent of the total weight of the mixture, and uniformly stirring.

Example 3

the particle size of all the raw materials is 15-60 mu m, and the preparation method of the modified nano silicon dioxide comprises the following steps: dissolving stearic acid and hydroxypropyl methylcellulose (30000 mPas) in 70% ethanol solution at 50 ℃, adding nano silicon dioxide, wherein the weight ratio of stearic acid to hydroxypropyl methylcellulose to nano silicon dioxide is 0.2:0.15:1, carrying out heat preservation and ultrasonic treatment for 2 hours, carrying out suction filtration, washing the obtained solid with absolute ethyl alcohol, then washing with water, and drying to obtain the compound. Weighing the raw material components in the table, uniformly mixing the components, adding water accounting for 25 percent of the total weight of the mixture, and uniformly stirring.

Example 4

The modified nano-silica is prepared according to the method of the embodiment 3, the raw material components are weighed according to the embodiment 3, the water reducing agent, the lithium sulfate, the calcium aluminate and the cellulose ether are firstly dissolved in 20 parts of water to prepare dispersion liquid, then the modified nano-silica is added into the dispersion liquid, the mixture is placed into a high-shear mixing stirrer to be stirred at a high speed for 30min, then the mixture is mixed with other raw materials, water accounting for 20 percent of the total weight of the mixture is added, and the mixture is stirred uniformly.

The performance of the floor materials prepared in the comparative examples 1-7 and the examples 1-4 is tested according to the test methods of concrete quality control standard GB/50164-2011 and test method standard GB/T50082-2009 for long-term performance and durability of common concrete, and the test results are shown in the following tables.

It can be seen from the test results that when the particle size of part of the raw materials is too large (for example, about 60 μm), it is difficult to form a floor material with high impermeability and corrosion resistance, even when the particle size of most of the raw materials is in a lower range (for example, about 15 μm), if the raw materials are mixed with a sheet-like structural material such as mica, it is still difficult to form a compact floor material, and the nano modified cement prepared by the conventional method (for example, nano silica added, nano silica modified by polypropylene and other materials, etc.) can not fully fill up the ground pores in the case of the raw materials containing mica, and the impermeability and corrosion resistance are poor, while by adopting the component formula of the invention, the nano silica modified by stearic acid and hypromellose can overcome the above defects, and the cement structure is still very easy to compact in the presence of mica and shell, thereby realizing high strength, high impermeability and high corrosion resistance.

Claims

1. An inorganic nano-silicon floor material is characterized in that the floor material is prepared from the following raw materials in parts by weight:

32-37 parts of ordinary portland cement with the strength grade of 42.5, 32-37 parts of composite portland cement with the strength grade of 32.5, 25-28 parts of heavy calcium carbonate, 6-10 parts of modified nano-silica, 3-6 parts of shells, 3-6 parts of mica, 3-6 parts of colored stone, 3-6 parts of colored sand, 3-6 parts of colored glass, 0.2-0.3 part of cellulose ether, 0.4-0.6 part of lithium sulfate, 0.2-0.3 part of calcium aluminate, 0.2-0.4 part of polycarboxylic acid water reducing agent, 1.8-2.2 parts of latex powder, 0.15-0.25 part of retarder and 0.25-0.35 part of defoaming agent;

2. The inorganic nanosilicon flooring material according to claim 1, wherein the hydroxypropylmethylcellulose has a viscosity of 20000 to 30000 mPa-s.

3. The inorganic nano-silicon floor material according to claim 2, wherein the weight ratio of stearic acid, hydroxypropyl methylcellulose and nano-silicon dioxide is 0.15-0.2: 0.1-0.15: 1-1.2.

4. The inorganic nanosilicon flooring material of claim 2, wherein the weight ratio of stearic acid, hydroxypropyl methylcellulose and nanosilicon dioxide is 0.2:0.15: 1.

5. The inorganic nano-silicon floor material according to any one of claims 1 to 4, wherein the latex powder is Acronal P5033.

6. The inorganic nanosilica floor material of any of claims 1 to 4, characterized in that the retarder is citric acid.

7. The inorganic nanosilica floor material according to any of claims 1 to 4, characterized in that the defoaming agent is a silicone-based defoaming agent.

8. The inorganic nano-silicon floor material according to any one of claims 1 to 4, wherein the floor material is prepared from the following raw materials in parts by weight:

34 parts of ordinary portland cement with the strength grade of 42.5, 34 parts of composite portland cement with the strength grade of 32.5, 26 parts of ground limestone, 8 parts of modified nano-silica, 5 parts of shell, 5 parts of mica, 5 parts of colored stone, 5 parts of colored sand, 5 parts of colored glass, 0.2 part of methyl cellulose ether with the viscosity of 10000-15000 mPa & s, 0.5 part of lithium sulfate, 0.3 part of calcium aluminate, 0.3 part of 2651F, 0.32 part of Acronal P50332 part, 0.2 part of citric acid and 0.3 part of fluorosilicone.

9. The inorganic nanosilicon flooring material of any of claims 1-4, characterized in that the flooring material is prepared by a method comprising: all the raw materials are uniformly mixed, water accounting for 22-25% of the total weight of the mixture is added, and the mixture is uniformly stirred.