CN111393134A - Silicate system-based modified bentonite body reinforcing agent - Google Patents
Silicate system-based modified bentonite body reinforcing agent Download PDFInfo
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- CN111393134A CN111393134A CN202010101503.3A CN202010101503A CN111393134A CN 111393134 A CN111393134 A CN 111393134A CN 202010101503 A CN202010101503 A CN 202010101503A CN 111393134 A CN111393134 A CN 111393134A
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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
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
- C04B33/131—Inorganic additives
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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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3427—Silicates other than clay, e.g. water glass
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- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3427—Silicates other than clay, e.g. water glass
- C04B2235/3436—Alkaline earth metal silicates, e.g. barium silicate
- C04B2235/3445—Magnesium silicates, e.g. forsterite
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- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/444—Halide containing anions, e.g. bromide, iodate, chlorite
- C04B2235/445—Fluoride containing anions, e.g. fluosilicate
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/447—Phosphates or phosphites, e.g. orthophosphate, hypophosphite
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/61—Mechanical properties, e.g. fracture toughness, hardness, Young's modulus or strength
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- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
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- Silicates, Zeolites, And Molecular Sieves (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a silicate system-based modified bentonite body reinforcing agent, which comprises the following components in parts by weight: 5-15 parts of modified sodium bentonite; 1-5 parts of sodium pyrophosphate; 5-15 parts of sodium silicate; 0.1-1 part of sodium fluosilicate; 0.1 to 1 portion of lithium magnesium silicate sodium salt. According to the invention, bentonite is modified, cations influencing the dispersion performance of the bentonite are treated, so that the bentonite has better dispersion performance, the modified bentonite has better adsorption performance, and sodium silicate, lithium magnesium sodium silicate and other substances have good exchange performance with the cations, so that clay has better plasticity.
Description
Technical Field
The invention relates to the technical field of ceramic industry, in particular to a silicate system-based modified bentonite body reinforcing agent.
Background
The ceramic product is a product with complex shape and large size and mass, and needs to consume a large amount of mineral resources and fuel. The thicker the wall thickness of the ceramic product, the higher the quality, the higher the consumption of raw materials and energy, and the higher the production cost. In recent decades, the ceramic industry in China has been growing at a two-digit rate, and the ceramic plays an irreplaceable role in beautifying the living environment of people and improving the living quality of people, but also causes huge burden on energy and environment. In order to reduce the production cost, reduce the labor intensity, improve the labor efficiency, save limited mineral resources and fuel energy, the necessary requirements for sustainable development of the ceramic industry are needed to develop thin-wall lightweight ceramic products.
The main raw material for preparing the ceramic is clay, and due to the non-regenerability of the clay, the ceramic industry has to use the clay containing more barren materials to produce various ceramic products, however, due to the inherent deficiency of the materials and the thinning of the ceramic products, the produced products have the defects of cracks, unfilled corners, deficient edges and the like, but the thinning of the ceramic products has great advantages in terms of saving resources and reducing emission compared with the traditional ceramic. However, the development of thinner ceramics is also a system engineering, and the ceramic body cannot be replaced by the function of the additive. After the wall thickness of the ceramic blank is reduced, the breaking load is rapidly reduced, and the deformation degree is obviously increased, so that the blank must have higher breaking strength and lower concentricity for reducing the thickness and the weight of the blank.
The bentonite is a non-metal mineral product with montmorillonite as a main mineral component, has strong hygroscopicity and expansibility, can absorb water with volume of 8-15 times of that of the bentonite, and can expand by several times to 30 times; in water medium, bentonite can be dispersed into gel and suspension, and the medium solution has certain viscosity, thixotropy and lubricity, and has strong cation exchange capacity and certain adsorption capacity on various gases, liquids and organic substances. Because the layered structure formed by the montmorillonite unit cell of the bentonite has certain cations, such as Cu, Mg, Na, K and the like, and the functions of the cations and the montmorillonite unit cell are unstable, different cations can link bentonite particles together, and the dispersing performance of the bentonite particles is influenced.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a silicate system-based modified bentonite body reinforcing agent, which solves the traditional problems and can greatly enhance the strength of a ceramic body without influencing the performance of slurry.
The invention is realized by adopting the following technical scheme:
the invention provides a silicate system-based modified bentonite body reinforcing agent, which comprises the following components in parts by weight:
5-15 parts of modified sodium bentonite;
1-5 parts of sodium pyrophosphate;
5-15 parts of sodium silicate;
0.1-1 part of sodium fluosilicate;
0.1 to 1 portion of lithium magnesium silicate sodium salt.
Further, the modified bentonite body reinforcing agent based on the silicate system comprises the following components in parts by weight:
10-15 parts of modified sodium bentonite;
1-3 parts of sodium pyrophosphate;
5-10 parts of sodium silicate;
0.1-1 part of sodium fluosilicate;
0.1 to 1 portion of lithium magnesium silicate sodium salt.
Further, the modified sodium bentonite comprises the following components in parts by weight: 60-80 parts of bentonite; 5-15 parts of a treating agent; 1-10 parts of an inorganic modifier; 20-50 parts of water.
Further, the cation exchange capacity of the modified sodium bentonite is 30mmol/100g-120mmol/100 g.
Further, the modification method of the modified sodium bentonite comprises the following steps:
putting bentonite into a reactor, heating and stirring, slowly adding water and a treating agent into the bentonite in sequence, kneading and stirring for 1-2 h, and heating to 50-80 ℃ to form a first mixed solution;
and adding an inorganic modifier into the first mixed solution, mixing and reacting for 2-3 h at the temperature of 80-120 ℃, taking out the materials, drying, and grinding to obtain the easily-dispersible modified sodium bentonite.
Further, the treating agent is prepared from the following components in a mass ratio of 1-1: 5, and sodium salt.
Further, the sodium salt is one or a combination of sodium carbonate, sodium bicarbonate and sodium silicate.
Further, the inorganic modifier is Al3+Pillaring agent, Fe3+Pillaring agent, Ti4+One of the pillaring agents.
Further, the mass ratio of the sodium silicate to the sodium fluosilicate is 4-8: 1.
further, the mass ratio of the sodium silicate to the lithium magnesium silicate sodium salt is 4-8: 1.
compared with the prior art, the invention has the beneficial effects that:
according to the invention, bentonite is modified, cations influencing the dispersion performance of the bentonite are treated, so that the bentonite has better dispersion performance, the modified bentonite has better adsorption performance, and sodium silicate, lithium magnesium sodium silicate and other substances have good exchange performance with the cations, so that clay has better plasticity.
Detailed Description
The present invention is further described below with reference to specific embodiments, and it should be noted that, without conflict, any combination between the embodiments or technical features described below may form a new embodiment.
The invention provides a silicate system-based modified bentonite body reinforcing agent, which comprises the following components in parts by weight:
5-15 parts of modified sodium bentonite;
1-5 parts of sodium pyrophosphate;
5-15 parts of sodium silicate;
0.1-1 part of sodium fluosilicate;
0.1 to 1 portion of lithium magnesium silicate sodium salt.
Specifically, the modified sodium bentonite comprises the following components in parts by weight: 60-80 parts of bentonite; 5-15 parts of a treating agent; 1-10 parts of an inorganic modifier; 20-50 parts of water. The modification method of the modified sodium bentonite comprises the following steps: putting bentonite into a reactor, heating and stirring, slowly adding water and a treating agent into the bentonite in sequence, kneading and stirring for 1-2 h, and heating to 50-80 ℃ to form a first mixed solution; and adding an inorganic modifier into the first mixed solution, mixing and reacting for 2-3 h at the temperature of 80-120 ℃, taking out the materials, drying, and grinding to obtain the easily-dispersible modified sodium bentonite.
Wherein the treating agent is prepared from the following components in a mass ratio of 1-1: 5, and sodium salt. The sodium salt is one or more of sodium carbonate, sodium bicarbonate and sodium silicate. The inorganic modifier is prepared from AlCl3/FeCl3/TiCl4With NaOH to corresponding pillaring agents, e.g. Al3+Pillaring agent, Fe3+Pillaring agent, Ti4+Pillaring agents, and the like.
The principle of the modified sodium bentonite is that the characteristics of expansibility and interlayer cation exchangeability of bentonite are utilized, ions of insoluble water or slightly soluble water in the bentonite are converted into soluble substances through a treating agent, the treating agent is compounded by ethylenediamine tetraacetic acid and sodium salt, the replacement effect is better, and then metal hydroxyl cations generated by hydrolysis of inorganic metal cations enter the interlayer of the bentonite to increase the interlayer spacing, after the bentonite is modified, the interlayer spacing is obviously increased, the specific surface area is also increased, and the adsorption effect is obviously improved. In one embodiment, the cation exchange capacity of the modified sodium bentonite is 30mmol/100g-120mmol/100 g.
The sodium lithium magnesium silicate has a nano microcrystalline structure and is dispersed in water to form a nano colorless transparent thixotropic gel. The crystal structure unit of the magnesium lithium silicate gel is a minute flake having a thickness in nanometers. The surface of the tablet is coated with exchangeable cations, mainly Na +. When the gel particles are mixed with water, the water is adsorbed to the surface of the flakes in contact with Na +, spreading the gel along the flakes, at which point the particles rapidly swell until the flakes separate. Because the surface of the slice is negatively charged and the end surface is positively charged, the end surface of the separated slice is attracted to the surface of another slice, thereby rapidly forming a colloid structure of a three-dimensional space, namely a card palace structure, and increasing the viscosity of the system.
The preparation process of the lithium magnesium silicate sodium salt comprises the following steps: mixing sodium, magnesium and lithium salt with sodium silicate at a certain speed and temperature to produce amorphous precipitate, treating at high temperature to form part of crystal, filtering, washing, drying and grinding to obtain fine white powder.
Further, the mass ratio of the sodium silicate to the sodium fluosilicate is 4-8: 1; the mass ratio of the sodium silicate to the lithium magnesium silicate sodium salt is 4-8: 1.
preferably, the modified bentonite body reinforcing agent based on the silicate system comprises the following components in parts by weight:
10-15 parts of modified sodium bentonite;
1-3 parts of sodium pyrophosphate;
5-10 parts of sodium silicate;
0.1-1 part of sodium fluosilicate;
0.1 to 1 portion of lithium magnesium silicate sodium salt.
The preparation method of the modified bentonite green body reinforcing agent based on the silicate system comprises the following steps: adding the modified sodium bentonite, sodium pyrophosphate, sodium silicate, sodium fluosilicate, lithium magnesium silicate sodium salt and water into a reaction kettle, heating to 80-120 ℃, stirring at constant temperature for 2-3 h, and then spray drying to obtain the modified bentonite blank reinforcing agent.
The using method of the reinforcing agent comprises the following specific operations: ball milling is carried out on the ceramic blank and the raw materials according to 0.1-0.3 percent of the dry material amount of the ceramic blank, and the ceramic blank and the raw materials can be used for granulation after being uniformly stirred. The reinforcing agent of the invention has small addition amount, the increase range of the green body strength is 0.25MPa-0.6MPa, the influence on the flow rate of slurry is small while the green body strength is increased, and the reinforcing agent can replace clay.
The following are specific examples of the present invention, and raw materials, equipments and the like used in the following examples can be obtained by purchasing them unless otherwise specified.
Example 1
Adding 5 parts of modified sodium bentonite, 1 part of sodium pyrophosphate, 5 parts of sodium silicate, 0.1 part of sodium fluosilicate, 0.1 part of lithium magnesium sodium silicate and water into a reaction kettle, heating to 90 ℃, stirring at constant temperature for 2 hours, and then spray-drying to obtain the modified bentonite blank reinforcing agent.
The method for modifying the modified sodium bentonite comprises the following steps: putting 70 parts of bentonite into a reactor, heating and stirring, slowly adding 50 parts of water and 10 parts of treating agent into the bentonite in turn, kneading and stirring for 1.5h, and heating to 80 ℃ to formA first mixed solution; and adding 3 parts of inorganic modifier into the first mixed solution, mixing and reacting for 3 hours, controlling the temperature at 120 ℃, taking out the materials, drying, and grinding to obtain the modified sodium bentonite easy to disperse. The treating agent is compounded by 1-1 mass ratio of ethylene diamine tetraacetic acid and sodium salt. The sodium salt is sodium carbonate. The inorganic modifier is Al3+A pillaring agent.
Example 2
Example 2 differs from example 1 in that: the reinforcing agent comprises the following components in parts by weight: 10 parts of modified sodium bentonite, 3 parts of sodium pyrophosphate, 10 parts of sodium silicate, 0.5 part of sodium fluosilicate and 0.5 part of lithium magnesium sodium silicate.
Example 3
Example 3 differs from example 1 in that: the reinforcing agent comprises the following components in parts by weight: 15 parts of modified sodium bentonite, 5 parts of sodium pyrophosphate, 15 parts of sodium silicate, 1 part of sodium fluosilicate and 1 part of lithium magnesium silicate sodium salt.
Example 4
Example 4 differs from example 1 in that: the reinforcing agent comprises the following components in parts by weight: 10 parts of modified sodium bentonite, 1 part of sodium pyrophosphate, 5 parts of sodium silicate, 0.1 part of sodium fluosilicate and 0.1 part of lithium magnesium sodium silicate.
Example 5
Example 5 differs from example 1 in that: the reinforcing agent comprises the following components in parts by weight: 12 parts of modified sodium bentonite, 2 parts of sodium pyrophosphate, 8 parts of sodium silicate, 0.5 part of sodium fluosilicate and 0.5 part of lithium magnesium sodium silicate.
Example 6
Example 6 differs from example 1 in that: the reinforcing agent comprises the following components in parts by weight: 15 parts of modified sodium bentonite, 3 parts of sodium pyrophosphate, 10 parts of sodium silicate, 1 part of sodium fluosilicate and 1 part of lithium magnesium silicate sodium salt.
Example 7
Example 7 differs from example 1 in that: the reinforcing agent comprises the following components in parts by weight: 6 parts of modified sodium bentonite, 3 parts of sodium pyrophosphate, 5 parts of sodium silicate, 1 part of sodium fluosilicate and 1 part of lithium magnesium silicate sodium salt.
In the above embodiments, each material is not limited to the above components, and each material may also be composed of other single components or multiple components described in the present invention, and the component parts of each material are not limited to the above parts, and the component parts of each material may also be a combination of other component parts described in the present invention, and are not described herein again.
Comparative example 1
Comparative example 1 is a reinforcing agent, which is different from example 7 in that the raw material of comparative example 1 does not use modified sodium bentonite, but uses conventional bentonite.
Comparative example 2
Comparative example 1 is a reinforcing agent, which is different from example 7 in that the raw material of comparative example 1 does not use lithium magnesium silicate sodium salt.
And (3) performance testing:
(1) test product
Examples 1 to 7 and comparative examples 1 to 2
(2) Experimental methods
According to the using method provided by the invention, the ceramic blank and the raw materials are ball-milled together according to 0.1% of the dry material amount of the ceramic blank to prepare slurry.
Slurry fluidity test: pouring the prepared slurry into a 100ml daubing-4 cup, standing for 3S, recording the time for the slurry to completely flow out by using a stopwatch, controlling the temperature of the slurry at 25 ℃, and taking the average value of three measurements to obtain the flow rate of the slurry.
And (3) green strength test, namely forming the prepared slurry on a test press at the pressure of 10MPa to obtain a test strip of 10mm × 10mm × 50mm, drying, and testing the strength of the test strip by using a three-point bending resistance instrument.
(3) The test results are given in table 1 below.
TABLE 1 test results
| Item | Green strength (MPa) | Fluidity(s) |
| Blank example | 0.36 | 43.5 |
| Comparative example 1 | 0.52 | 40.1 |
| Comparative example 2 | 0.42 | 46.9 |
| Example 1 | 0.61 | 45.2 |
| Example 2 | 0.77 | 44.9 |
| Example 3 | 0.86 | 43.8 |
| Example 4 | 0.65 | 44.5 |
| Example 5 | 0.79 | 44.2 |
| Example 6 | 0.88 | 44.1 |
| Example 7 | 0.96 | 43.1 |
As can be seen from the data in Table 1, compared with comparative examples 1 and 2, the strength of the ceramic blank can be remarkably improved by using a small amount of the reinforcing agent of the invention, the increase range of the blank strength is 0.25MPa-0.6MPa, and the influence on the flow rate of slurry is small while the strength of the blank is increased.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (10)
1. A silicate system-based modified bentonite body reinforcing agent is characterized by comprising the following components in parts by weight:
5-15 parts of modified sodium bentonite;
1-5 parts of sodium pyrophosphate;
5-15 parts of sodium silicate;
0.1-1 part of sodium fluosilicate;
0.1 to 1 portion of lithium magnesium silicate sodium salt.
2. The silicate system-based modified bentonite body enhancer as claimed in claim 1, characterized by comprising the following components in parts by weight:
10-15 parts of modified sodium bentonite;
1-3 parts of sodium pyrophosphate;
5-10 parts of sodium silicate;
0.1-1 part of sodium fluosilicate;
0.1 to 1 portion of lithium magnesium silicate sodium salt.
3. The silicate system-based modified bentonite matrix enhancer as claimed in claim 1, wherein the modified sodium bentonite comprises the following components in parts by weight: 60-80 parts of bentonite; 5-15 parts of a treating agent; 1-10 parts of an inorganic modifier; 20-50 parts of water.
4. The silicate system-based modified bentonite precursor enhancer as claimed in claim 3, wherein the cation exchange capacity of the modified sodium bentonite is 30mmol/100g-120mmol/100 g.
5. The silicate system-based modified bentonite precursor enhancer as claimed in claim 4, wherein the modification method of the modified sodium bentonite comprises the following steps:
putting bentonite into a reactor, heating and stirring, slowly adding water and a treating agent into the bentonite in sequence, kneading and stirring for 1-2 h, and heating to 50-80 ℃ to form a first mixed solution;
and adding an inorganic modifier into the first mixed solution, mixing and reacting for 2-3 h at the temperature of 80-120 ℃, taking out the materials, drying, and grinding to obtain the easily-dispersible modified sodium bentonite.
6. The silicate system-based modified bentonite body enhancer as claimed in claim 3, wherein the treating agent is prepared from a mixture of 1-1: 5, and sodium salt.
7. The silicate system-based modified bentonite body enhancer as claimed in claim 6, wherein the sodium salt is one or more combination of sodium carbonate, sodium bicarbonate and sodium silicate.
8. The silicate system-based modified bentonite body enhancer as claimed in claim 3, wherein the inorganic modifier is Al3+Pillaring agent, Fe3+Pillaring agent, Ti4+One of the pillaring agents.
9. The silicate system-based modified bentonite body enhancer as claimed in claim 1, wherein the mass ratio of the sodium silicate to the sodium fluorosilicate is 4-8: 1.
10. the silicate system-based modified bentonite body enhancer as claimed in claim 1, wherein the mass ratio of the sodium silicate to the lithium magnesium silicate sodium salt is 4-8: 1.
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| CN114436617A (en) * | 2020-11-06 | 2022-05-06 | 必照岩土科技(南京)有限公司 | Lithium magnesium silicate bentonite composite nano material and preparation method thereof |
| CN116768599A (en) * | 2023-06-15 | 2023-09-19 | 东莞市唯美陶瓷工业园有限公司 | Reinforcing slurry for improving strength of ceramic blank, and preparation method and application thereof |
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