CN115594483B - Thermochromic low-temperature sintering colored sand and preparation method thereof - Google Patents
Thermochromic low-temperature sintering colored sand and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/34—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders
- C04B28/344—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders the phosphate binder being present in the starting composition solely as one or more phosphates
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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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00482—Coating or impregnation materials
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Abstract
The invention discloses a thermochromic low-temperature sintering colored sand and a preparation method thereof, wherein copper tailing sand grains are used as base materials, the outer surfaces of the sand grains are wrapped with thermochromic coatings, and the thermochromic coatings comprise: thermochromic pigment, binder, caustic dolomite powder, talc, mineralizer; the thermochromic pigment comprises the following raw materials in parts by mass: 18 parts of formaldehyde-urea mixed solution, 1 part of heat-sensitive dye, 2 parts of bisphenol AF, 7 parts of tetradecanol, 1 part of modifier, 15 parts of 3wt% of Arabic gum solution and 5 parts of 10wt% of ammonium chloride solution; the invention solves the problem of easy adhesion in the process of producing the color sand in the prior art, and the color sand prepared by the invention has rich color system, high color degree, simple preparation process, low sintering temperature and good water resistance, wear resistance and weather resistance.
Description
Technical Field
The invention belongs to the field of coatings, and particularly relates to thermochromic low-temperature sintering colored sand and a preparation method thereof.
Background
The color sand has the advantages of various colors, strong third dimension, good wear resistance, firmness and the like, and is widely applied to building decoration, ink stone aggregate, high-grade paint, ground and roof materials for improving the functionality and the aesthetic property of the materials. The colored sand is prepared by processing natural sand stone as a substrate and various colorants, and is divided into natural colored sand and artificial colored sand; the natural colored sand is prepared from various natural colored ores through processing, has soft color, simple preparation process and strong stereoscopic impression, but the color difference is easy to occur in different batches of products due to the ore difference in each place, and the natural colored sand has smaller hardness and is not wear-resistant, so that the natural colored sand is only suitable for some decorative materials with smaller bearing pressure; the artificial colored sand is obtained by artificially coloring white or light-colored quartz sand, and has the advantages of uniform color, bright color, rich color, high hardness and good wear resistance. Because mine resources are limited, the environment damage can be caused by the excessive exploitation of natural colored sand ore, and the natural colored sand is gradually replaced by artificial colored sand due to poor controllability of the mine sources and difficult control of the product quality, the artificial colored sand is popular with people due to rich colors, stable quality and good weather resistance. The method for manually preparing the color sand has various methods, such as a high-temperature sintering method, a resin curing method, a normal-temperature dyeing method, a ceramic color glaze method and the like, and the color sand prepared by the high-temperature sintering method has the advantages of lasting color, no color change, acid and alkali resistance, high temperature resistance and the like, so the method is widely accepted by the masses.
In the prior art, as in Chinese patent CN104193208B, a high-temperature sintered colored sand and a preparation method thereof are disclosed, and the colored sand prepared by the invention comprises the following components: silicate ore particles and surface colourThe surface toner layer is formed by calcining color paste coated on the surface of silicate mineral grains at high temperature. The preparation method of the colored sand comprises the following steps: selecting and screening silicate ore particles; and (3) preparing color paste: mixing water glass, kaolin, industrial borax and inorganic pigment with water according to the required color condition, and ball milling; mixing the prepared color paste with silicate ore particles in a rotary roller furnace according to the weight ratio, and drying; mixing and drying the materials by a rotary roller furnace, calcining at high temperature, and delivering the calcined materials to an outlet of a calciner; and (5) cooling and storing. Finally cooling to obtain the product high-temperature sintered color sand. The method is easy to operate, can realize continuous production, can easily adjust the color of the color sand, further ensures the consistency of the color sand, and has simple and quick production process, but the color sand prepared by the method needs to be calcined at 600-1100 ℃, has higher requirements on equipment at high temperature, has high energy consumption, and does not accord with the theme of energy conservation and environmental protection advocated by China. And as Chinese patent CN110451835B, a high-wear-resistance low-temperature sintered artificial color sand and a preparation method thereof are disclosed, and the artificial color sand mainly comprises quartz sand, inorganic pigment and an inner and outer double-layer coating agent. Wherein, the quartz sand is 100 parts, the inorganic pigment is 1-2 parts, the inner coating agent is 1-20 parts, and the outer coating agent is 1-20 parts. The fineness of the quartz sand is 40-100 meshes, and the main chemical composition of the quartz sand is SiO 2 90-96％，Al 2 O 3 1-2％，Fe 2 O 3 +K 2 O1-3%. The inner coating agent is a self-made water-based silicon-based modifier, and the outer coating agent is a self-made water-based aluminum-based modifier. And (5) preparing the color sand through low-temperature sintering. The invention can be realized at a lower temperature, and the prepared product has various color and low production cost, and the invention can not well solve the problem of bonding between coated particles only by stirring every 15 minutes in the drying process, and can also cause stripping between pigment and sand grains, thereby further generating the problems of poor quality, low yield and the like of the color sand.
Disclosure of Invention
In order to solve the problems, the invention provides the thermochromic low-temperature sintering colored sand and the preparation method thereof, which not only solve the problem of easy adhesion among sand grains, but also remarkably improve the hardness, the water resistance, the heat resistance and the wear resistance of the colored sand product.
The aim of the invention can be achieved by the following technical scheme:
the thermochromic low-temperature sintering color sand takes 12-32 mesh copper tailing sand grains as a base material, and comprises the following main chemical components: siO (SiO) 2 73.6％，Al 2 O 3 11.7％，CaO 5.4％，MgO 2.8％，Fe 2 O 3 5.3%; and wrapping the thermochromic coating on the outer surface of the copper tailing sand grains. The thermochromic coating further comprises: thermochromic pigment, binder, caustic dolomite powder, talc, mineralizer; wherein the weight portions of the components are as follows: 100 parts of copper tailing sand grains, 8-10 parts of thermochromic pigment, 10-15 parts of binder, 1-2 parts of caustic dolomite powder, 0.5-1 part of talcum and 1-2 parts of mineralizer;
the thermochromic pigment comprises the following raw materials in parts by mass: 18 parts of formaldehyde-urea mixed solution, 1 part of heat-sensitive dye, 2 parts of bisphenol AF, 7 parts of tetradecanol, 1 part of modifier, 15 parts of 3wt% of Arabic gum solution and 5 parts of 10wt% of ammonium chloride solution.
Further, the raw materials of the binder are as follows: 85wt% of phosphoric acid solution, aluminum hydroxide powder, distilled water and modified fly ash, wherein the mass ratio of the components is 20:6:8:1; the preparation process comprises the following steps: adding 85wt% phosphoric acid water solution into distilled water for dilution, adding aluminum hydroxide powder, stirring for 30 minutes at 130 ℃, cooling to room temperature, adding modified fly ash, and stirring for 10 minutes to obtain the modified fly ash.
Further, the modifier of the modified fly ash is a silane coupling agent, the raw materials of the modified fly ash are fly ash and the silane coupling agent, and the mass ratio of the fly ash to the silane coupling agent is 50:3, a step of; the preparation process of the modified fly ash comprises the following steps: drying 100 parts of fly ash, stirring for 10min at 100 ℃, adding 3 parts of silane coupling agent, keeping the ambient temperature at 120 ℃, continuously stirring for 10min, adding 3 parts of silane coupling agent, stirring for 15min, and cooling to room temperature to obtain the modified fly ash.
Further, the heat-sensitive dye is at least one of heat-sensitive green, heat-sensitive yellow, heat-sensitive red and heat-sensitive blue.
Further, the modifier is prepared from absolute ethyl alcohol, distilled water, tetraethyl orthosilicate and phenyl triethoxysilane according to a mass ratio of 504:430:20:1; the preparation process comprises the following steps: mixing absolute ethyl alcohol, distilled water and tetraethyl orthosilicate according to a set proportion, adjusting the pH value of the solution to be 3, stirring for 60 minutes at 60 ℃, adding phenyltriethoxysilane, and stirring for 30 minutes to obtain the modifier.
Further, the mineralizer is alkali ash.
The preparation method of the thermochromic low-temperature sintered colored sand comprises the following steps:
(1) Pretreatment of copper tailing sand grains: selecting waste copper tailings, grinding the copper tailings to be 12-32 meshes in granularity, repeatedly washing the copper tailings to remove surface soluble impurities, and then drying the copper tailings;
(2) Preparation of thermochromic pigment: mixing formalin (formaldehyde content 37 wt%), urea and distilled water according to a mass ratio of 5:2:10, stirring until the mixture is dissolved, adjusting the pH value of the solution to be 8, and finally stirring at 75 ℃ for 60 minutes to obtain formaldehyde-urea mixed solution; mixing a thermosensitive dye, bisphenol AF and tetradecanol according to a set proportion, stirring for 60 minutes at 90 ℃, cooling to 70 ℃, mixing and stirring with a 3wt% acacia solution heated to 70 ℃ for 30 minutes, adding a formaldehyde-urea mixed solution, stirring for 60 minutes, adjusting the pH value of the solution to be 3.5 and stirring for 15 minutes, adding a 10wt% ammonium chloride solution and a modifier and stirring for 50 minutes, adjusting the pH value of the solution to be 2-2.5, stirring for 30 minutes, and cooling to room temperature to obtain a thermochromic pigment;
(3) Preparing color sand: mixing the pretreated copper tailing sand grains with a binder according to a set proportion for 3-5 minutes, starting cold air flow, cooling to-5 ℃ to 10 ℃, adding thermochromic pigment, caustic dolomite powder and talcum, fully mixing for 10-15 minutes, enabling the pigment to be uniformly wrapped on the surface of the copper tailing sand grains, adding 1-2 parts of mineralizer, fully stirring for 5-8 minutes, blowing at 20 ℃, carrying out stirring and drying treatment, fully drying, placing the mixture at 200-280 ℃ for sintering for 60-75 minutes, preserving heat at 80-100 ℃ for 15-20 minutes, discharging, and naturally cooling to obtain the product.
Further, in the preparation process of the colored sand, the rotating speed of the copper tailing sand grains and the thermochromic pigment after being mixed is 1000-1300r/min, the rotating speed of the mineralizer after being added is 800-1000r/min, and the rotating speed of the colored sand after being stirred and dried is 300-500r/min.
Compared with the prior art, the invention has the following technical effects:
1. according to the thermochromic low-temperature sintering colored sand and the preparation method thereof, the modified fly ash in the adhesive is subjected to chemical reaction with the phosphoric acid, so that the linear structure of the adhesive is changed into a three-dimensional structure, the curing is promoted, the temperature of the curing reaction is reduced, the time of the curing reaction is shortened, the curing reaction can be performed even under the condition of room temperature, the energy consumption is reduced, the hardness and the wear resistance of the cured coating are improved, and the waterproof performance of the coating is improved.
2. According to the thermochromic low-temperature sintered color sand and the preparation method thereof, the fly ash modified by the silane coupling agent is added into the adopted binder, and the silane coupling agent and the fly ash undergo a grafting reaction, so that the self-catalysis effect of the binder in the curing reaction can be enhanced, the curing temperature of the binder can be further reduced, the viscosity of the binder can be improved, and the stability of the color sand can be further enhanced.
3. According to the thermochromic low-temperature sintering colored sand and the preparation method thereof, the adopted thermosensitive dye changes into a colored structure when meeting bisphenol AF, and the color of the colored sand can be changed by changing the thermosensitive dye, so that the color system is rich.
4. According to the thermochromic low-temperature sintered color sand and the preparation method thereof, the adopted modifier can reduce the particle size of the thermochromic pigment, and the hydrophobic property of the pigment after film formation can be improved, so that the water resistance of a color sand product is improved.
5. According to the thermochromic low-temperature sintering colored sand and the preparation method thereof, the mineralizer alkali ash can form a solid solution with sand grains, so that the activation of crystal lattices is promoted, the growth of crystals is accelerated, the glossiness of a coating on the surface of the sand grains is improved, and a small amount of alkali ash is added to form a eutectic substance, so that the sintering temperature can be obviously reduced, and the production cost is saved.
6. According to the thermochromic low-temperature sintering colored sand and the preparation method thereof, sand grains and pigment are fully and uniformly mixed by adopting a higher rotating speed in the process of preparing the colored sand, so that the pigment is uniformly coated on the surface of the colored sand; the pigment is mixed with the mineralizer at a slightly high rotating speed, and the mutual coordination of the components in the pigment can reduce the temperature of the curing reaction, so that the curing reaction can be carried out at room temperature, the curing reaction can be accelerated, and the glossiness of the prepared colored sand is obviously improved; and then the color sand is stirred and dried at a lower rotating speed, and under the stirring state, the components in the pigment are mutually matched, so that the adhesive force between the pigment and the sand grains is enhanced, the adhesion between the sand grains can be effectively prevented, and meanwhile, the pigment forms a compact thermochromic coating with good waterproof property, wear resistance and heat resistance on the surface of the sand grains under the action of a binder, thereby not only achieving the effect of saving energy, but also remarkably improving the quality of the prepared color sand.
Drawings
FIG. 1 is a flow chart of a method for preparing thermochromic low-temperature sintered colored sand according to the invention;
FIG. 2 is a sample graph of the colored sand prepared in example 1.
Detailed Description
The invention is further described below in connection with the preferred embodiments, and neither the endpoints of the ranges disclosed in the invention nor any of the values are limited to the precise range or value, and such range or value should be understood to include values near the range or value; for a range of values, one or more new ranges of values can be obtained in combination with each other between the endpoints of each range, between the endpoints of each range and the individual point values, and between the individual point values, and are to be considered as specifically disclosed herein; materials, reagents and the like used in the following examples are commercially available unless otherwise specified; the experimental methods in the following examples are conventional methods unless otherwise specified. The parts of the raw materials in the examples are all parts by mass.
Example 1
The thermochromic low-temperature sintering colored sand is prepared from 100 parts of 32-mesh copper tailing sand grains serving as a base material, wherein the chemical composition of the copper tailing sand grains is as follows: siO (SiO) 2 73.6％，Al 2 O 3 11.7％，CaO 5.4％，MgO 2.8％，Fe 2 O 3 5.3%; the copper tailing sand grains are coated with a thermochromic coating.
The invention adopts the copper tailing sand grains as the base material, and can replace quartz sand due to higher content of silicon oxide in the copper tailings, and the cost of mining and processing raw materials can be saved by replacing conventional quartz sand with the copper tailing sand grains, so that the production cost is greatly reduced, the environment is not damaged, the treatment cost of the tailings can be saved, and a certain contribution is made to the social environment.
The thermochromic coating comprises the following components in parts by mass as shown in table 1:
table 1 thermochromic coating composition
| Thermochromic pigments | 8 parts of |
| Adhesive agent | 10 parts of |
| Caustic dolomite powder | 1 part of |
| Talc | 0.5 part |
| Alkali ash | 1 part of |
The mineralizer alkali ash adopted by the invention can form a solid solution with sand grains, promote lattice activation, accelerate crystal growth, improve the glossiness of a coating on the surface of the sand grains, and the addition of a small amount of alkali ash can obviously reduce the sintering temperature and save the production cost.
The binder comprises the following components in parts by weight as shown in Table 2:
TABLE 2 binder composition
| 85wt% phosphoric acid solution | 5.7 parts of |
| Aluminum hydroxide powder | 1.7 parts of |
| Distilled water | 2.3 parts of |
| Fly ash modified by silane coupling agent | 0.3 part |
The preparation process of the adhesive comprises the following steps: adding 85wt% phosphoric acid water solution into distilled water for dilution, adding aluminum hydroxide powder, stirring for 30 minutes at 130 ℃, cooling to room temperature, adding modified fly ash, and stirring for 10 minutes to obtain the modified fly ash.
The modified fly ash in the binder is the fly ash modified by the silane coupling agent, and the silane coupling agent and the fly ash undergo a grafting reaction, so that the self-catalytic effect of the binder in the curing reaction can be enhanced, the curing temperature of the binder can be further reduced, the viscosity of the binder can be improved, and the stability of the color sand can be further enhanced; and the modified fly ash and phosphoric acid are subjected to chemical reaction, so that the linear structure of the binder is changed into a three-dimensional structure, the curing is promoted, the temperature of the curing reaction is reduced, the time of the curing reaction is shortened, the curing reaction can be performed even under the condition of room temperature, the energy consumption is reduced, the hardness and the wear resistance of the coating after curing can be improved, and the waterproof performance of the coating can be improved.
The thermochromic pigment comprises the following components in parts by mass as shown in Table 3:
TABLE 3 thermochromic pigment Components
The modifier comprises the following components in parts by weight as shown in Table 4:
TABLE 4 modifier Components
| Absolute ethyl alcohol | 0.084 part |
| Distilled water | 0.072 parts |
| Tetraethoxysilane (TEOS) | 0.003 part |
| Phenyl triethoxy silane | 0.001 part |
The preparation process of the modifier comprises the following steps: mixing absolute ethyl alcohol, distilled water and tetraethyl orthosilicate according to the mass ratio, adjusting the pH value of the solution to be 3, stirring for 60 minutes at 60 ℃, adding phenyltriethoxysilane, and stirring for 30 minutes to obtain the modifier.
The modifier adopted by the invention can reduce the particle size of the thermochromic pigment, and can improve the hydrophobic property of the pigment after film formation, thereby improving the water resistance of the color sand product.
The preparation method of the thermochromic low-temperature sintered colored sand comprises the following steps:
(1) Pretreatment of copper tailing sand grains: selecting waste copper tailings, grinding the copper tailings to be 32 meshes in granularity, repeatedly washing 100 parts of copper tailings sand grains to remove surface soluble impurities, and then drying;
(2) Preparation of thermochromic pigment: mixing and stirring formalin, urea and distilled water according to a mass ratio of 5:2:10 until the formalin, the urea and the distilled water are dissolved, adjusting the pH value of the solution to be 8, and finally stirring the mixture at 75 ℃ for 60 minutes to obtain formaldehyde-urea mixed solution; mixing thermal blue, bisphenol AF and tetradecanol according to a set proportion, stirring for 60 minutes at 90 ℃, cooling to 70 ℃, mixing and stirring for 30 minutes with 3wt% of Arabic gum solution heated to 70 ℃, adding formaldehyde-urea mixed solution, stirring for 60 minutes, adjusting the pH value of the solution to be 3.5 and stirring for 15 minutes, adding 10wt% of ammonium chloride solution and modifier and stirring for 50 minutes, adjusting the pH value of the solution to be 2, stirring for 30 minutes, and cooling to room temperature to obtain thermochromic pigment;
(3) Preparing color sand: mixing the pretreated copper tailing sand grains with a binder according to a set proportion for 5 minutes, starting cold air flow, cooling to-5 ℃, adding thermochromic pigment, caustic dolomite powder and talcum, fully mixing for 12 minutes at a rotating speed of 1000r/min to ensure that the pigment is uniformly wrapped on the surface of the copper tailing sand grains, adding alkali ash, fully stirring for 5 minutes at a rotating speed of 900r/min, blowing at 20 ℃, stirring and drying at a rotating speed of 500r/min, fully drying, sintering the mixture at 250 ℃ for 70 minutes, preserving heat at 100 ℃ for 18 minutes, discharging, and naturally cooling to obtain the product.
According to the invention, after sand grains and a binder are fully mixed, the binder and the sand grain surface are fully contacted and adhered together, the viscosity of the binder surface adhered to the sand grains can be reduced by starting cold air flow, caustic dolomite powder and talcum are added and adhered to the sand grain surface together with thermochromic pigment, so that the problem of adhesion between sand grains can be effectively prevented, and the color sand hardness can be improved, meanwhile, the dolomite powder and the talcum are also used as fillers, pigment can be better adhered to the color sand surface, holes are easily generated on the color sand coating surface along with evaporation of water in the solidification reaction process, the product quality is poor, holes generated on the color sand coating surface can be filled by adding the dolomite powder and the talcum, the coating hardness is improved, the color sand quality is improved, then a mineralizer is added, the sand grains are subjected to stirring and drying treatment, the sand grains are further prevented from being adhered together, finally, the temperature is raised to enable the viscosity of the binder surface to be recovered, the pigment is firmly adhered to the surface, the caustic dolomite powder and the talcum powder are added, the sand grain surface is not easy to be adhered, the sand grains are difficult to be adhered, the mineralizer can be formed with the mineralizer, the crystal lattice is enabled to be solidified, the surface is enabled to be reduced, and the sintering temperature is reduced, the sintering temperature is enabled to achieve, and the purposes of saving the crystal lattice can be achieved.
Example 2
The thermochromic low-temperature sintering colored sand is prepared from 100 parts of 24-mesh copper tailing sand grains serving as a base material, wherein the chemical composition of the copper tailing sand grains is as follows: siO (SiO) 2 73.6％，Al 2 O 3 11.7％，CaO 5.4％，MgO 2.8％，Fe 2 O 3 5.3%; the copper tailing sand grains are coated with a thermochromic coating.
The thermochromic coating comprises the following components in parts by mass as shown in Table 5:
table 5 thermochromic coating composition
| Thermochromic pigments | 9 parts of |
| Adhesive agent | 12 parts of |
| Caustic dolomite powder | 1.5 parts by weight |
| Talc | 1 part of |
| Alkali ash | 2 parts of |
The binder comprises the following components in parts by weight as shown in Table 6:
TABLE 6 binder composition
| 85wt% phosphoric acid solution | 6.84 parts |
| Aluminum hydroxide powder | 2.04 parts by weight |
| Distilled water | 2.76 parts |
| Modified by silane coupling agentsFly ash | 0.36 part |
The preparation process of the adhesive comprises the following steps: adding 85wt% phosphoric acid water solution into distilled water for dilution, adding aluminum hydroxide powder, stirring for 30 minutes at 130 ℃, cooling to room temperature, adding modified fly ash, and stirring for 10 minutes to obtain the modified fly ash.
The thermochromic pigment comprises the following components in parts by mass as shown in Table 7:
TABLE 7 thermochromic pigment Components
The modifier comprises the following components in parts by weight as shown in Table 8:
TABLE 8 modifier Components
| Absolute ethyl alcohol | 0.097 part |
| Distilled water | 0.083 part |
| Tetraethoxysilane (TEOS) | 0.0038 parts |
| Phenyl triethoxy silane | 0.0002 part |
The preparation process of the modifier comprises the following steps: mixing absolute ethyl alcohol, distilled water and tetraethyl orthosilicate according to the mass ratio, adjusting the pH value of the solution to be 3, stirring for 60 minutes at 60 ℃, adding phenyltriethoxysilane, and stirring for 30 minutes to obtain the modifier.
The preparation method of the thermochromic low-temperature sintered colored sand comprises the following steps:
(1) Pretreatment of copper tailing sand grains: selecting waste copper tailings, grinding the copper tailings to be 24 meshes, repeatedly washing 100 parts of copper tailings sand grains to remove surface soluble impurities, and then drying;
(2) Preparation of thermochromic pigment: mixing and stirring formalin, urea and distilled water according to a mass ratio of 5:2:10 until the formalin, the urea and the distilled water are dissolved, adjusting the pH value of the solution to be 8, and finally stirring the mixture at 75 ℃ for 60 minutes to obtain formaldehyde-urea mixed solution; mixing the thermosensitive red, the bisphenol AF and the tetradecanol according to a set proportion, stirring for 60 minutes at 90 ℃, cooling to 70 ℃, mixing and stirring for 30 minutes with the 3wt% acacia solution heated to 70 ℃, adding the formaldehyde-urea mixed solution, stirring for 60 minutes, adjusting the pH value of the solution to be 3.5 and stirring for 15 minutes, adding the 10wt% ammonium chloride solution and the modifier and stirring for 50 minutes, adjusting the pH value of the solution to be 2.5, stirring for 30 minutes, and cooling to room temperature to obtain the thermochromic pigment;
(3) Preparing color sand: mixing the pretreated copper tailing sand grains with a binder according to a set proportion for 3 minutes, starting cold air flow, cooling to 0 ℃, adding thermochromic pigment, caustic dolomite powder and talcum, fully mixing for 10 minutes at the rotating speed of 1100r/min to ensure that the pigment is uniformly wrapped on the surface of the copper tailing sand grains, adding alkali ash, fully stirring for 8 minutes at the rotating speed of 800r/min, blowing at 20 ℃, carrying out stirring and drying treatment at the rotating speed of 400r/min, fully drying, sintering the mixture at 200 ℃ for 60 minutes, preserving heat at 90 ℃ for 20 minutes, discharging, and naturally cooling to obtain the product.
Example 3
The thermochromic low-temperature sintering colored sand is prepared from 100 parts of 12-mesh copper tailing sand grains serving as a base material, wherein the chemical composition of the copper tailing sand grains is as follows: siO (SiO) 2 73.6％，Al 2 O 3 11.7％，CaO 5.4％，MgO 2.8％，Fe 2 O 3 5.3%; the copper tailing sand grains are coated with a thermochromic coating.
The thermochromic coating comprises the following components in parts by mass as shown in Table 9:
table 9 thermochromic coating compositions
| Thermochromic pigments | 10 parts of |
| Adhesive agent | 15 parts of |
| Caustic dolomite powder | 2 parts of |
| Talc | 1 part of |
| Alkali ash | 1.5 parts by weight |
The binder comprises the following components in parts by weight as shown in Table 10:
table 10 binder composition
| 85wt% phosphoric acid solution | 8.55 parts |
| Aluminum hydroxide powder | 2.55 parts |
| Distilled water | 3.45 parts |
| Fly ash modified by silane coupling agent | 0.45 part |
The preparation process of the adhesive comprises the following steps: adding 85wt% phosphoric acid water solution into distilled water for dilution, adding aluminum hydroxide powder, stirring for 30 minutes at 130 ℃, cooling to room temperature, adding modified fly ash, and stirring for 10 minutes to obtain the modified fly ash.
The thermochromic pigment comprises the following components in parts by mass as shown in Table 11:
table 11 thermochromic pigment Components
| Formaldehyde-urea mixed solution | 3.673 parts |
| Thermosensitive yellow | 0.205 part |
| Bisphenol AF | 0.408 part |
| Tetradecanol | 1.429 parts |
| Modifying agent | 0.204 part |
| 3wt% gum arabic solution | 3.061 parts |
| 10wt% ammonium chloride solution | 1.02 parts |
The modifier comprises the following components in parts by weight as shown in Table 12:
table 12 modifier Components
| Absolute ethyl alcohol | 0.107 part |
| Distilled water | 0.092 part |
| Tetraethoxysilane (TEOS) | 0.004 part |
| Phenyl triethoxy silane | 0.001 part |
The preparation process of the modifier comprises the following steps: mixing absolute ethyl alcohol, distilled water and tetraethyl orthosilicate according to the mass ratio, adjusting the pH value of the solution to be 3, stirring for 60 minutes at 60 ℃, adding phenyltriethoxysilane, and stirring for 30 minutes to obtain the modifier.
The preparation method of the thermochromic low-temperature sintered colored sand comprises the following steps:
(1) Pretreatment of copper tailing sand grains: selecting waste copper tailings, grinding the copper tailings to be 12 meshes in granularity, repeatedly washing 100 parts of copper tailings sand grains to remove surface soluble impurities, and then drying;
(2) Preparation of thermochromic pigment: mixing and stirring formalin, urea and distilled water according to a mass ratio of 5:2:10 until the formalin, the urea and the distilled water are dissolved, adjusting the pH value of the solution to be 8, and finally stirring the mixture at 75 ℃ for 60 minutes to obtain formaldehyde-urea mixed solution; mixing thermal yellow, bisphenol AF and tetradecanol according to a set proportion, stirring for 60 minutes at 90 ℃, cooling to 70 ℃, mixing and stirring with 3wt% of Arabic gum solution heated to 70 ℃ for 30 minutes, adding formaldehyde-urea mixed solution, stirring for 60 minutes, adjusting the pH value of the solution to be 3.5 and stirring for 15 minutes, adding 10wt% of ammonium chloride solution and modifier and stirring for 50 minutes, adjusting the pH value of the solution to be 2, stirring for 30 minutes, and cooling to room temperature to obtain thermochromic pigment;
(3) Preparing color sand: mixing the pretreated copper tailing sand grains with a binder according to a set proportion for 4 minutes, starting cold air flow, cooling to 10 ℃, adding thermochromic pigment, caustic dolomite powder and talcum, fully mixing for 15 minutes at the rotating speed of 1300r/min to ensure that the pigment is uniformly wrapped on the surface of the copper tailing sand grains, adding alkali ash, fully stirring for 7 minutes at the rotating speed of 1000r/min, blowing at 20 ℃, carrying out stirring and drying treatment at the rotating speed of 500r/min, fully drying, sintering the mixture at 280 ℃ for 75 minutes, preserving heat at 80 ℃ for 15 minutes, discharging, and naturally cooling to obtain the product.
Comparative example 1
Substantially the same as in example 1, but with the following modifications:
in the preparation process of the colored sand, the added binder is not added with modified fly ash.
Comparative example 2
Substantially the same as in example 1, but with the following modifications:
in the preparation process of the colored sand, the mineralizer added into the colored sand is calcium chloride.
Comparative example 3
Substantially the same as in example 1, but with the following modifications:
in the preparation process of the colored sand, caustic dolomite powder and talcum are not added.
Evaluation of effect of implementation
The excellent effects achieved by the present invention are further illustrated by specific experiments.
Firstly, the thermochromic low-temperature sintering color sand prepared by the specific embodiment is respectively prepared into templates, and the templates are subjected to performance test. The specific results are shown below:
appearance performance:
when the examples 1-3 and the comparative examples 1-3 were observed, the colored sand particles of the examples 1-3 and the comparative examples 1-2 were distinguished, and the colored sand of the comparative example 3 had a small amount of bonding between the particles; and the gloss of comparative example 2 is significantly inferior to that of examples 1-3 and comparative examples 1, 3; the thermochromatic low-temperature sintering color sand prepared by the method has good glossiness, and the problem of adhesion among color sand particles can be effectively solved.
Water resistance test:
the water resistance test was carried out for 720 hours for examples 1 to 3 and comparative examples 1 to 3, and the specific test results are shown in the following table:
TABLE 13 Water resistance test Table
| Project | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| 240 hours | No change | No change | No change | No change | No change | No change |
| 480 hours | No change | No change | No change | No change | No change | No change |
| 720 hours | No change | No change | No change | Slight discoloration | Slight discoloration | No change |
It can be observed that the color sand of the examples 1-3 and the comparative example 3 have no obvious change, while the color sand of the comparative examples 1-2 has slight fading, which indicates that the thermochromic low-temperature sintered color sand prepared by the invention has good waterproof performance.
Abrasion resistance test:
the same degree of abrasion resistance test was conducted for examples 1 to 3 and comparative examples 1 to 3, and the specific test results are shown in the following table:
table 14 abrasion resistance test table
| Project | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| First-order friction | No change | No change | No change | No change | No change | No change |
| Two-stage friction | No change | No change | No change | No change | No change | No change |
| Three-stage friction | No change | No change | No change | Slightly fall off | Slightly fall off | No change |
It can be observed that the examples 1-3 and the comparative example 3 have no obvious change, but the coatings of the color sand of the comparative examples 1-2 slightly fall off, which proves that the thermochromic low-temperature sintering color sand prepared by the invention has good wear resistance.
Temperature change test:
the temperature change test was performed by placing examples 1 to 3 and comparative examples 1 to 3 in the same environment at a temperature ranging from 0℃to 40℃and the specific test results are shown in the following table:
table 15 temperature change test table
It can be observed that at 0℃to 13℃the colour of example 1 and comparative examples 1 to 3 is blue, the colour of example 2 is red and the colour of example 3 is yellow; at 13-28 ℃, the color of each of examples 1 and comparative examples 1-3 is lightened by blue, the color of example 2 is lightened by red, and the color of example 3 is lightened by yellow; at 28 ℃ to 40 ℃, the colors of example 1 and comparative examples 1 to 3 are all changed to light purple, the color of example 2 is changed to light pink, and the color of example 3 is changed to white; from the above phenomena, the thermochromic low-temperature sintered color sand prepared by the method has rich color systems and good color changing performance along with temperature change.
Compared with the prior art, the method has the advantages of low cost, low sintering temperature, simple process and the like, can be used for producing various specifications and colors of color sand, and can meet the technical requirements on water resistance, weather resistance, wear resistance, freezing resistance and the like of the color sand. In the process, the thermal-sensitive pigment is selected, and different pigment formulas are adopted, so that color sand products with different colors can be obtained, the color system is rich, and the requirements of the masses can be met. The use of the binder can enable the thermochromic pigment to be wetted on the surface of the copper tailing sand grains, uniformly dispersed and firmly adhered on the surface of the sand grains, and the added modified fly ash can reduce the curing reaction temperature of the binder, so that the binder can undergo curing reaction at room temperature, and the aim of saving energy is achieved. The added mineralizer alkali ash can reduce the sintering temperature of the color sand and save energy. The color sand prepared by the invention has the characteristics of good water resistance, high temperature resistance, large adhesive force and the like, and can enable pigment to be better adhered on the surface of sand grains.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and improvements could be made by those skilled in the art without departing from the inventive concept, which falls within the scope of the present invention.
Claims (4)
1. The thermochromic low-temperature sintered color sand is characterized in that: taking 12-32 mesh copper tailing sand grains as a base material, and wrapping a thermochromic coating on the outer surfaces of the copper tailing sand grains, wherein the thermochromic coating comprises the following raw materials: thermochromic pigment, binder, caustic dolomite powder, talc, mineralizer; wherein the weight portions of the components are as follows: 100 parts of copper tailing sand grains, 8-10 parts of thermochromic pigment, 10-15 parts of binder, 1-2 parts of caustic dolomite powder, 0.5-1 part of talcum and 1-2 parts of mineralizer;
the thermochromic pigment comprises the following raw materials in parts by mass: 18 parts of formaldehyde-urea mixed solution, 1 part of heat-sensitive dye, 2 parts of bisphenol AF, 7 parts of tetradecanol, 1 part of modifier, 15 parts of 3wt% of Arabic gum solution and 5 parts of 10wt% of ammonium chloride solution;
the raw materials of the adhesive are as follows: 85wt% of phosphoric acid solution, aluminum hydroxide powder, distilled water and modified fly ash, wherein the mass ratio of the components is 20:6:8:1; the preparation process comprises the following steps: adding 85wt% phosphoric acid solution into distilled water for dilution, adding aluminum hydroxide powder, stirring for 30 minutes at 130 ℃, cooling to room temperature, adding modified fly ash, and stirring for 10 minutes to obtain the modified fly ash; the modifier of the modified fly ash is a silane coupling agent;
the modifier is prepared from absolute ethyl alcohol, distilled water, tetraethyl orthosilicate and phenyl triethoxysilane according to the mass ratio of 504:430:20:1; the preparation process comprises the following steps: mixing absolute ethyl alcohol, distilled water and tetraethyl orthosilicate according to a set proportion, adjusting the pH value of the solution to be 3, stirring for 60 minutes at 60 ℃, adding phenyltriethoxysilane, and stirring for 30 minutes to obtain the modifier;
the preparation method of the thermochromic low-temperature sintering colored sand comprises the following steps of:
(1) Pretreatment of copper tailing sand grains: selecting waste copper tailings, grinding the copper tailings to be 12-32 meshes in granularity, repeatedly washing the copper tailings to remove surface soluble impurities, and then drying the copper tailings;
(2) Preparation of thermochromic pigment: mixing and stirring formalin, urea and distilled water according to a mass ratio of 5:2:10 until the formalin, the urea and the distilled water are dissolved, adjusting the pH value of the solution to be 8, and finally stirring the mixture at 75 ℃ for 60 minutes to obtain formaldehyde-urea mixed solution; mixing a thermosensitive dye, bisphenol AF and tetradecanol according to a set proportion, stirring for 60 minutes at 90 ℃, cooling to 70 ℃, mixing and stirring with a 3wt% acacia solution heated to 70 ℃ for 30 minutes, adding a formaldehyde-urea mixed solution, stirring for 60 minutes, adjusting the pH value of the solution to be 3.5 and stirring for 15 minutes, adding a 10wt% ammonium chloride solution and a modifier and stirring for 50 minutes, adjusting the pH value of the solution to be 2-2.5, stirring for 30 minutes, and cooling to room temperature to obtain a thermochromic pigment;
(3) Preparing color sand: mixing the pretreated copper tailing sand grains with a binder according to a set proportion for 3-5 minutes, starting cold air flow, cooling to-5 ℃ to 10 ℃, adding thermochromic pigment, caustic dolomite powder and talcum, fully mixing for 10-15 minutes, enabling the pigment to be uniformly wrapped on the surface of the copper tailing sand grains, adding 1-2 parts of mineralizer, fully stirring for 5-8 minutes, blowing at 20 ℃, carrying out stirring and drying treatment, fully drying, placing the mixture at 200-280 ℃ for sintering for 60-75 minutes, preserving heat at 80-100 ℃ for 15-20 minutes, discharging, and naturally cooling to obtain the product.
2. The thermochromic low-temperature sintered colored sand of claim 1, wherein the heat-sensitive dye is at least one of heat-sensitive green, heat-sensitive yellow, heat-sensitive red and heat-sensitive blue.
3. The thermochromic low-temperature sintered colored sand of claim 1, wherein the mineralizer is an alkali ash.
4. The thermochromic low-temperature sintered colored sand according to claim 1, wherein in the preparation process of the colored sand, the rotation speed of the copper tailing sand grains mixed with the thermochromic pigment is 1000-1300r/min, the rotation speed of the mineralizer added is 800-1000r/min, and the rotation speed of the colored sand subjected to stirring and drying is 300-500r/min.
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