阅读说明：本技术 基于多孔方石英粉的抗菌人造石制备方法及其抗菌人造石 (Preparation method of antibacterial artificial stone based on porous cristobalite powder and antibacterial artificial stone ) 是由 高忠麟 舒诚 于 2020-08-12 设计创作，主要内容包括：本发明公开了基于多孔方石英粉的抗菌人造石制备方法及其抗菌人造石,一种基于多孔方石英粉的抗菌人造石制备方法,包括制备多孔方石英粉、附着杀菌离子、覆载二氧化硅凝胶层、球磨和压制和热固化处理步骤。本技术方案提出一种基于多孔方石英粉的抗菌人造石制备方法,有利于提高人造石的抗菌率,且制备过程能耗低,成本低,以克服现有技术中的不足之处。进而提出一种上述基于多孔方石英粉的抗菌人造石制备方法制备的抗菌人造石,其抗菌效果好。(The invention discloses a preparation method of an antibacterial artificial stone based on porous cristobalite powder and the antibacterial artificial stone, and the preparation method of the antibacterial artificial stone based on the porous cristobalite powder comprises the steps of preparing the porous cristobalite powder, attaching bactericidal ions, coating a silicon dioxide gel layer, ball milling, pressing and thermosetting treatment. The technical scheme provides the preparation method of the antibacterial artificial stone based on the porous cristobalite powder, which is beneficial to improving the antibacterial rate of the artificial stone, and the preparation process has low energy consumption and low cost so as to overcome the defects in the prior art. Further, the antibacterial artificial stone prepared by the preparation method based on the porous cristobalite powder is good in antibacterial effect.)

1. The preparation method of the antibacterial artificial stone based on the porous cristobalite powder is characterized by comprising the following steps of:

preparing porous cristobalite powder: mixing diatomite and sodium fluosilicate, mixing and stirring a sodium chloride solution with the mixed diatomite and sodium fluosilicate to form a mixture A, and roasting the mixture A after the mixture A is dried to obtain porous cristobalite powder;

attaching bactericidal ions: mixing silver nitrate and zinc nitrate, adding water to prepare a sterilizing solution, soaking porous cristobalite powder in the sterilizing solution, and drying and roasting the porous cristobalite powder after soaking to obtain porous cristobalite powder attached with sterilizing ions;

coating a silica gel layer: mixing a sodium silicate solution and a nitric acid solution until the pH value of a titration neutralization reaction is 6-8, mixing the porous cristobalite powder attached with bactericidal ions with a mixed solution of the sodium silicate solution and the nitric acid to form a mixture C, and drying and baking the mixture C to obtain porous cristobalite powder coated with a silicon dioxide gel layer;

ball milling: adding the porous cristobalite powder coated with the silica gel layer into a ball mill for ball milling to form antibacterial micro powder;

pressing and heat curing treatment: and mixing the antibacterial micro powder with artificial stone filler and a binder, and performing pressing and thermosetting treatment to form the antibacterial artificial stone.

2. The method for preparing an antibacterial artificial stone based on porous cristobalite powder according to claim 1, wherein the method comprises the following steps: according to the mass ratio, the mixing ratio of the diatomite, the sodium fluosilicate and the sodium chloride solution is (400-600): (3-7): 600, and the concentration of the sodium chloride solution is 15-17%.

3. The method for preparing an antibacterial artificial stone based on porous cristobalite powder according to claim 2, wherein the method comprises the following steps: according to the mass percentage, the silicon dioxide content of the diatomite is more than or equal to 88 percent, and the ferric oxide content of the diatomite is less than or equal to 3 percent.

4. The method for preparing an antibacterial artificial stone based on porous cristobalite powder according to claim 1, wherein the method comprises the following steps: in the step of preparing the porous cristobalite powder, the roasting temperature of the porous cristobalite powder is 800-1000 ℃, and the roasting time of the porous cristobalite powder is 11-13 hours.

5. The method for preparing an antibacterial artificial stone based on porous cristobalite powder according to claim 1, wherein the method comprises the following steps: in the step of attaching the bactericidal ions, the mixing ratio of the silver nitrate, the zinc nitrate and the water is 10: 30: (100-200).

6. The method for preparing an antibacterial artificial stone based on porous cristobalite powder according to claim 1, wherein the method comprises the following steps: in the step of ball milling, the fineness of the antibacterial micro powder is 180-220 meshes.

7. The method for preparing an antibacterial artificial stone based on porous cristobalite powder according to claim 1, wherein the method comprises the following steps:

according to the mass ratio, the mixing ratio of the antibacterial micro powder to the artificial stone filler to the binder is (8-10): (75-80): (13-15).

8. The method for preparing an antibacterial artificial stone based on porous cristobalite powder according to claim 7, wherein the method comprises the following steps: the adhesive comprises the following raw materials in parts by weight: 8-12 parts of unsaturated resin, 1-2 parts of curing agent, 0-1 part of accelerator and 1-2 parts of coupling agent.

9. The method for preparing an antibacterial artificial stone based on porous cristobalite powder according to claim 8, wherein the method comprises the steps of: the unsaturated resin is o-benzene unsaturated resin, the curing agent is cobalt octoate, the accelerator is methyl ethyl ketone peroxide, and the coupling agent is KH 570;

the artificial stone filler is any one of quartz stone filler, marble filler or feldspar filler.

10. An antibacterial artificial stone is characterized in that: the method for preparing the antibacterial artificial stone based on the porous cristobalite powder according to any one of claims 1 to 9.

Technical Field

The invention relates to the field of antibacterial artificial stones, in particular to a preparation method of an antibacterial artificial stone based on porous cristobalite powder and an antibacterial artificial stone thereof.

Background

With the technical progress of stone materials, consumers have increasingly high requirements on the influence of stone materials on the home environment, and particularly, stone materials with the functions of sterilization and antibiosis have become very popular abroad and have a basic requirement on stone materials.

In the conventional techniques for producing artificial antibacterial stones, resins are widely used as carriers for the antibacterial agents, and some carriers for the antibacterial agents include glass and zeolite, but porous cristobalite has not been used as a carrier for the antibacterial agents.

Disclosure of Invention

The invention aims to provide a preparation method of an antibacterial artificial stone based on porous cristobalite powder, which is beneficial to improving the antibacterial rate of the artificial stone, and has low energy consumption and low cost in the preparation process so as to overcome the defects in the prior art.

The invention also aims to provide the antibacterial artificial stone prepared by the preparation method of the antibacterial artificial stone based on the porous cristobalite powder, which has a good antibacterial effect.

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

a preparation method of an antibacterial artificial stone based on porous cristobalite powder comprises the following steps:

preparing porous cristobalite powder: mixing diatomite and sodium fluosilicate, mixing and stirring a sodium chloride solution with the mixed diatomite and sodium fluosilicate to form a mixture A, and roasting the mixture A after the mixture A is dried to obtain porous cristobalite powder;

attaching bactericidal ions: mixing silver nitrate and zinc nitrate, adding water to prepare a sterilizing solution, soaking porous cristobalite powder in the sterilizing solution, and drying and roasting the porous cristobalite powder after soaking to obtain porous cristobalite powder attached with sterilizing ions;

coating a silica gel layer: mixing a sodium silicate solution and a nitric acid solution until the pH value of a titration neutralization reaction is 6-8, mixing the porous cristobalite powder attached with bactericidal ions with a mixed solution of the sodium silicate solution and the nitric acid to form a mixture C, and drying and baking the mixture C to obtain porous cristobalite powder coated with a silicon dioxide gel layer;

ball milling: adding the porous cristobalite powder coated with the silica gel layer into a ball mill for ball milling to form antibacterial micro powder;

pressing and heat curing treatment: and mixing the antibacterial micro powder with artificial stone filler and a binder, and performing pressing and thermosetting treatment to form the antibacterial artificial stone.

Preferably, the mixing ratio of the diatomite, the sodium fluosilicate and the sodium chloride solution is (400-600): (3-7): 600, and the concentration of the sodium chloride solution is 15-17%.

Preferably, according to the mass percentage, the silicon dioxide content of the diatomite is more than or equal to 88 percent, and the ferric oxide content of the diatomite is less than or equal to 3 percent.

Preferably, in the step of preparing the porous cristobalite powder, the roasting temperature of the porous cristobalite powder is 800-1000 ℃, and the roasting time of the porous cristobalite powder is 11-13 hours.

Preferably, in the step of attaching the bactericidal ions, the mixing ratio of the silver nitrate, the zinc nitrate and the water is 10: 30: (100-200).

Preferably, in the step of ball milling, the fineness of the antibacterial micro powder is 180-220 meshes.

Preferably, the mixing ratio of the antibacterial micro powder to the artificial stone filler to the binder is (8-10): (75-80): (13-15).

Preferably, the binder consists of the following raw material components in parts by mass: 8-12 parts of unsaturated resin, 1-2 parts of curing agent, 0-1 part of accelerator and 1-2 parts of coupling agent.

Preferably, the unsaturated resin is o-benzene type unsaturated resin, the curing agent is cobalt octoate, the accelerator is methyl ethyl ketone peroxide, and the coupling agent is KH 570;

the artificial stone filler is any one of quartz stone filler, marble filler or feldspar filler.

An antibacterial artificial stone is prepared by the preparation method of the antibacterial artificial stone based on the porous cristobalite powder.

The invention has the beneficial effects that: the technical scheme provides the preparation method of the antibacterial artificial stone based on the porous cristobalite powder, which is beneficial to improving the antibacterial rate of the artificial stone, and the preparation process has low energy consumption and low cost so as to overcome the defects in the prior art. Further, the antibacterial artificial stone prepared by the preparation method based on the porous cristobalite powder is good in antibacterial effect.

Drawings

The drawings are further illustrative of the invention and the content of the drawings does not constitute any limitation of the invention.

FIG. 1 is an X-ray diffraction pattern of porous cristobalite powder in the step of preparing the porous cristobalite powder according to the method for preparing an antibacterial artificial stone based on the porous cristobalite powder of the present invention.

Detailed Description

A preparation method of an antibacterial artificial stone based on porous cristobalite powder comprises the following steps:

preparing porous cristobalite powder: mixing diatomite and sodium fluosilicate, mixing and stirring a sodium chloride solution with the mixed diatomite and sodium fluosilicate to form a mixture A, and roasting the mixture A after the mixture A is dried to obtain porous cristobalite powder;

attaching bactericidal ions: mixing silver nitrate and zinc nitrate, adding water to prepare a sterilizing solution, soaking porous cristobalite powder in the sterilizing solution, and drying and roasting the porous cristobalite powder after soaking to obtain porous cristobalite powder attached with sterilizing ions;

coating a silica gel layer: mixing a sodium silicate solution and a nitric acid solution until the pH value of a titration neutralization reaction is 6-8, mixing the porous cristobalite powder attached with bactericidal ions with a mixed solution of the sodium silicate solution and the nitric acid to form a mixture C, and drying and baking the mixture C to obtain porous cristobalite powder coated with a silicon dioxide gel layer;

ball milling: adding the porous cristobalite powder coated with the silica gel layer into a ball mill for ball milling to form antibacterial micro powder;

pressing and heat curing treatment: and mixing the antibacterial micro powder with artificial stone filler and a binder, and performing pressing and thermosetting treatment to form the antibacterial artificial stone.

In the technology of manufacturing antibacterial artificial stone, resin is widely used as a carrier of the antibacterial agent, glass and zeolite are used as carriers of the antibacterial agent, and porous cristobalite is not used as the carrier of the antibacterial agent.

According to the technical scheme, the preparation method of the antibacterial artificial stone based on the porous cristobalite powder adopts the cheap porous diatomite with large specific surface area, strong adsorption performance on various metal ions and high chemical stability as the raw material, and silicon dioxide (SiO) in the diatomite is sintered₂Glassy state) into cristobalite (SiO)₂Tetragonal phase), on the premise of keeping the original porous and adsorption performance of the diatomite, the hardness of the sintered diatomite is improved from the original Mohs hardness of 1-1.5 to 6.5 after the diatomite is converted into cristobalite, the density of the diatomite reaches 1.3-1.45 g/cm3, and the specific surface area reaches 30-40 m²(ii) in terms of/g, as shown in FIG. 1. The porous cristobalite obtained by sintering the diatomite reserves the adsorption performance of the diatomite on various metal ions, and can be used as a better carrier of bactericidal ions. The improvement of the surface porosity of the cristobalite crystal particles is beneficial to storing a large amount of bactericidal ions, thereby ensuring the release concentration and the sustained release capacity of the bactericidal ions. The strength and hardness of the cristobalite crystal are improved, and the influence on the quality of the artificial stone caused by the introduction of the diatomite is avoided. Furthermore, sodium fluosilicate and sodium chloride are mineralizers, and are fired together with diatomite, so that the reduction of the conversion temperature of the cristobalite phase is facilitated, and the energy consumption and the production cost in the preparation process can be effectively reduced.

Further, according to the technical scheme, after the silver nitrate and the zinc nitrate are mixed, water is added to prepare a sterilizing solution, the porous cristobalite powder is soaked in the sterilizing solution, and after the soaking is finished, the porous cristobalite powder is dried and roasted to obtain the porous cristobalite powder attached with sterilizing ions.

Furthermore, the technical scheme also comprises that a silica gel layer is coated on the porous cristobalite powder attached with the bactericidal ions and serves as a carrier of the bactericidal ions, so that after the bactericidal ions with dissolubility are dissolved out from the surface of the carrier powder, the bactericidal ions are kept on the surface of the carrier in a centralized manner under the action of the silica gel layer.

Preferably, in an embodiment of the present technical solution, the step of coating the silica gel layer includes: the sodium silicate solution is prepared from 1 part of sodium silicate and 20 parts of water, and the nitric acid solution is prepared from 1 part of nitric acid and 10 parts of water. Mixing a sodium silicate solution and a nitric acid solution until the pH value of the titration neutralization reaction is 7, mixing 800-1000 parts of porous cristobalite powder attached with bactericidal ions with 120-250 parts of a mixed solution of the sodium silicate solution and the nitric acid to form a mixture C, aging the mixture C for 20 minutes in a constant-temperature environment of 60 ℃, filtering and washing, drying in a constant-temperature environment of 105 ℃, crushing into powder, and baking in a muffle furnace at 600 ℃ for 1 hour.

Preferably, the activation and drying steps are also included between the ball milling and pressing and the heat curing treatment: activating the antibacterial micro powder by using an activating solution, and then putting the activated antibacterial micro powder into an oven for drying treatment; wherein the activating solution consists of the following raw material components: 70% of methanol, 10% of water and 20% of surfactant.

In order to uniformly disperse the antibacterial micro powder in the artificial stone raw material, reduce the deposition phenomenon of the antibacterial micro powder and enhance the dispersion and bonding strength of the antibacterial micro powder in the artificial stone raw material, the technical scheme firstly activates the antibacterial micro powder by using an activation solution. Specifically, the activating solution adopted by the technical scheme comprises 70% of methanol, 10% of water and 20% of surfactant. Firstly, mixing 70% of methanol and 10% of water solution to form a mixed solution, then adjusting the pH value of the mixed solution to 4-5 with acetic acid for dilution, then adding 20% of surfactant to form an activated solution, putting the antibacterial micro powder into a rotary cylinder for spraying with the activated solution, and finally putting the antibacterial powder sprayed with the activated solution into a 110 ℃ oven for drying treatment for 3 hours. Preferably, the surfactant is KH570, i.e. gamma-methacryloxypropyltrimethoxysilane.

Further, the mixing ratio of the diatomite, the sodium fluosilicate and the sodium chloride solution is (400-600): (3-7): 600, and the concentration of the sodium chloride solution is 15-17%.

In the technical scheme, the introduction of the sodium fluosilicate and the sodium chloride is beneficial to reducing the conversion temperature of the cristobalite phase, so that the energy consumption and the production cost in the preparation process can be effectively reduced, and when the addition amounts of the sodium fluosilicate and the sodium chloride are too low, the improvement of the conversion rate of the cristobalite phase is not facilitated, and the reduction of the sterilization effect is easily caused; when the addition amounts of sodium fluorosilicate and sodium chloride are too high, the alkali metal sodium easily reacts with diatomaceous earth to form a glassy state, so that a cristobalite phase cannot be formed.

Further, according to the mass percentage, the silicon dioxide content of the diatomite is more than or equal to 88 percent, and the ferric oxide content of the diatomite is less than or equal to 3 percent.

In the technical scheme, the diatomite with the silicon dioxide content of 88% or more needs to be selected, and if the diatomite with the silicon dioxide content of less than 88% is selected, a glass phase is easy to appear in the firing process, so that the cristobalite conversion rate is reduced, and even the cristobalite phase is not generated.

Furthermore, in the technical scheme of the invention, the diatomite with the ferric oxide content of below 0.3% is selected, and when the ferric oxide content in the diatomite is too high, the whiteness of the fired cristobalite is low, and the requirements of manufacturers or consumers on white or light-colored antibacterial artificial stones cannot be met.

Further, in the step of preparing the porous cristobalite powder, the calcination temperature of the porous cristobalite powder is 800 to 1000 ℃, and the calcination time of the porous cristobalite powder is 11 to 13 hours.

The specific surface area of the porous cristobalite is mainly reserved by the original loose property, the particle irregularity and the existence of porosity of the diatomite, and the size and the number of the pore diameters can be changed along with the change of the sintering temperature or the change of the heat preservation time, so that the specific surface area of the antibacterial micropowder is changed together.

In order to enable the fired porous cristobalite powder to have a certain porosity, facilitate the attachment of bactericidal ions and ensure the bactericidal effect of the antibacterial micro powder, the roasting temperature of the porous cristobalite powder is limited to 800-1000 ℃, and the roasting time of the porous cristobalite powder is limited to 11-13 hours.

Preferably, in the step of preparing the porous cristobalite powder, the calcination temperature of the porous cristobalite powder is 1000 ℃, and the calcination time of the porous cristobalite powder is 12 hours.

In the step of attaching the bactericidal ions, the mixing ratio of the silver nitrate, the zinc nitrate and the water is 10: 30: (100-200).

In an embodiment of the present technical solution, a mixing ratio of silver nitrate, zinc nitrate and water is 10: 30: (100-200), the porous cristobalite powder is favorably attached with more bactericidal ions, so that the bactericidal effect of the antibacterial micro powder is ensured.

Further, in the step of ball milling, the fineness of the antibacterial micro powder is 180-220 meshes.

According to the technical scheme, the fineness of the antibacterial micro powder is limited to 180-220 meshes, the antibacterial micro powder is introduced into the artificial stone and can be used as a bactericide to ensure a better sterilizing effect, and the antibacterial micro powder is also used as a filler of stone, so that the applicability of the antibacterial micro powder is improved.

Preferably, the fineness of the antibacterial micro powder is 200 meshes.

Further, according to the mass ratio, the mixing ratio of the antibacterial micro powder, the artificial stone filler and the binder is (8-10): (75-80): (13-15).

In the technical scheme, the mixing proportion of the antibacterial micro powder, the artificial stone filler and the binder is defined as (8-10): (75-80): (13-15), which is beneficial to the antibacterial artificial stone to achieve the best sterilization effect.

Further, the binder consists of the following raw material components in parts by mass: 8-12 parts of unsaturated resin, 1-2 parts of curing agent, 0-1 part of accelerator and 1-2 parts of coupling agent.

The adhesive in the technical scheme consists of unsaturated resin, a curing agent, an accelerant and a coupling agent, wherein the unsaturated resin is the main adhesive component of the artificial stone and is responsible for adhering the artificial stone filler into stone with high strength. The curing agent, also called initiator, can generate free radicals to initiate the polymerization reaction between the styrene monomer in the unsaturated resin and the unsaturated resin to form the thermosetting resin after being decomposed. The accelerator can help the curing agent to accelerate the curing reaction and shorten the curing time. The coupling agent plays a role in combining the inorganic material with organic resin after the surface of the inorganic material is activated.

Further, the unsaturated resin is o-benzene type unsaturated resin, the curing agent is cobalt octoate, the accelerator is methyl ethyl ketone peroxide, and the coupling agent is KH 570;

the artificial stone filler is any one of quartz stone filler, marble filler or feldspar filler.

The unsaturated resin generally has an o-benzene type, an m-benzene type and a p-benzene type, and the technical scheme ensures that the o-benzene type unsaturated resin is beneficial to bonding the artificial stone filler into a stone with high strength, and has low cost and good effect.

The technical scheme is that cobalt octoate is added into a binder formula as an accelerator, so that the curing agent can generate enough free radicals to meet the requirements of curing reaction.

Because the technical scheme is to produce the artificial stone, the main component of the artificial stone is silicon dioxide, and in order to match the coupling agent with the raw material, KH570 (gamma-methacryloxypropyltrimethoxysilane) is adopted as the coupling agent in the technical scheme.

Further, the artificial stone filler in the technical scheme can be any one of quartz stone filler, marble filler or feldspar filler.

Preferably, the quartz stone filler comprises the following raw material components: 60-75 parts of quartz sand, 25-35 parts of quartz powder and 0-5 parts of inorganic metal oxide colorant, wherein the fineness of the quartz sand is less than or equal to 100 meshes, and the fineness of the quartz powder is more than or equal to 325 meshes; the marble filler comprises the following raw material components:

specifically, the quartz stone filler of the technical scheme is prepared by grading quartz sand with the fineness of less than or equal to 100 meshes and quartz powder with the fineness of more than or equal to 325 meshes, so that the smallest gap of the quartz stone is favorably ensured, the hardness and the strength of the quartz stone are enhanced, the using amount of unsaturated resin is reduced, and the production cost of the quartz stone is reduced. The quartz stone filler also comprises 0-5 parts of inorganic metal oxide colorant, so that the artificial stone can be colored, and the use experience of consumers is improved. More preferably, the inorganic metal oxide colorant is iron oxide.

Preferably, the marble filler comprises the following raw material components: 60-70 parts of marble powder, 60-75 parts of limestone sand, 60-75 parts of calcite sand, 60-75 parts of dolomite sand, 25-40 parts of marble powder, 25-40 parts of limestone powder, 25-40 parts of calcite powder, 25-40 parts of dolomite powder, 0-3 parts of titanium dioxide, 0-4 parts of inorganic metal oxide colorant and 0-2 parts of carbon powder.

Preferably, the feldspar filler comprises the following raw material components: 40-75 parts of feldspar sand, 20-40 parts of marble sand, 0-30 parts of quartz sand, 25-40 parts of feldspar powder, 0-30 parts of marble powder, 0-20 parts of quartz powder, 0-5 parts of titanium dioxide, 0-6 parts of inorganic metal oxide colorant and 0-4 parts of carbon powder.

An antibacterial artificial stone is prepared by the preparation method of the antibacterial artificial stone based on the porous cristobalite powder.

The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.