CN110723905A - Brown high-strength reagent bottle glass material and preparation method thereof - Google Patents
Brown high-strength reagent bottle glass material and preparation method thereof Download PDFInfo
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- CN110723905A CN110723905A CN201911069508.6A CN201911069508A CN110723905A CN 110723905 A CN110723905 A CN 110723905A CN 201911069508 A CN201911069508 A CN 201911069508A CN 110723905 A CN110723905 A CN 110723905A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/002—Use of waste materials, e.g. slags
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/04—Opacifiers, e.g. fluorides or phosphates; Pigments
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/02—Compositions for glass with special properties for coloured glass
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Abstract
The invention discloses a brown high-strength reagent bottle glass material and a preparation method thereof, and the brown high-strength reagent bottle glass material comprises components such as zinc oxide, boron trioxide, silicon dioxide, aluminum oxide, an additive, calcium oxide and the like, wherein the silicon dioxide is used as a main framework for forming glass and exists in a glass network generation form, and silica tetrahedral groups form an irregular continuous network structure of the glass; the diboron trioxide mainly exists in the form of boron-oxygen tetrahedrons and boron-oxygen triangles, and forms a network structure of the glass together with silicon-oxygen tetrahedrons of the silicon dioxide; according to the invention, the high-strength brown reagent bottle glass is prepared by adjusting the content of each component and changing the components. The invention has reasonable component design and simple process operation, not only effectively realizes the preparation of the brown high-strength glass frit, but also adds the components such as rare earth oxide and the like, so that the prepared reagent bottle glass frit has better hydrophobic property, excellent acid and alkali resistance and higher practicability.
Description
Technical Field
The invention relates to the technical field of glass processing, in particular to brown high-strength reagent bottle glass frit and a preparation method thereof.
Background
The borosilicate glass has good fire resistance and high physical strength, and compared with common glass, the borosilicate glass has no toxic or side effect, and the mechanical property, the thermal stability, the water resistance, the alkali resistance, the acid resistance and other properties are greatly improved. Borosilicate glass is an important material for the manufacture of high durability glassware, such as beakers and test tubes. Of course, it has many applications, such as vacuum tubes, aquarium heaters, flashlight lenses, professional lighters, pipes, glass ball art, high quality beverage glassware, solar heat-utilizing vacuum tubes, etc.
In some production medicaments or chemical industry, the multi-purpose borosilicate glass reagent bottle is stored, chemical reagents in the borosilicate glass reagent bottle are difficult to avoid spilling and leaking when in use, so that the borosilicate glass reagent bottle is required to have higher chemical stability, acid resistance and alkali resistance, and the strength of the reagent bottle has certain requirements, which is a problem to be solved urgently.
Disclosure of Invention
The invention aims to provide brown high-strength reagent bottle glass frit and a preparation method thereof, and aims to solve the problems in the prior art.
In order to achieve the purpose, the invention provides the following technical scheme:
the brown high-strength reagent bottle glass material comprises the following raw material components: 30-40 parts of zinc oxide, 20-30 parts of boron trioxide, 20-35 parts of silicon dioxide, 5-10 parts of aluminum oxide, 1-3 parts of additive, 0.8-1.8 parts of calcium oxide, 0.5-2 parts of potassium oxide, 2-4 parts of sodium oxide, 3-12 parts of brown glass slag and 3-7 parts of brown organic pigment.
Preferably, the glass frit further comprises the following raw material components: 9-27 parts of sodium alginate, 3-10 parts of 2-thenoyl trifluoroacetone, 2-8 parts of europium chloride, 3-8 parts of gelatin, 3-6 parts of calcium carbonate and 8-18 parts of surface treating agent.
The invention discloses a brown high-strength reagent bottle glass material which comprises components such as zinc oxide, boron trioxide, silicon dioxide, aluminum oxide, an additive, calcium oxide and the like, wherein the silicon dioxide is used as a main framework for forming glass and exists in a glass network generation form, and silica tetrahedral groups form an irregular continuous network structure of the glass; the diboron trioxide mainly exists in the form of boron-oxygen tetrahedrons and boron-oxygen triangles, and forms a network structure of the glass together with silicon-oxygen tetrahedrons of the silicon dioxide; zinc oxide exists in a glass network structure as a network exosome oxide, and is formed and exists in a zinc-oxygen octahedron mode; the high-strength brown reagent bottle glass is prepared by adjusting the content of each component and changing the components.
In the invention, an additive is also added in the preparation process of the reagent bottle glass, wherein the additive is rare earth oxide and is any one or a mixture of more of neodymium oxide, yttrium oxide and gadolinium oxide; the rare earth oxide doped reagent bottle glass has excellent chemical stability, and the rare earth oxide has an aggregation effect on other components in the reagent bottle glass, so that the acid resistance and the alkali resistance of the reagent bottle glass can be effectively improved.
Preferably, the surface treatment agent comprises the following raw material components: by weight, 6-14 parts of cerium oxide, 10-30 parts of lanthanum nitrate solution and 5-20 parts of dodecafluoroheptyl propyl trimethoxy silicon.
Preferably, the additive is any one or a mixture of more of neodymium oxide, yttrium oxide and gadolinium oxide.
When the glass is prepared, sodium alginate, 2-thenoyl trifluoroacetone, europium chloride, gelatin and calcium carbonate are added, the sodium alginate can perform chemical reaction with the calcium carbonate, molecular chains are crosslinked and wound to form hydrogel with a three-dimensional network structure, but the aperture of single sodium alginate gel is larger, because the gelatin pair is added for blending, the gelatin has better compatibility and can be combined with the sodium alginate to form a tighter gel network, and meanwhile, due to the hydrogen bond action among the gelatin molecules and between the gelatin molecules and the sodium alginate, the gel network is further tight; when the glass matrix is prepared, the gel network and the glass network structure can be mutually wound and combined, so that the structural compactness of the glass matrix is improved, and the strength, the mechanical property and the chemical stability of the prepared reagent bottle glass are improved.
The invention also designs a surface treating agent for treating the surface of the prepared glass substrate, wherein the glass substrate is treated by cerium oxide suspension, cerium oxide nanoparticles have positive charges, and the surface of the glass substrate can have a large number of hydroxyl groups after being cleaned, so that under the action of the charges, the cerium oxide particles can be adsorbed on the surface of the glass and are combined by covalent bonds, and the surface roughness of the glass substrate is improved; and then treating the glass by using a lanthanum nitrate solution, constructing a nano structure on the surface of a glass substrate by using a hydrothermal method, and performing self-assembly modification by using dodecafluoroheptyl propyl trimethoxy silicon to form a layer of super-hydrophobic protective film on the surface of the glass substrate, so that the surface of the reagent bottle glass has excellent hydrophobic property, and the service life of the glass is prolonged.
Preferably, the preparation method of the brown high-strength reagent bottle glass frit comprises the following steps:
1) preparing raw materials;
2) melting to obtain a glass matrix;
3) carrying out surface treatment on the glass substrate by using a surface treating agent;
4) and finishing the operation to obtain a finished product.
Preferably, the method comprises the following steps:
1) preparing raw materials:
2) melting to obtain a glass matrix:
a) putting the 2-thenoyl trifluoroacetone prepared in the step 1) into a beaker, dissolving with absolute ethyl alcohol, adding a sodium hydroxide solution, adjusting the pH to 7.5-8.5, adding the europium chloride prepared in the step 1), heating for reaction, spin-drying reaction liquid after the reaction is finished, washing, filtering, and vacuum-drying to obtain a material A;
b) stirring the sodium alginate prepared in the step 1) at normal temperature until the sodium alginate is completely dissolved to form sodium alginate sol; dissolving the gelatin prepared in the step 1) in water bath, slowly dropping the sodium alginate sol into the gelatin, stirring and mixing, adding calcium carbonate, and continuously stirring to obtain mixed gel; then the mixed gel is dehydrated in vacuum and is placed in an ethanol solvent for soaking to obtain a material B;
c) dissolving the material A prepared in the step 2) with absolute ethyl alcohol, then putting the material A into the material B prepared in the step 3), stirring at normal temperature for 24-26h, performing suction filtration, sequentially soaking the materials in distilled water, absolute ethyl alcohol, DMF (dimethyl formamide) and acetone for 1-1.5h each time, and filtering and washing after soaking; soaking in ethanol solution to obtain material C;
d) mixing and stirring the zinc oxide, boron trioxide, silicon dioxide, aluminum oxide, calcium oxide, potassium oxide, sodium oxide, brown glass slag and brown organic pigment prepared in the step 1) at a high speed, adding the material C prepared in the step C), continuously stirring, putting the mixture into a glass melting furnace, melting the mixture into molten glass by adopting an all-electric melting method, heating to 1400-1600 ℃, clarifying, homogenizing, and cooling the molten glass to 1250 ℃ to obtain a glass substrate;
3) the surface treating agent is used for carrying out surface treatment on the glass substrate:
a) taking the glass substrate prepared in the step 2), cleaning, taking the cerium oxide prepared in the step 1), preparing a cerium oxide suspension, diluting, putting the glass substrate into the cerium oxide suspension, soaking for 20-30min, rinsing with deionized water, and drying with nitrogen;
b) taking the dried glass substrate, putting the glass substrate into a high-pressure reaction kettle, adding the lanthanum nitrate solution prepared in the step 1), sealing the high-pressure kettle, putting the high-pressure kettle into a drying box, keeping the temperature at 115-125 ℃, taking out the glass substrate after hydrothermal for 3-3.5h, and cleaning and drying the glass substrate; dissolving the dodecafluoroheptyl propyl trimethoxy silicon prepared in the step 1) in absolute ethyl alcohol, stirring to be uniform, soaking the hydrothermal glass substrate in the dodecafluoroheptyl propyl trimethoxy silicon solution in a thermostatic water bath at the temperature of 25-35 ℃ for 24-26 hours, taking out the glass substrate, baking and curing in an oven, and cooling to room temperature;
4) cleaning and drying to obtain a finished product.
Preferably, the method comprises the following steps:
1) preparing raw materials:
A. weighing zinc oxide, boron trioxide, silicon dioxide, aluminum oxide, calcium oxide, potassium oxide, sodium oxide, brown glass residue and brown organic pigment according to a proportion for later use;
B. weighing sodium alginate, 2-thenoyltrifluoroacetone, europium chloride, gelatin, calcium carbonate, cerium oxide, lanthanum nitrate solution and dodecafluoroheptyl propyl trimethoxy silicon in proportion for later use; preparing materials of each component in the step 1), so that operators can conveniently perform subsequent reaction treatment;
2) melting to obtain a glass matrix:
a) putting the 2-thenoyltrifluoroacetone prepared in the step 1) into a beaker, dissolving with absolute ethanol, adding a sodium hydroxide solution, adjusting the pH to 7.5-8.5, adding the europium chloride prepared in the step 1), heating for reaction for 12-14h, spin-drying the reaction solution, washing, filtering, and vacuum-drying to obtain a material A; in the step a) of the step 2), europium chloride and 2-thenoyl trifluoroacetone react to generate a binary rare earth complex, and the complex can be combined with sodium alginate to improve the comprehensive performance of gel;
b) stirring the sodium alginate prepared in the step 1) at normal temperature until the sodium alginate is completely dissolved to form sodium alginate sol; dissolving the gelatin prepared in the step 1) in water bath at 55-65 ℃, slowly dropping the sodium alginate sol into the gelatin, stirring and mixing for 25-35min, adding calcium carbonate, and continuously stirring for 30-40min to obtain mixed gel; vacuum dehydrating the mixed gel, and soaking in ethanol solvent for 25-35min to obtain material B; in the step b) of the step 2), sodium alginate and gelatin are mutually wound and combined to form a cross-linked network structure, and the cross-linked network structure can be mutually combined with a subsequently generated glass network system structure so as to improve the structural stability and compactness of the reagent bottle glass;
c) dissolving the material A prepared in the step 2) with absolute ethyl alcohol, then putting the material A into the material B prepared in the step 3), stirring at normal temperature for 24-26h, performing suction filtration, sequentially soaking the materials in distilled water, absolute ethyl alcohol, DMF (dimethyl formamide) and acetone for 1-1.5h each time, and filtering and washing after soaking; soaking in ethanol solution for 1-2h to obtain material C; in the step 3), the binary rare earth complex and the mixed gel network generated in the step b) are mutually combined, so that the comprehensive performance of the binary rare earth complex is improved;
d) mixing and stirring the zinc oxide, boron trioxide, silicon dioxide, aluminum oxide, calcium oxide, potassium oxide, sodium oxide, brown glass slag and brown organic pigment prepared in the step 1) at a high speed for 20-30min, adding the material C prepared in the step C), continuously stirring for 30-40min, putting the mixture into a glass melting furnace, melting the mixture into molten glass by adopting an all-electric melting method, heating to 1400-1600 ℃, clarifying, homogenizing, and cooling the molten glass to 1150-1250 ℃ to obtain a glass substrate; mixing the prepared composite material C with raw materials of all components of the glass, adding rare earth oxide, and melting to obtain a glass matrix;
3) the surface treating agent is used for carrying out surface treatment on the glass substrate:
a) taking the glass substrate prepared in the step 2), cleaning, taking the cerium oxide prepared in the step 1), preparing a cerium oxide suspension, diluting, putting the glass substrate into the cerium oxide suspension, soaking for 20-30min, rinsing with deionized water, and drying with nitrogen; in the step a), the surface of the prepared glass substrate is pretreated by cerium oxide suspension, so that the surface roughness of the glass substrate is improved;
b) taking the dried glass substrate, putting the glass substrate into a high-pressure reaction kettle, adding the lanthanum nitrate solution prepared in the step 1), sealing the high-pressure kettle, putting the high-pressure kettle into a drying box, keeping the temperature at 115-125 ℃, taking out the glass substrate after hydrothermal for 3-3.5h, and cleaning and drying the glass substrate; dissolving the dodecafluoroheptyl propyl trimethoxy silicon prepared in the step 1) in absolute ethyl alcohol, stirring for 2-3h until the solution is uniform, soaking the hydrothermal glass substrate in the dodecafluoroheptyl propyl trimethoxy silicon solution for 24-26h under the condition of a constant-temperature water bath at 25-35 ℃, taking out the glass substrate, baking the glass substrate in an oven at the temperature of 150-; in the step b), a nano network is constructed on the surface of a glass matrix through hydrothermal treatment of a lanthanum nitrate solution, and then self-assembly modification is carried out through a dodecafluoroheptyl propyl trimethoxy silicon solution to form a super-hydrophobic film, so that the prepared glass material has excellent hydrophobic performance;
4) cleaning and drying to obtain a finished product.
Preferably, in the step a) of the step 3), the glass substrate is firstly placed in an ultraviolet-ozone cleaning instrument for cleaning for 20-30min, then is ultrasonically cleaned for 20-30min by acetone, then is placed in the ultraviolet-ozone cleaning instrument for cleaning for 15-20min, and then is placed in a cerium oxide suspension for soaking
In the step a) of the step 3), the surface of the glass substrate is cleaned, and dirt on the surface of the glass substrate is cleaned and removed, so that more (-OH) can be exposed on the surface of the glass substrate, and the subsequent adsorption of cerium oxide is facilitated.
Compared with the prior art, the invention has the beneficial effects that:
firstly, europium chloride and 2-thenoyl trifluoroacetone react to generate a binary rare earth complex; the gelatin and the sodium alginate are mutually wound and combined to form a compact gel network, and the gel network is mutually combined with the prepared binary rare earth complex, so that the comprehensive performance of the gel network can be improved; adding materials such as silicon dioxide and diboron trioxide, mixing and melting to prepare glass liquid, wherein the sodium alginate-gelatin network in the glass liquid can be mutually combined with components such as silicon dioxide, and the compactness of the silicon dioxide network generated in the preparation of the glass substrate is improved; meanwhile, due to the addition of the rare earth oxide, the network compactness of the prepared glass material is further improved, and the glass material has excellent chemical stability and mechanical property and high glass strength.
Meanwhile, after the glass matrix is obtained, the surface of the glass matrix is subjected to self-assembly modification through cerium oxide, lanthanum nitrate solution and dodecafluoroheptyl propyl trimethoxy silicon solution to form a super-hydrophobic film, so that the prepared glass material has excellent hydrophobic property.
The invention discloses a brown high-strength reagent bottle glass material and a preparation method thereof, which have the advantages of reasonable component design and simple process operation, not only effectively realize the preparation of the brown high-strength glass material, but also add components such as rare earth oxide and the like, so that the prepared reagent bottle glass material has better hydrophobic property, excellent acid and alkali resistance and higher practicability.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
s1: preparing raw materials;
s2: putting 2-thenoyl trifluoroacetone into a beaker, dissolving with absolute ethyl alcohol, adding a sodium hydroxide solution, adjusting the pH to 7.5, adding europium chloride, heating for reaction for 12 hours, spin-drying the reaction solution, washing, filtering, and vacuum-drying to obtain a material A;
s3: taking sodium alginate, stirring at normal temperature until the sodium alginate is completely dissolved to form sodium alginate sol; dissolving gelatin in 55 deg.C water bath, slowly dripping sodium alginate sol into gelatin, stirring and mixing for 25min, adding calcium carbonate, and stirring for 30min to obtain mixed gel; then the mixed gel is dehydrated in vacuum and is placed in an ethanol solvent for soaking for 25min to obtain a material B;
s4: dissolving the material A in absolute ethyl alcohol, adding the material B into the material A, stirring for 24 hours at normal temperature, performing suction filtration, sequentially soaking the material in distilled water, absolute ethyl alcohol, DMF (dimethyl formamide) and acetone for 1 hour each time, and filtering and washing after soaking; soaking in ethanol solution for 1h to obtain material C;
s5: mixing and stirring zinc oxide, boron trioxide, silicon dioxide, aluminum oxide, calcium oxide, potassium oxide, sodium oxide, brown glass slag and brown organic pigment at a high speed for 20min, adding the material C, continuously stirring for 30min, putting the mixture into a glass melting furnace, melting the mixture into molten glass by an all-electric melting method, heating to 1400 ℃, clarifying, homogenizing, and cooling the molten glass to 1150 ℃ to obtain a glass substrate;
s6: cleaning a glass substrate in an ultraviolet-ozone cleaning instrument for 20min, then ultrasonically cleaning the glass substrate with acetone for 20min, and then cleaning the glass substrate in the ultraviolet-ozone cleaning instrument for 15 min; taking cerium oxide, preparing a cerium oxide suspension, diluting, placing the glass substrate in the cerium oxide suspension, soaking for 20min, rinsing with deionized water, and drying with nitrogen;
putting the dried glass substrate into a high-pressure reaction kettle, adding a lanthanum nitrate solution, sealing the high-pressure kettle, putting the high-pressure kettle into a drying box, keeping the temperature at 115 ℃, carrying out hydrothermal treatment for 3 hours, taking out the glass substrate, cleaning and drying; dissolving dodecafluoroheptyl propyl trimethoxy silicon in absolute ethyl alcohol, stirring for 2 hours until the solution is uniform, soaking the hydrothermal glass substrate in dodecafluoroheptyl propyl trimethoxy silicon solution in a thermostatic water bath at the temperature of 25 ℃ for 24 hours, taking out the glass substrate, baking the glass substrate in an oven at the temperature of 150 ℃ for 1 hour, and cooling to the room temperature;
s7: and (3) placing the cooled glass substrate on a round-mouth machine for burning, cleaning and drying to obtain a finished product.
In this embodiment, the glass frit comprises the following raw material components: by weight, 30 parts of zinc oxide, 20 parts of boron trioxide, 20 parts of silicon dioxide, 5 parts of aluminum oxide, 1 part of additive, 0.8 part of calcium oxide, 0.5 part of potassium oxide, 2 parts of sodium oxide, 3 parts of brown glass slag and 3 parts of brown organic pigment; the glass material also comprises the following raw material components: by weight, 9 parts of sodium alginate, 3 parts of 2-thenoyltrifluoroacetone, 2 parts of europium chloride, 3 parts of gelatin, 3 parts of calcium carbonate and 8 parts of surface treating agent.
Wherein the surface treating agent comprises the following raw material components: by weight, 6 parts of cerium oxide, 10 parts of lanthanum nitrate solution and 5 parts of dodecafluoroheptyl propyl trimethoxy silicon; the additive is neodymium oxide.
Example 2:
s1: preparing raw materials;
s2: putting 2-thenoyl trifluoroacetone into a beaker, dissolving with absolute ethyl alcohol, adding a sodium hydroxide solution, adjusting the pH to 8, adding europium chloride, heating for reaction for 13 hours, spin-drying the reaction solution, washing, filtering, and vacuum-drying to obtain a material A;
s3: taking sodium alginate, stirring at normal temperature until the sodium alginate is completely dissolved to form sodium alginate sol; dissolving gelatin in water bath at 60 deg.C, slowly dripping sodium alginate sol into gelatin, stirring and mixing for 30min, adding calcium carbonate, and stirring for 35min to obtain mixed gel; then the mixed gel is dehydrated in vacuum and is placed in an ethanol solvent for soaking for 30min to obtain a material B;
s4: dissolving the material A in absolute ethyl alcohol, adding the material B into the material A, stirring at normal temperature for 25h, performing suction filtration, sequentially soaking the material in distilled water, absolute ethyl alcohol, DMF (dimethyl formamide) and acetone for 1.2h each time, and filtering and washing after soaking; soaking in ethanol solution for 1.5h to obtain material C;
s5: mixing and stirring zinc oxide, boron trioxide, silicon dioxide, aluminum oxide, calcium oxide, potassium oxide, sodium oxide, brown glass slag and brown organic pigment at a high speed for 25min, adding the material C, continuously stirring for 35min, putting the mixture into a glass melting furnace, melting the mixture into molten glass by an all-electric melting method, heating to 1500 ℃, clarifying, homogenizing, and cooling the molten glass to 1200 ℃ to obtain a glass substrate;
s6: cleaning a glass substrate in an ultraviolet-ozone cleaning instrument for 25min, then ultrasonically cleaning the glass substrate with acetone for 25min, and then cleaning the glass substrate in the ultraviolet-ozone cleaning instrument for 18 min; taking cerium oxide, preparing a cerium oxide suspension, diluting, placing the glass substrate in the cerium oxide suspension, soaking for 25min, rinsing with deionized water, and drying with nitrogen;
putting the dried glass substrate into a high-pressure reaction kettle, adding a lanthanum nitrate solution, sealing the high-pressure kettle, putting the high-pressure kettle into a drying box, keeping the temperature at 120 ℃, carrying out hydrothermal treatment for 3.2 hours, taking out the glass substrate, and cleaning and drying the glass substrate; dissolving dodecafluoroheptyl propyl trimethoxy silicon in absolute ethyl alcohol, stirring for 2.5 hours until the solution is uniform, soaking the glass substrate after hydrothermal treatment in a dodecafluoroheptyl propyl trimethoxy silicon solution for 25 hours in a constant-temperature water bath at the temperature of 30 ℃, taking out the glass substrate, baking the glass substrate in an oven at the temperature of 155 ℃ for 1.1 hours, and cooling to room temperature;
s7: and (3) placing the cooled glass substrate on a round-mouth machine for burning, cleaning and drying to obtain a finished product.
In this embodiment, the glass frit comprises the following raw material components: by weight, 35 parts of zinc oxide, 25 parts of diboron trioxide, 28 parts of silicon dioxide, 8 parts of aluminum oxide, 2 parts of additive, 1 part of calcium oxide, 1.5 parts of potassium oxide, 3 parts of sodium oxide, 8 parts of brown glass slag and 5 parts of brown organic pigment; the glass material also comprises the following raw material components: by weight, 18 parts of sodium alginate, 8 parts of 2-thenoyltrifluoroacetone, 6 parts of europium chloride, 5 parts of gelatin, 4 parts of calcium carbonate and 12 parts of surface treating agent.
Wherein the surface treating agent comprises the following raw material components: by weight, 8 parts of cerium oxide, 20 parts of lanthanum nitrate solution and 15 parts of dodecafluoroheptyl propyl trimethoxy silicon; the additive is yttrium oxide.
Example 3:
s1: preparing raw materials;
s2: putting 2-thenoyl trifluoroacetone into a beaker, dissolving with absolute ethyl alcohol, adding a sodium hydroxide solution, adjusting the pH to 8.5, adding europium chloride, heating for 14 hours for reaction, spin-drying the reaction solution, washing, filtering, and vacuum-drying to obtain a material A;
s3: taking sodium alginate, stirring at normal temperature until the sodium alginate is completely dissolved to form sodium alginate sol; dissolving gelatin in 65 deg.C water bath, slowly dripping sodium alginate sol into gelatin, stirring and mixing for 35min, adding calcium carbonate, and stirring for 40min to obtain mixed gel; vacuum dehydrating the mixed gel, and soaking in ethanol solvent for 35min to obtain material B;
s4: dissolving the material A in absolute ethyl alcohol, adding the material B into the material A, stirring at normal temperature for 26 hours, performing suction filtration, sequentially soaking the material in distilled water, absolute ethyl alcohol, DMF (dimethyl formamide) and acetone for 1.5 hours each time, and filtering and washing after soaking; soaking in ethanol solution for 2h to obtain material C;
s5: mixing and stirring zinc oxide, boron trioxide, silicon dioxide, aluminum oxide, calcium oxide, potassium oxide, sodium oxide, brown glass slag and brown organic pigment at a high speed for 30min, adding the material C, continuously stirring for 40min, putting the mixture into a glass melting furnace, melting the mixture into molten glass by an all-electric melting method, heating to 1600 ℃, clarifying, homogenizing, and cooling the molten glass to 1250 ℃ to obtain a glass substrate;
s6: cleaning a glass substrate in an ultraviolet-ozone cleaning instrument for 30min, then ultrasonically cleaning the glass substrate with acetone for 30min, and then cleaning the glass substrate in the ultraviolet-ozone cleaning instrument for 20 min; taking cerium oxide, preparing a cerium oxide suspension, diluting, placing the glass substrate in the cerium oxide suspension, soaking for 30min, rinsing with deionized water, and drying with nitrogen;
putting the dried glass substrate into a high-pressure reaction kettle, adding a lanthanum nitrate solution, sealing the high-pressure kettle, putting the high-pressure kettle into a drying box, keeping the temperature at 125 ℃, carrying out hydrothermal treatment for 3.5 hours, taking out the glass substrate, and cleaning and drying the glass substrate; dissolving dodecafluoroheptyl propyl trimethoxy silicon in absolute ethyl alcohol, stirring for 3 hours until the solution is uniform, soaking the hydrothermal glass substrate in dodecafluoroheptyl propyl trimethoxy silicon solution in a constant-temperature water bath at 35 ℃ for 26 hours, taking out the glass substrate, baking the glass substrate in an oven at 160 ℃ for 1.2 hours, and cooling to room temperature;
s7: and (3) placing the cooled glass substrate on a round-mouth machine for burning, cleaning and drying to obtain a finished product.
In this embodiment, the glass frit comprises the following raw material components: by weight, 40 parts of zinc oxide, 30 parts of boron trioxide, 35 parts of silicon dioxide, 10 parts of aluminum oxide, 3 parts of additive, 1.8 parts of calcium oxide, 2 parts of potassium oxide, 4 parts of sodium oxide, 12 parts of brown glass slag and 7 parts of brown organic pigment; the glass material also comprises the following raw material components: 27 parts of sodium alginate, 10 parts of 2-thenoyl trifluoroacetone, 8 parts of europium chloride, 8 parts of gelatin, 6 parts of calcium carbonate and 18 parts of surface treating agent.
Wherein the surface treating agent comprises the following raw material components: by weight, 14 parts of cerium oxide, 30 parts of lanthanum nitrate solution and 20 parts of dodecafluoroheptyl propyl trimethoxy silicon; the additive is gadolinium oxide.
Example 4:
s1: preparing raw materials;
s2: putting 2-thenoyl trifluoroacetone into a beaker, dissolving with absolute ethyl alcohol, adding a sodium hydroxide solution, adjusting the pH to 8, adding europium chloride, heating for reaction for 13 hours, spin-drying the reaction solution, washing, filtering, and vacuum-drying to obtain a material A;
s3: taking sodium alginate, stirring at normal temperature until the sodium alginate is completely dissolved to form sodium alginate sol; dissolving gelatin in water bath at 60 deg.C, slowly dripping sodium alginate sol into gelatin, stirring and mixing for 30min, adding calcium carbonate, and stirring for 35min to obtain mixed gel; then the mixed gel is dehydrated in vacuum and is placed in an ethanol solvent for soaking for 30min to obtain a material B;
s4: dissolving the material A in absolute ethyl alcohol, adding the material B into the material A, stirring at normal temperature for 25h, performing suction filtration, sequentially soaking the material in distilled water, absolute ethyl alcohol, DMF (dimethyl formamide) and acetone for 1.2h each time, and filtering and washing after soaking; soaking in ethanol solution for 1.5h to obtain material C;
s5: mixing and stirring zinc oxide, boron trioxide, silicon dioxide, aluminum oxide, calcium oxide, potassium oxide, sodium oxide, brown glass slag and brown organic pigment at a high speed for 25min, adding the material C, continuously stirring for 35min, putting the mixture into a glass melting furnace, melting the mixture into molten glass by an all-electric melting method, heating to 1500 ℃, clarifying, homogenizing, and cooling the molten glass to 1200 ℃ to obtain a glass substrate;
s6: cleaning a glass substrate in an ultraviolet-ozone cleaning instrument for 25min, then ultrasonically cleaning the glass substrate with acetone for 25min, and then cleaning the glass substrate in the ultraviolet-ozone cleaning instrument for 18 min; taking cerium oxide, preparing a cerium oxide suspension, diluting, placing the glass substrate in the cerium oxide suspension, soaking for 25min, rinsing with deionized water, and drying with nitrogen;
putting the dried glass substrate into a high-pressure reaction kettle, adding a lanthanum nitrate solution, sealing the high-pressure kettle, putting the high-pressure kettle into a drying box, keeping the temperature at 120 ℃, carrying out hydrothermal treatment for 3.2 hours, taking out the glass substrate, and cleaning and drying the glass substrate; dissolving dodecafluoroheptyl propyl trimethoxy silicon in absolute ethyl alcohol, stirring for 2.5 hours until the solution is uniform, soaking the glass substrate after hydrothermal treatment in a dodecafluoroheptyl propyl trimethoxy silicon solution for 25 hours in a constant-temperature water bath at the temperature of 30 ℃, taking out the glass substrate, baking the glass substrate in an oven at the temperature of 155 ℃ for 1.1 hours, and cooling to room temperature;
s7: and (3) placing the cooled glass substrate on a round-mouth machine for burning, cleaning and drying to obtain a finished product.
In this embodiment, the glass frit comprises the following raw material components: by weight, 35 parts of zinc oxide, 25 parts of diboron trioxide, 28 parts of silicon dioxide, 8 parts of aluminum oxide, 2 parts of additive, 1 part of calcium oxide, 1.5 parts of potassium oxide, 3 parts of sodium oxide, 8 parts of brown glass slag and 5 parts of brown organic pigment; the glass material also comprises the following raw material components: by weight, 18 parts of sodium alginate, 8 parts of 2-thenoyltrifluoroacetone, 6 parts of europium chloride, 5 parts of gelatin, 4 parts of calcium carbonate and 12 parts of surface treating agent.
Wherein the surface treating agent comprises the following raw material components: by weight, 8 parts of cerium oxide, 20 parts of lanthanum nitrate solution and 15 parts of dodecafluoroheptyl propyl trimethoxy silicon; the additive is a mixture of neodymium oxide, yttrium oxide and gadolinium oxide.
Example (b):
examples 1 to 4 were all prepared according to the technical scheme disclosed in the present invention, and the obtained glasses were used as samples, and the mechanical properties thereof were respectively detected, and it was found that the highest compressive strength thereof could reach 379MPa, the highest flexural strength thereof could reach 48MPa, and the impact resistance thereof was excellent.
Meanwhile, the acid and alkali resistance tests of the glass samples prepared in examples 1-4 show that the glass samples have excellent acid and alkali resistance, the surface water contact angle can reach 158 degrees at most, and the glass samples have excellent hydrophobic property.
And (4) conclusion: the invention not only effectively realizes the preparation of the brown high-strength glass frit, but also adds the components such as rare earth oxide and the like, so that the prepared glass frit for the reagent bottle has better hydrophobic property, excellent acid and alkali resistance and higher practicability.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (8)
1. The brown high-strength reagent bottle glass material is characterized in that: the glass frit comprises the following raw material components: 30-40 parts of zinc oxide, 20-30 parts of boron trioxide, 20-35 parts of silicon dioxide, 5-10 parts of aluminum oxide, 1-3 parts of additive, 0.8-1.8 parts of calcium oxide, 0.5-2 parts of potassium oxide, 2-4 parts of sodium oxide, 3-12 parts of brown glass slag and 3-7 parts of brown organic pigment.
2. The brown high strength reagent bottle frit according to claim 1, wherein: the glass material also comprises the following raw material components: 9-27 parts of sodium alginate, 3-10 parts of 2-thenoyl trifluoroacetone, 2-8 parts of europium chloride, 3-8 parts of gelatin, 3-6 parts of calcium carbonate and 8-18 parts of surface treating agent.
3. The brown high strength reagent bottle frit according to claim 2, wherein: the surface treating agent comprises the following raw material components: by weight, 6-14 parts of cerium oxide, 10-30 parts of lanthanum nitrate solution and 5-20 parts of dodecafluoroheptyl propyl trimethoxy silicon.
4. The brown high strength reagent bottle frit according to claim 1, wherein: the additive is any one or a mixture of more of neodymium oxide, yttrium oxide and gadolinium oxide.
5. A preparation method of brown high-strength reagent bottle glass frit is characterized by comprising the following steps: the method comprises the following steps:
1) preparing raw materials;
2) melting to obtain a glass matrix;
3) carrying out surface treatment on the glass substrate by using a surface treating agent;
4) and finishing the operation to obtain a finished product.
6. The method for preparing the brown high-strength reagent bottle glass frit as claimed in claim 5, wherein the method comprises the following steps: the method comprises the following steps:
1) preparing raw materials:
2) melting to obtain a glass matrix:
a) putting the 2-thenoyl trifluoroacetone prepared in the step 1) into a beaker, dissolving with absolute ethyl alcohol, adding a sodium hydroxide solution, adjusting the pH to 7.5-8.5, adding the europium chloride prepared in the step 1), heating for reaction, spin-drying reaction liquid after the reaction is finished, washing, filtering, and vacuum-drying to obtain a material A;
b) stirring the sodium alginate prepared in the step 1) at normal temperature until the sodium alginate is completely dissolved to form sodium alginate sol; dissolving the gelatin prepared in the step 1) in water bath, slowly dropping the sodium alginate sol into the gelatin, stirring and mixing, adding calcium carbonate, and continuously stirring to obtain mixed gel; then the mixed gel is dehydrated in vacuum and is placed in an ethanol solvent for soaking to obtain a material B;
c) dissolving the material A prepared in the step 2) with absolute ethyl alcohol, then putting the material A into the material B prepared in the step 3), stirring at normal temperature for 24-26h, performing suction filtration, sequentially soaking the materials in distilled water, absolute ethyl alcohol, DMF (dimethyl formamide) and acetone for 1-1.5h each time, and filtering and washing after soaking; soaking in ethanol solution to obtain material C;
d) mixing and stirring the zinc oxide, boron trioxide, silicon dioxide, aluminum oxide, calcium oxide, potassium oxide, sodium oxide, brown glass slag and brown organic pigment prepared in the step 1) at a high speed, adding the material C prepared in the step C), continuously stirring, putting the mixture into a glass melting furnace, melting the mixture into molten glass by adopting an all-electric melting method, heating to 1400-1600 ℃, clarifying, homogenizing, and cooling the molten glass to 1250 ℃ to obtain a glass substrate;
3) the surface treating agent is used for carrying out surface treatment on the glass substrate:
a) taking the glass substrate prepared in the step 2), cleaning, taking the cerium oxide prepared in the step 1), preparing a cerium oxide suspension, diluting, putting the glass substrate into the cerium oxide suspension, soaking for 20-30min, rinsing with deionized water, and drying with nitrogen;
b) taking the dried glass substrate, putting the glass substrate into a high-pressure reaction kettle, adding the lanthanum nitrate solution prepared in the step 1), sealing the high-pressure kettle, putting the high-pressure kettle into a drying box, keeping the temperature at 115-125 ℃, taking out the glass substrate after hydrothermal for 3-3.5h, and cleaning and drying the glass substrate; dissolving the dodecafluoroheptyl propyl trimethoxy silicon prepared in the step 1) in absolute ethyl alcohol, stirring to be uniform, soaking the hydrothermal glass substrate in the dodecafluoroheptyl propyl trimethoxy silicon solution in a thermostatic water bath at the temperature of 25-35 ℃ for 24-26 hours, taking out the glass substrate, baking and curing in an oven, and cooling to room temperature;
4) cleaning and drying to obtain a finished product.
7. The method for preparing the brown high-strength reagent bottle glass frit as claimed in claim 6, wherein the method comprises the following steps: the method comprises the following steps:
1) preparing raw materials:
A. weighing zinc oxide, boron trioxide, silicon dioxide, aluminum oxide, calcium oxide, potassium oxide, sodium oxide, brown glass residue and brown organic pigment according to a proportion for later use;
B. weighing sodium alginate, 2-thenoyltrifluoroacetone, europium chloride, gelatin, calcium carbonate, cerium oxide, lanthanum nitrate solution and dodecafluoroheptyl propyl trimethoxy silicon in proportion for later use;
2) melting to obtain a glass matrix:
a) putting the 2-thenoyltrifluoroacetone prepared in the step 1) into a beaker, dissolving with absolute ethanol, adding a sodium hydroxide solution, adjusting the pH to 7.5-8.5, adding the europium chloride prepared in the step 1), heating for reaction for 12-14h, spin-drying the reaction solution, washing, filtering, and vacuum-drying to obtain a material A;
b) stirring the sodium alginate prepared in the step 1) at normal temperature until the sodium alginate is completely dissolved to form sodium alginate sol; dissolving the gelatin prepared in the step 1) in water bath at 55-65 ℃, slowly dropping the sodium alginate sol into the gelatin, stirring and mixing for 25-35min, adding calcium carbonate, and continuously stirring for 30-40min to obtain mixed gel; vacuum dehydrating the mixed gel, and soaking in ethanol solvent for 25-35min to obtain material B;
c) dissolving the material A prepared in the step 2) with absolute ethyl alcohol, then putting the material A into the material B prepared in the step 3), stirring at normal temperature for 24-26h, performing suction filtration, sequentially soaking the materials in distilled water, absolute ethyl alcohol, DMF (dimethyl formamide) and acetone for 1-1.5h each time, and filtering and washing after soaking; soaking in ethanol solution for 1-2h to obtain material C;
d) mixing and stirring the zinc oxide, the boron trioxide, the silicon dioxide, the aluminum oxide, the calcium oxide, the potassium oxide, the sodium oxide, the brown glass slag and the brown organic pigment prepared in the step 1) at a high speed for 20-30min, adding the material C prepared in the step C), continuously stirring for 30-40min,
putting the mixture into a glass melting furnace, melting the mixture into molten glass by adopting an all-electric melting method, heating to 1400-1600 ℃, clarifying, homogenizing, and cooling the molten glass to 1150-1250 ℃ to obtain a glass matrix;
3) the surface treating agent is used for carrying out surface treatment on the glass substrate:
a) taking the glass substrate prepared in the step 2), cleaning, taking the cerium oxide prepared in the step 1), preparing a cerium oxide suspension, diluting, putting the glass substrate into the cerium oxide suspension, soaking for 20-30min, rinsing with deionized water, and drying with nitrogen;
b) taking the dried glass substrate, putting the glass substrate into a high-pressure reaction kettle, adding the lanthanum nitrate solution prepared in the step 1), sealing the high-pressure kettle, putting the high-pressure kettle into a drying box, keeping the temperature at 115-125 ℃, taking out the glass substrate after hydrothermal for 3-3.5h, and cleaning and drying the glass substrate; dissolving the dodecafluoroheptyl propyl trimethoxy silicon prepared in the step 1) in absolute ethyl alcohol, stirring for 2-3h until the solution is uniform, soaking the hydrothermal glass substrate in the dodecafluoroheptyl propyl trimethoxy silicon solution for 24-26h under the condition of a constant-temperature water bath at 25-35 ℃, taking out the glass substrate, baking the glass substrate in an oven at the temperature of 150-;
4) cleaning and drying to obtain a finished product.
8. The method for preparing the brown high-strength reagent bottle glass frit as claimed in claim 7, wherein the method comprises the following steps: in the step a) of the step 3), the glass substrate is firstly placed in an ultraviolet-ozone cleaning instrument for cleaning for 20-30min, then is ultrasonically cleaned for 20-30min by acetone, then is placed in the ultraviolet-ozone cleaning instrument for cleaning for 15-20min, and then is placed in a cerium oxide suspension for soaking.
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