WO2022142074A1 - 可溶性杀菌玻璃和可溶性杀菌玻璃的制备方法 - Google Patents

可溶性杀菌玻璃和可溶性杀菌玻璃的制备方法 Download PDF

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WO2022142074A1
WO2022142074A1 PCT/CN2021/094116 CN2021094116W WO2022142074A1 WO 2022142074 A1 WO2022142074 A1 WO 2022142074A1 CN 2021094116 W CN2021094116 W CN 2021094116W WO 2022142074 A1 WO2022142074 A1 WO 2022142074A1
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Prior art keywords
glass
oxide
soluble
zinc
sterilization
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PCT/CN2021/094116
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English (en)
French (fr)
Inventor
杨青波
高源�
熊明
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无锡小天鹅电器有限公司
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Priority to JP2023537415A priority Critical patent/JP2023554483A/ja
Publication of WO2022142074A1 publication Critical patent/WO2022142074A1/zh

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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
    • 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
    • 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
    • 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
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • C03C3/19—Silica-free oxide glass compositions containing phosphorus containing boron
    • 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
    • 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
    • C03C4/0035—Compositions for glass with special properties for soluble glass for controlled release of a compound incorporated in said glass
    • 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
    • C03C2204/00—Glasses, glazes or enamels with special properties
    • C03C2204/02—Antibacterial glass, glaze or enamel

Definitions

  • the present application relates to the technical field of inorganic antibacterial materials, in particular, to a soluble sterilization glass and a preparation method of a soluble sterilization glass.
  • Antibacterial materials are a class of functional materials with bactericidal and antibacterial properties, which mainly achieve antibacterial effects by adding antibacterial agents.
  • Antibacterial agents are mainly divided into three categories: natural biological, organic and inorganic antibacterial agents.
  • chitosan and sorbic acid are widely studied. These antibacterial agents are safe and environmentally friendly and have good antibacterial properties. However, due to their poor heat resistance, short efficacy period and limited production conditions, it is difficult to achieve industrialization.
  • Organic antibacterial agents use organic acids, phenols, quaternary ammonium salts, benzimidazoles and other organic compounds as antibacterial components, which can effectively inhibit the reproduction of harmful bacteria and molds, but have poor stability, easy decomposition, and are usually toxic. .
  • Inorganic antibacterial agents are mainly used to obtain antibacterial materials by adding metals or their ions with antibacterial ability to porous materials such as zeolite, silica gel, or glass. Compared with organic and biological antibacterial materials, inorganic antibacterial materials have the characteristics of good persistence, broad-spectrum antibacterial, heat resistance and safety.
  • Zinc-loaded antibacterial glass materials have been widely used because of their excellent antibacterial effect and good safety.
  • the present application aims to solve at least one of the above technical problems.
  • the first object of the present application is to provide a soluble germicidal glass.
  • the second objective of the present application is to provide a method for preparing a soluble sterilization glass.
  • an embodiment of the present application provides a soluble sterilization glass, comprising: zinc oxide, 0.2 to 10 parts by mass; boron oxide, 1 to 20 parts by mass; calcium oxide, 10 parts by mass Parts by mass to 30 parts by mass; phosphorus oxide, 30 parts by mass to 70 parts by mass.
  • Zinc ion is an inorganic fungicide with good bactericidal effect, stable performance and low cost.
  • the technical solution provides a ternary oxide soluble sterilization glass with boron oxide, calcium oxide and phosphorus oxide as main components.
  • the addition and ratio control of phosphorus oxide and boron oxide can make zinc ions release slowly in boron, calcium and phosphorus at a reasonable rate.
  • the applicant found in the process of realizing the present application that the addition of phosphorus oxide can increase the dissolution rate of zinc ions and promote the release of silver ions.
  • the addition of boron oxide can reduce the dissolution rate of zinc ions and inhibit the release of silver ions. Therefore, this technical solution controls the addition amount and specific ratio of phosphorus oxide and boron oxide (ie, the content of phosphorus oxide is 30 to 70 parts by mass, and the content of boron oxide is 1 to 20 parts by mass). Therefore, the technical solution can reasonably control the slow-release rate and slow-release efficiency of zinc ions in the soluble sterilization glass.
  • the addition of calcium oxide can appropriately reduce the melting temperature of the soluble sterilization glass, reduce the production cost of the soluble sterilization glass, and improve the production efficiency of the soluble sterilization glass.
  • the content of zinc oxide is controlled to be 0.2 to 10 parts by mass, and the above content of zinc oxide can ensure the long-term release of zinc ions in the soluble sterilization glass and ensure the sterilization effect of the soluble sterilization glass.
  • the soluble sterilization glass further includes: a colorant, 0.0001 to 0.0008 parts by mass.
  • the colorant includes at least one of the following or a combination thereof: cobalt oxide, manganese oxide, iron oxide, copper oxide, and cadmium sulfide.
  • the soluble sterilization glass further includes: cerium oxide, 0.0001 to 0.0006 parts by mass.
  • Adding cerium oxide to the soluble germicidal glass can increase the ratio of high-valent zinc ions in the zinc ions used as germicidal agents. Therefore, the addition of cerium oxide can improve the sterilization effect and sterilization efficiency of the soluble sterilization glass of the embodiments of the present application.
  • the zinc ions in the soluble sterilization glass include tetravalent zinc ions.
  • the soluble sterilization glass including tetravalent zinc ions not only has better sustained release effect, but also has better sterilization. Effect.
  • the thickness of the soluble sterilization glass ranges from 3 mm to 5 mm; and/or the length of the soluble sterilization glass ranges from 5 mm to 8 mm.
  • the soluble sterilization glass of the above size can meet the production and processing requirements of most household appliances, and has a relatively reasonable slow-release period and excellent slow-release efficiency.
  • the soluble sterilization glass of the above-mentioned size can be cooled in time under natural conditions, and is not prone to bursting or cracking.
  • the qualified rate of the finished product during molding is high, and the internal stress is small. Even if the annealing process is not implemented, it also has good mechanical strength and Thermal stability.
  • melting the mixture to obtain molten glass includes: melting the mixture in a temperature range of 950 degrees Celsius to 1350 degrees Celsius for a duration of 0.5 to 2 hours to obtain molten glass.
  • the above temperature regime can ensure sufficient melting of each metal oxide, and ensure that the present embodiment can obtain homogeneous and clear soluble sterilization glass.
  • the preparation method before the process of melting the mixture to obtain the molten glass, the preparation method further includes: preheating the mixture.
  • the purpose of the preheating process is to further effectively discharge the impurities and gases in the raw materials, avoid excessive bubbles in the molten glass during the melting process, and ensure that the texture of the soluble sterilization glass is firm and dense.
  • the above preheating conditions can effectively remove impurities and gases in the raw materials.
  • Preheating the metal mold before cooling and forming prevents the molten glass from bursting during pouring and forming.
  • preheating the metal mold includes: preheating the metal mold to a temperature range of 200 degrees Celsius to 300 degrees Celsius.
  • the above temperature regime for preheating the metal mold can effectively prevent the glass from bursting during cooling and forming. Improve yield.
  • the raw materials include zinc source raw materials, and the zinc source raw materials include at least one of the following or a combination thereof: zinc nitrate, zinc chloride, zinc sulfate, zinc oxide; and/or the raw materials include boron source raw materials, and the boron source raw materials include boric acid and/or the raw material includes a calcium source raw material, and the calcium source raw material includes at least one of the following or a combination thereof: calcium carbonate, calcium nitrate, calcium sulfate, calcium phosphate, calcium chloride, calcium oxide; and/or the raw material includes a phosphorus source raw material,
  • the phosphorus source material includes at least one of the following or a combination thereof: calcium phosphate, ammonium phosphate, and phosphorus oxide.
  • Raw materials including zinc, boron, calcium and phosphorus can be added directly in the form of oxides or in the form of salt compounds. Among them, compared with using metal oxides as raw materials, using metal salt compounds as raw materials can improve the degree of homogeneity and clarity of glass.
  • FIG. 2 is the second flow chart of the steps of a method for preparing a soluble sterilization glass according to an embodiment of the present application
  • FIG. 3 is the third step flow chart of the method for preparing soluble sterilization glass according to an embodiment of the present application
  • FIG. 4 is the fourth step flow chart of a method for preparing a soluble sterilization glass according to an embodiment of the present application
  • FIG. 5 is the fifth step flow chart of the method for preparing soluble sterilization glass according to an embodiment of the present application.
  • FIG. 6 is the sixth flowchart of the steps of a method for preparing a soluble sterilization glass according to an embodiment of the present application.
  • the soluble sterilization glass of the embodiment of the present application includes: zinc oxide (ZnO and/or ZnO 2 ), the addition amount of zinc oxide is 0.2 to 10 parts by mass; boron oxide (B 2 O 3 ), the addition amount of boron oxide is 1 to 20 parts by mass; calcium oxide (CaO), the amount of calcium oxide added is 10 to 30 parts by mass; phosphorus oxide (P 2 O 5 ), the amount of phosphorus oxide added is 30 to 70 parts by mass .
  • the materials of the soluble germicidal glass in this embodiment specifically include: zinc oxide, 0.2 parts by mass; boron oxide, 19.8 parts by mass; calcium oxide, 10 parts by mass; and phosphorus oxide, 70 parts by mass.
  • the materials of the soluble sterilization glass in this embodiment specifically include: zinc oxide, 10 parts by mass; boron oxide, 10 parts by mass; calcium oxide, 30 parts by mass; and phosphorus oxide, 50 parts by mass.
  • the soluble glass refers to a soluble sterilization glass that can release one or more functional ions slowly and stably in a liquid such as water.
  • the functional ions in the embodiments of the present application are specifically zinc ions (Zn 2+ and/or Zn 4+ ).
  • Zinc ions have good sterilization and disinfection effects, occupy the lattice of metal oxide glass in the form of doping, and are stably released over time in the environment of being soaked or flushed by liquid to achieve long-term bactericidal effect .
  • the soluble sterilization glass added with zinc ions can be used in home appliances such as washing machines and air conditioners to sterilize the washing water of washing machines or the indoor space where air conditioners are placed.
  • home appliances such as washing machines and air conditioners to sterilize the washing water of washing machines or the indoor space where air conditioners are placed.
  • one of the problems existing in the related art is that the slow-release performance of zinc ions to achieve the bactericidal function is not ideal.
  • the slow-release performance of zinc ions in the soluble sterilization glass of the related art is difficult to control.
  • the zinc ion-doped soluble sterilization glass placed in the washing machine as an example, within a fixed washing program and washing time range, if the release rate of zinc ions in the soluble sterilization glass is too fast, the zinc ions will be released earlier. , and cause the sterilization effect of the washing machine to decline in the later use process, or even lose the sterilization effect. If the release rate of zinc ions in the soluble sterilization glass is too slow, the sterilization effect of the washing machine in the entire use process is not satisfactory, and it is difficult to achieve effective sterilization of clothing or home textiles.
  • the embodiment of the present application provides a ternary oxide soluble sterilization glass with boron oxide, calcium oxide and phosphorus oxide as main components .
  • the soluble sterilization glass further includes a colorant, and the colorant is added in an amount of 0.0001 to 0.0008 parts by mass.
  • the content of the colorant in the soluble germicidal glass of this embodiment may be 0.0001 parts by mass or 0.0004 parts by mass or 0.0008 parts by mass.
  • the purpose of adding colorant is to adjust and control the color of soluble germicidal glass. Among them, those skilled in the art can flexibly select and adjust the added amount and specific type of the colorant within the above range.
  • the colorant can be added and mixed with the matrix raw materials such as boron oxide, calcium oxide and phosphorus oxide during the batching process. After melting and cooling, a soluble germicidal glass with a uniform color is obtained.
  • the colorant includes any or all of the following metal oxides: cobalt oxide (Co 2 O 3 ), manganese oxide (MnO 2 ), iron oxide (Fe 2 O 3 and /or Fe 3 O 4 ), copper oxide (CuO), cadmium sulfide (CdS).
  • the colorant of the present embodiment is a metal oxide colorant. Metal oxide colorants are stable in performance, resistant to high temperatures and not easily decomposed.
  • the soluble sterilization glass further includes: cerium oxide, and the addition amount of cerium oxide is 0.0001 parts by mass to 0.0006 parts by mass.
  • the content of cerium oxide in the soluble germicidal glass of this embodiment may be 0.0001 parts by mass or 0.0003 parts by mass or 0.0006 parts by mass.
  • Cerium ions (Ce 3+ ) as rare earth elements are characterized by abundant energy levels and high valence. Adding cerium oxide to the boron calcium phosphorus ternary oxide soluble germicidal glass can increase the ratio of high-valent zinc ions (ie: tetravalent zinc ions) in the zinc ions used as germicides. Therefore, the addition of cerium oxide can improve the sterilization effect and sterilization efficiency of the soluble sterilization glass of the embodiments of the present application.
  • the zinc ions in the soluble germicidal glass include tetravalent zinc ions.
  • tetravalent zinc ions have higher sterilization effect and sterilization efficiency. Therefore, the soluble sterilization glass including tetravalent zinc ions not only has a better sustained release effect, but also Has better bactericidal effect.
  • the soluble germicidal glass further includes at least one of the following or a combination thereof: lithium oxide, sodium oxide, potassium oxide, magnesium oxide, silicon oxide, and aluminum oxide.
  • Alkali metal oxides or alkaline earth metal oxides including lithium oxide, sodium oxide and potassium oxide have relatively active physical and chemical properties, and can effectively reduce the melting point (ie: melting temperature) of the soluble germicidal glass.
  • the addition of silica and alumina can promote glass formation and increase the viscosity and mechanical strength of soluble germicidal glass.
  • Magnesium oxide can improve the clarity of molten glass and the gloss and refractive index of soluble sterilization glass after molding.
  • the zinc ion dissolution amount obtained by the test in this embodiment under the temperature condition of 30 degrees Celsius and the test time of 24 hours is 1 mg zinc ion/g water to 500 mg zinc ion/g water, that is: 10 mg/(g ⁇ 1L ⁇ 24Hrs ⁇ 30°C)) to 500 (mg/(g ⁇ 1L ⁇ 24Hrs ⁇ 30°C)).
  • the thickness of the soluble germicidal glass ranges from 3 mm to 5 mm. Soluble germicidal glass is available in lengths ranging from 5mm to 8mm.
  • the size and shape of the soluble sterilization glass are consistent with the size and shape of the forming mold used.
  • the soluble sterilization glass of this embodiment can be prepared into a sheet shape, a plate shape or a block shape, and can also be prepared into a spherical shape or a quasi-spherical shape.
  • the sustained-release efficiency and sustained-release period of zinc ions were influenced by the size and shape of the soluble germicidal glass.
  • the soluble sterilization glass prepared by using the above-mentioned mold can meet the production and processing requirements of most household appliances, and has a relatively reasonable sustained release period and excellent sustained release efficiency.
  • the soluble sterilization glass of the above-mentioned size can be cooled in time under natural conditions, and is not prone to bursting or cracking.
  • the qualified rate of the finished product during molding is high, and the internal stress is small. Even if the annealing process is not implemented, it also has good mechanical strength and Thermal stability.
  • FIG. 1 is one of the flow charts of the steps of a method for preparing a soluble sterilization glass according to an embodiment of the present application.
  • the preparation method of the soluble sterilization glass according to the embodiment of the present application includes:
  • Step S104 melting the mixture to obtain molten glass
  • Step S106 cooling the glass liquid to obtain a soluble sterilization glass.
  • the content of zinc oxide as a germicidal agent is 0.2 wt % to 10 wt %, and the content of boron oxide is 1 wt % to 20wt%, the content of calcium oxide is 10wt% to 30wt%, and the content of phosphorus oxide is 30wt% to 70wt%.
  • the proportional relationship of each oxide in the soluble sterilization glass is limited by mass fraction.
  • the raw materials can be directly weighed according to the proportional relationship in the above step S102.
  • the original weighing ratio can be determined according to the conversion relationship between the molar mass and the mass fraction of each raw material. If liquid raw materials are used, in this embodiment, the original weighing ratio can be determined according to the conversion relationship between volume concentration and mass fraction.
  • the mass ratio of each raw material in the total raw materials is as follows: the proportion of silver nitrate is 3wt%; the proportion of calcium phosphate is 78wt%; the proportion of sodium phosphate is The proportion of ammonium phosphate is 0.9%; the proportion of boric acid is 5.9wt%; the proportion of zinc oxide is 2.55wt%; the proportion of copper oxide is 0.4wt%; the proportion of cobalt oxide is 0.05wt% %; the proportion of cerium oxide is 0.5wt%.
  • the weighing process of the embodiment of the present application can be realized by using an analytical balance, and the mixing and grinding of raw materials can be realized by small mixing equipment such as agate mortar or planetary ball mill, and realized by resistance furnace or muffle furnace.
  • small mixing equipment such as agate mortar or planetary ball mill, and realized by resistance furnace or muffle furnace.
  • the mixture placed in the platinum crucible is melted, and finally the glass liquid in the platinum crucible is poured onto the aluminum plate mold or the iron plate mold to cool and form.
  • the weighing process of the embodiment of the present application can be realized by using a large scale, the mixing and grinding of the raw materials can be realized by a mixer, and the melting and cooling of the mixture can be realized by large equipment such as a kiln. .
  • step S106 may be natural cooling, furnace cooling, or water quenching.
  • step S104 can be performed in an atmospheric environment, or in a reducing atmosphere or an inert gas.
  • an annealing process may also be implemented in this embodiment to eliminate the internal stress of the soluble sterilization glass.
  • the temperature range of the annealing process is 200 degrees Celsius to 500 degrees Celsius, and the annealing time is 2 hours to 4 hours.
  • the method for preparing the soluble germicidal glass in the embodiment of the present application can obtain the soluble germicidal glass according to any embodiment of the present application.
  • the preparation method of the soluble germicidal glass in the embodiment of the present application has all the beneficial effects of the soluble germicidal glass in any embodiment of the present application. It should be noted in particular that the soluble germicidal glass is doped with excellent sustained-release performance and reasonable sustained-release efficiency. Controllable zinc ion fungicide.
  • melting the mixture to obtain molten glass includes: melting the mixture in a temperature range of 950 degrees Celsius to 1350 degrees Celsius for a duration of 0.5 to 2 hours to obtain molten glass.
  • FIG. 2 is the second flow chart of the steps of a method for preparing a soluble sterilization glass according to an embodiment of the present application. As shown in FIG. 2 , the preparation method of the soluble sterilization glass of this embodiment includes:
  • Step S204 melting the mixture in a temperature range of 950 degrees Celsius to 1350 degrees Celsius for a duration of 0.5 hours to 2 hours to obtain molten glass;
  • the temperature regime in the melting process adopted in step S204 of this embodiment can ensure sufficient melting of each metal oxide, and ensure that this embodiment can obtain homogeneous and clear soluble sterilization glass.
  • the preparation method before the process of melting the mixture to obtain the molten glass, the preparation method further includes: preheating the mixture.
  • FIG. 3 is the third flow chart of the steps of a method for preparing a soluble sterilization glass according to an embodiment of the present application. As shown in FIG. 3 , the preparation method of the soluble sterilization glass of this embodiment includes:
  • Step S304 preheating the mixture
  • Step S306 melting the mixture to obtain molten glass
  • the purpose of the preheating process is to further effectively discharge the impurities and gases in the raw materials, avoid excessive bubbles in the molten glass during the melting process, and ensure that the texture of the soluble sterilization glass is firm and dense.
  • preheating the mixture includes: preheating the mixture for a duration of 0.5 hours to 1.5 hours in a temperature range of 250 degrees Celsius to 350 degrees Celsius.
  • FIG. 4 is the fourth flow chart of the steps of a method for preparing a soluble sterilization glass according to an embodiment of the present application. As shown in FIG. 4 , the preparation method of the soluble sterilization glass of this embodiment includes:
  • Step S404 preheating the mixture for a duration of 0.5 hours to 1.5 hours in a temperature range of 250 degrees Celsius to 350 degrees Celsius;
  • Step S406 melting the mixture to obtain molten glass
  • the mixture is preheated in a temperature range of 250 degrees Celsius to 350 degrees Celsius, and the preheating time is more than 0.5 hours, but not more than 1.5 hours.
  • the above preheating conditions can effectively remove impurities and gases in the raw materials.
  • cooling and forming molten glass to obtain molten glass includes: preheating a metal mold; pouring molten glass into the metal mold and naturally cooling and forming to obtain molten glass.
  • FIG. 5 is the fifth flow chart of the steps of a method for preparing a soluble sterilization glass according to an embodiment of the present application. As shown in FIG. 5 , the preparation method of the soluble sterilization glass of this embodiment includes:
  • Step S504 melting the mixture to obtain molten glass
  • Step S506 preheating the metal mold
  • Step S508 pour the glass liquid into the metal mold and naturally cool to form to obtain a soluble sterilization glass.
  • the metal mold of this embodiment may be a metal mold with better heat resistance and thermal conductivity, such as an aluminum mold or an iron mold.
  • the purpose of preheating the metal mold before cooling and forming is to prevent the molten glass from bursting during the pouring and forming process.
  • Natural cooling molding refers to placing the metal mold containing the molten glass in a room temperature environment (such as between 20 degrees Celsius and 30 degrees Celsius) and naturally cooling until the liquid glass liquid becomes a solid block glass body.
  • preheating the metal mold includes: preheating the metal mold to a temperature range of 200 degrees Celsius to 300 degrees Celsius.
  • Fig. 6 is the sixth flow chart of the steps of a method for preparing a soluble sterilization glass according to an embodiment of the present application. As shown in FIG. 6 , the preparation method of the soluble sterilization glass of this embodiment includes:
  • Step S604 melting the mixture to obtain molten glass
  • Step S606 preheating the metal mold to a temperature range of 200 degrees Celsius to 300 degrees Celsius;
  • Step S608 pour the molten glass into the metal mold and naturally cool to form to obtain a soluble sterilization glass.
  • the metal mold is preheated in a temperature range of 200 degrees Celsius to 300 degrees Celsius, and the preheating time may be 1 hour to 2 hours.
  • two resistance furnaces can be respectively used to realize the melting of the raw material and the preheating of the metal mold.
  • the heating rate for heating the raw material and the heating rate for preheating the metal mold can be selected and adjusted by those skilled in the art according to the performance of the heating equipment.
  • the resistance furnace that preheats the metal mold can be turned on when the raw material approaches or reaches the melting temperature, so that the preheated metal mold with a suitable temperature can be taken out and used in time after the mixture is melted and the molten glass is obtained.
  • the raw materials include zinc source raw materials
  • the zinc source raw materials include at least one of the following or a combination thereof: zinc nitrate (Zn(NO 3 ) 2 ), zinc chloride (ZnCl 2 ), zinc sulfate (ZnSO 4 ), zinc oxide (ZnO).
  • the raw materials include boron source raw materials, and the boron source raw materials include boric acid (H 3 BO 3 ).
  • the raw materials include calcium source raw materials
  • the calcium source raw materials include at least one of the following or a combination thereof: calcium carbonate (CaCO 3 ), calcium nitrate (Ca(NO 3 ) 2 ), calcium sulfate ( CaSO 4 ), calcium phosphate (Ca(H 2 PO 4 ) 2 or CaHPO 4 ), calcium chloride (CaCl 2 ), calcium oxide (CaO).
  • the raw materials include phosphorus source raw materials
  • the phosphorus source raw materials include at least one of the following or a combination thereof: calcium phosphate (Ca(H 2 PO 4 ) 2 or CaHPO 4 ), ammonium phosphate ((NH 2 PO 4 ) 2 4 ) 3 PO 4 ), phosphorus oxide (P 2 O 5 ).
  • the zinc source raw material is a raw material for supplying zinc oxide.
  • the boron source raw material, the calcium source raw material, and the phosphorus source raw material are, in order, a raw material for providing boron oxide, a raw material for providing calcium oxide, and a raw material for providing phosphorus oxide.
  • the raw materials including zinc, boron, calcium and phosphorus can be directly added in the form of oxides (that is, zinc oxide, boron oxide, calcium oxide and phosphorus oxide are directly used as raw materials), or they can be added through salt compounds.
  • Form addition such as: zinc chloride, boric acid, calcium carbonate, various phosphates, calcium phosphates and other substances as raw materials).
  • the concentration and rate of zinc ion release in the soluble sterilizing glass can be effectively controlled, so as to ensure that the soluble sterilizing glass can effectively achieve sterilization for a long time.

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Abstract

一种可溶性杀菌玻璃和可溶性杀菌玻璃的制备方法。可溶性杀菌玻璃的材料包括：氧化锌，0.2质量份至10质量份；氧化硼，1质量份至20质量份；氧化钙，10质量份至30质量份；氧化磷，30质量份至70质量份。制备的可溶性杀菌玻璃能够提高可溶性杀菌玻璃中作为杀菌剂的锌离子的缓释性能，使得锌离子以合理的速率缓释，由此提高可溶性杀菌玻璃的杀菌效率和杀菌效果。

Description

可溶性杀菌玻璃和可溶性杀菌玻璃的制备方法
本申请要求于2020年12月31日提交到中国国家知识产权局的申请号为202011638430.8、发明名称为“可溶性杀菌玻璃和可溶性杀菌玻璃的制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及无机抗菌材料的技术领域，具体而言，涉及一种可溶性杀菌玻璃和一种可溶性杀菌玻璃的制备方法。
背景技术
抗菌材料是具有杀菌、抗菌性能的一类功能材料，其主要通过加入抗菌剂达到抗菌的作用。抗菌剂主要分为天然生物、有机和无机抗菌剂三类。
天然抗菌剂中研究较多的有壳聚糖和山梨酸等，这类抗菌剂安全环保且抗菌性好，但由于其耐热性差、药效期短且生产条件有限，难以实现产业化。
有机抗菌剂以有机酸类、酚类、季铵盐类、苯并咪唑类等有机物为抗菌成分，能有效抑制有害细菌、霉菌的繁殖，但稳定性较差、易分解，且通常毒性较大。
无机抗菌剂主要是将具有抗菌能力的金属或其离子加入沸石、硅胶等多孔材料或玻璃等材料中，获得抗菌材料。相比有机和生物抗菌材料，无机抗菌材料具有持效性好、广谱抗菌、耐热性和安全性好的特点。
在诸多无机抗菌剂中，锌是性能较好、使用较为广泛的抗菌剂之一，载锌抗菌玻璃材料因为抗菌效果优良且安全性好，因而有着广泛的应用研究。
然而，相关技术中存在的其中一项不足是：载锌抗菌玻璃材料的缓释性能不够理想。
发明内容
本申请旨在解决上述技术问题的至少之一。
为此，本申请的第一目的在于提供一种可溶性杀菌玻璃。
本申请的第二目的在于提供一种可溶性杀菌玻璃的制备方法。
为了实现本申请的第一目的，本申请的实施例提供了一种可溶性杀菌玻璃，包括：氧化锌，0.2质量份至10质量份；氧化硼，1质量份至20质量份；氧化钙，10质量份至30质量份；氧化磷，30质量份至70质量份。
锌离子是杀菌效果好并且性能稳定、成本较为低廉的无机杀菌剂。为了合理地控制锌离子在可溶性杀菌玻璃中的缓释速度和缓释效率，本技术方案提供了一种以氧化硼、氧化钙和氧化磷为主要成分的三元氧化物可溶性杀菌玻璃。氧化磷和氧化硼的添加与比例控制，能够使得锌离子在硼钙磷中以合理地速率进行缓释。具体而言，不限于任何理论地，申请人在实现本申请的过程中发现，氧化磷的添加能够增大锌离子的溶解率并促进银离子的释放。相反地，氧化硼的添加则能够降低锌离子的溶解率并抑制银离子的释放。因此，本技术方案对氧化磷和氧化硼的添加量与具体比例进行控制(即：氧化磷的含量为30质量份至70质量份，氧化硼的含量1质量份至20质量份)。由此，本技术方案能够对可溶性杀菌玻璃中锌离子的缓释速度和缓释效率进行合理控制。此外，氧化钙的加入能够适当降低可溶性杀菌玻璃的熔融温度，降低可溶性杀菌玻璃的生产成本，并提高可溶性杀菌玻璃的生产效率。还需要说明的是，本技术方案将氧化锌的含量控制为0.2质量份至10质量份，上述含量的氧化锌能够保证可溶性杀菌玻璃中锌离子的长效释放，保证可溶性杀菌玻璃的杀菌效果。
另外，本申请上述实施例提供的技术方案还可以具有如下附加技术特征：
上述技术方案中，可溶性杀菌玻璃还包括：着色剂，0.0001质量份至0.0008质量份。
添加着色剂的目的在于对可溶性杀菌玻璃的颜色进行调整和控制，以便满足用户的多样化需求。
上述任一技术方案中，着色剂包括以下至少之一或其组合：氧化钴、氧化锰、氧化铁、氧化铜、硫化镉。
本技术方案采用的着色剂具体为金属氧化物着色剂。金属氧化物着色剂的性能稳定，并且耐高温、不易分解。
上述任一技术方案中，可溶性杀菌玻璃还包括：氧化铈，0.0001质量份至0.0006质量份。
向可溶性杀菌玻璃中添加氧化铈，能够提高作为杀菌剂的锌离子中高价锌离子的比例。因此，氧化铈的添加能够提高本申请实施例的可溶性杀菌玻璃的杀菌效果和杀菌效率。
上述任一技术方案中，可溶性杀菌玻璃中的锌离子包括四价态锌离子。
相比于二价态锌离子而言，四价态锌离子的杀菌效果和杀菌效率更高，因此，包括四价态锌离子的可溶性杀菌玻璃不仅缓释效果更加优异，亦具有更优的杀菌效果。
上述任一技术方案中，可溶性杀菌玻璃还包括以下至少之一或其组合：氧化锂、氧化钠、氧化钾、氧化镁、氧化硅、氧化铝。
包括氧化锂、氧化钠和氧化钾的碱金属氧化物或碱土金属氧化物具有较为活泼的理化性能，能够有效降低可溶性杀菌玻璃的熔点。氧化硅和氧化铝的添加能够促进玻璃形成，提高可溶性杀菌玻璃的粘度和机械强度。氧化镁则能够提高熔融玻璃液的澄清程度和成型后的可溶性杀菌玻璃的光泽度和折射率。
上述任一技术方案中，可溶性杀菌玻璃中的锌离子的溶出量为1毫克锌离子/克水至500毫克锌离子/克水。
本技术方案能够有效地控制可溶性杀菌玻璃中锌离子释放的浓度和速率，以保证可溶性杀菌玻璃长期且有效地实现杀菌作用。
上述任一技术方案中，可溶性杀菌玻璃的厚度范围为3毫米至5毫米；和/或可溶性杀菌玻璃的长度范围为5毫米至8毫米。
上述尺寸的可溶性杀菌玻璃可满足多数家电产品的生产加工需求，并且具有相对合理的缓释周期和优异的缓释效率。此外，上述尺寸的可溶性杀菌玻璃能够及时地在自然条件下冷却，不易出现炸裂或碎裂，其成型时的成品合格率高，内应力小，即使不实施退火工艺，亦具有良好的机械强度和热稳定性。
为了实现本申请的第二目的，本申请的实施例提供了一种可溶性杀菌玻璃的制备方法，包括：按氧化锌：氧化硼：氧化钙：氧化磷＝(0.2-10)：(1-20)：(10-30)：(30-70)的质量比称量原料并将原料混合，获得混合物；将混合物熔融，获得玻璃液；将玻璃液冷却成型，获得可溶性杀菌玻璃。
本申请实施例的可溶性杀菌玻璃的制备方法能够获得如本申请任一实施例的可溶性杀菌玻璃，因此本申请实施例的可溶性杀菌玻璃的制备方法具有如 本申请任一实施例的可溶性杀菌玻璃的全部有益效果，在此不再赘述。
上述技术方案中，将混合物熔融，获得玻璃液，包括：将混合物在950摄氏度至1350摄氏度的温度范围内进行时长为0.5小时至2小时的熔融，获得玻璃液。
上述温度制度能够保证各金属氧化物的充分熔融，并保证本实施方式能够获得均质澄清的可溶性杀菌玻璃。
上述技术方案中，在将混合物熔融，获得玻璃液的处理前，制备方法还包括：对混合物进行预热。
预热工艺的目的是进一步有效排出原料中的杂质和气体，避免玻璃液在熔融过程中过多地产生气泡，以保证可溶性杀菌玻璃的质地坚实致密。
上述技术方案中，对混合物进行预热，包括：在250摄氏度至350摄氏度的温度范围内对混合物进行时长为0.5小时至1.5小时的预热。
上述预热条件可有效去除原料中的杂质和气体。
上述技术方案中，将玻璃液冷却成型，获得玻璃液，包括：将金属模具进行预热；将玻璃液倒入金属模具并自然冷却成型，获得可溶性杀菌玻璃。
在冷却成型前对金属模具进行预热可避免玻璃液在倾倒和成型过程中炸裂。
上述技术方案中，对金属模具进行预热，包括：将金属模具预热至200摄氏度至300摄氏度的温度范围。
上述对金属模具进行预热的温度制度可有效避免玻璃在冷却成型时炸裂。提高成品率。
上述技术方案中，原料包括锌源原料，锌源原料包括以下至少之一或其组合：硝酸锌、氯化锌、硫酸锌、氧化锌；和/或原料包括硼源原料，硼源原料包括硼酸；和/或原料包括钙源原料，钙源原料包括以下至少之一或其组合：碳酸钙、硝酸钙、硫酸钙、磷酸钙、氯化钙、氧化钙；和/或原料包括磷源原料，磷源原料包括以下至少之一或其组合：磷酸钙、磷酸铵、氧化磷。
包括锌、硼、钙和磷的原料可直接通过氧化物的形式添加，亦可通过盐类化合物的形式添加。其中，相比于以金属氧化物为原料，以金属盐类化合物作为原料能够提高玻璃的均质程度和澄清度。
本申请的附加方面和优点将在下面的描述部分中变得明显，或通过本申请的实践了解到。
附图说明
本申请的上述和/或附加的方面和优点从结合下面附图对实施例的描述中将变得明显和容易理解，其中：
图1为本申请一个实施例的可溶性杀菌玻璃制备方法的步骤流程图之一；
图2为本申请一个实施例的可溶性杀菌玻璃制备方法的步骤流程图之二；
图3为本申请一个实施例的可溶性杀菌玻璃制备方法的步骤流程图之三；
图4为本申请一个实施例的可溶性杀菌玻璃制备方法的步骤流程图之四；
图5为本申请一个实施例的可溶性杀菌玻璃制备方法的步骤流程图之五；
图6为本申请一个实施例的可溶性杀菌玻璃制备方法的步骤流程图之六。
具体实施方式
为了能够更清楚地理解本申请的上述目的、特征和优点，下面结合附图和具体实施方式对本申请进行进一步的详细描述。需要说明的是，在不冲突的情况下，本申请的实施例及实施例中的特征可以相互组合。
在下面的描述中阐述了很多具体细节以便于充分理解本申请，但是，本申请还可以采用其他不同于在此描述的其他方式来实施，因此，本申请的保护范围并不受下面公开的具体实施例的限制。
下面参照图1至图6描述本申请一些实施例的可溶性杀菌玻璃和可溶性杀菌玻璃的制备方法。
本申请实施例的可溶性杀菌玻璃包括：氧化锌(ZnO和/或ZnO 2)，氧化锌的添加量为0.2质量份至10质量份；氧化硼(B 2O 3)，氧化硼的添加量为1质量份至20质量份；氧化钙(CaO)，氧化钙的添加量为10质量份至30质量份；氧化磷(P 2O 5)，氧化磷的添加量为30质量份至70质量份。
举例而言，本施例的可溶性杀菌玻璃的材料具体包括：氧化锌，0.2质量份；氧化硼，19.8质量份；氧化钙，10质量份；氧化磷，70质量份。
再次举例而言，本施例的可溶性杀菌玻璃的材料具体包括：氧化锌，10 质量份；氧化硼，10质量份；氧化钙，30质量份；氧化磷，50质量份。
本申请实施例的目的在于提供一种可溶性玻璃。其中，可溶性玻璃是指在例如水的液体中能够缓慢且稳定地释放一种或多种功能离子的可溶性杀菌玻璃。本申请实施例的功能离子具体为锌离子(Zn 2+和/或Zn 4+)。锌离子具有良好的杀菌消毒效果，其以掺杂的形式占据金属氧化物玻璃的晶格，并在被液体浸泡或冲刷的环境下随着时间的推移变化稳定释放，以实现长效的杀菌作用。
添加锌离子的可溶性杀菌玻璃可被应用于洗衣机、空调器等家电用品中，用于对洗衣机的洗涤用水或放置空调器的室内空间进行杀菌。然而，相关技术中存在的其中一项问题是：实现杀菌功能的锌离子的缓释性能不够理想。
具体而言，锌离子在相关技术的可溶性杀菌玻璃中的缓释性能难以被控制。以放置于洗衣机中的锌离子掺杂可溶性杀菌玻璃举例而言，在固定的洗涤程序和洗涤时间范围内，如果可溶性杀菌玻璃中锌离子的释放速度过快，则锌离子会较早地释放完，并导致洗衣机在后期使用过程中杀菌效果下降，甚至失去杀菌效果。如果可溶性杀菌玻璃中锌离子的释放速度过慢，则导致洗衣机在整个使用过程中的杀菌效果均不够理想，难以实现对衣物或家纺用品的有效杀菌。
不限于任何理论地，申请人在实现本申请实施例的过程中发现，锌离子的缓释速度受到锌离子的添加量和作为基质材料的可溶性玻璃的组分与配比的影响。因此，为了合理地控制锌离子在可溶性杀菌玻璃中的缓释速度和缓释效率，本申请实施例提供了一种以氧化硼、氧化钙和氧化磷为主要成分的三元氧化物可溶性杀菌玻璃。其中，氧化硼、氧化钙和氧化磷的质量比为氧化硼：氧化钙：氧化磷＝(1-20)：(10-30)：(30-70)。上述组分和配比的原料可落入玻璃形成区内。氧化磷和氧化硼的添加与比例控制，能够使得锌离子在硼钙磷中以合理地速率进行缓释。氧化磷的添加能够增大锌离子的溶解率并促进锌离子的释放，而氧化硼的添加则能够降低锌离子的溶解率并抑制锌离子的释放。因此，本实施例通过控制磷硼之间的配比，能够对可溶性杀菌玻璃中锌离子的缓释速度和缓释效率进行合理控制。此外，氧化钙的加入能够适当降低可溶性杀菌玻璃的熔融温度，降低可溶性杀菌玻璃的生产成本，并提高可溶性杀菌玻璃的生产效率。还需要说明的是，本实施例将氧化锌的含量控制为0.2质量份至 10质量份，上述含量的氧化锌能够保证可溶性杀菌玻璃中锌离子的长效释放，保证可溶性杀菌玻璃的杀菌效果。
在本申请实施例的部分实施方式中，可溶性杀菌玻璃还包括：着色剂，着色剂的添加量为0.0001质量份至0.0008质量份。举例而言，本施例的可溶性杀菌玻中着色剂的含量可为0.0001质量份或0.0004质量份或0.0008质量份。添加着色剂的目的在于对可溶性杀菌玻璃的颜色进行调整和控制。其中，本领域技术人员可在上述范围内，对着色剂的添加量以及具体种类进行灵活选择和调节。着色剂可在配料的过程中与氧化硼、氧化钙和氧化磷等基质原料共同添加和相互混合，在对可溶性杀菌玻璃进入熔融加热的过程中，着色剂在熔融玻璃液中均匀地分布，以在熔融和冷却后，获得颜色均匀一致的可溶性杀菌玻璃。
在本申请实施例的部分实施方式中，着色剂包括以下金属氧化物中的任一者或全部：氧化钴(Co 2O 3)、氧化锰(MnO 2)、氧化铁(Fe 2O 3和/或Fe 3O 4)、氧化铜(CuO)、硫化镉(CdS)。本实施方式的着色剂具体为金属氧化物着色剂。金属氧化物着色剂的性能稳定，并且耐高温、不易分解。
在本申请实施例的部分实施方式中，可溶性杀菌玻璃还包括：氧化铈，氧化铈的添加量0.0001质量份至0.0006质量份。举例而言，本施例的可溶性杀菌玻中氧化铈的含量可为0.0001质量份或0.0003质量份或0.0006质量份。作为稀土元素的铈离子(Ce 3+)具有能级丰富和化合价较高的特点。向硼钙磷三元氧化物可溶性杀菌玻璃中添加氧化铈，能够提高作为杀菌剂的锌离子中高价锌离子(即：四价态锌离子)的比例。因此，氧化铈的添加能够提高本申请实施例的可溶性杀菌玻璃的杀菌效果和杀菌效率。
在本申请实施例的部分实施方式中，可溶性杀菌玻璃中的锌离子包括四价态锌离子。如上文所言，相比于二价态锌离子而言，四价态锌离子的杀菌效果和杀菌效率更高，因此，包括四价态锌离子的可溶性杀菌玻璃不仅缓释效果更加优异，亦具有更优的杀菌效果。
在本申请实施例的部分实施方式中，可溶性杀菌玻璃还包括以下至少之一或其组合：氧化锂、氧化钠、氧化钾、氧化镁、氧化硅、氧化铝。包括氧化锂、氧化钠和氧化钾的碱金属氧化物或碱土金属氧化物具有较为活泼的理化性能，能够有效降低可溶性杀菌玻璃的熔点(即：熔融温度)。氧化硅和氧化铝的添 加能够促进玻璃形成，提高可溶性杀菌玻璃的粘度和机械强度。氧化镁则能够提高熔融玻璃液的澄清程度和成型后的可溶性杀菌玻璃的光泽度和折射率。
在本申请实施例的部分实施方式中，可溶性杀菌玻璃中的锌离子的溶出量为1毫克锌离子/克水至500毫克锌离子/克水。本实施方式中，锌离子的溶出量通过以下方式测试：采用5C滤纸过滤锌离子溶出液，制成测定试样。在制成测定试样后，利用锌离子计、原子吸收光谱分析装置、电感耦合等离子体质谱仪(ICP-MS)等能够测定锌离子浓度的测试分析装置测定试样中的锌离子浓度。本实施方式测试获得的在30摄氏度的温度条件下和24小时的测试时间下的锌离子溶出量为1毫克锌离子/克水至500毫克锌离子/克水，即：1(mg/(g·1L·24Hrs·30℃))至500(mg/(g·1L·24Hrs·30℃))。
在本申请实施例的部分实施方式中，可溶性杀菌玻璃的厚度范围为3毫米至5毫米。可溶性杀菌玻璃的长度范围为5毫米至8毫米。可溶性杀菌玻璃的尺寸和形状与所采用成型模具的尺寸和形状一致。本实施方式的可溶性杀菌玻璃可制备成片状或板状或块状，亦可制备成球形或类球形等形状。锌离子的缓释效率和缓释周期收到可溶性杀菌玻璃的尺寸和形状的影响。采用上述尺寸的型模具制备的可溶性杀菌玻璃可满足多数家电产品的生产加工需求，并且具有相对合理的缓释周期和优异的缓释效率。此外，上述尺寸的可溶性杀菌玻璃能够及时地在自然条件下冷却，不易出现炸裂或碎裂，其成型时的成品合格率高，内应力小，即使不实施退火工艺，亦具有良好的机械强度和热稳定性。
图1为本申请一个实施例的可溶性杀菌玻璃制备方法的步骤流程图之一。如图1所示，本申请实施例的可溶性杀菌玻璃制备方法包括：
步骤S102，按氧化锌：氧化硼：氧化钙：氧化磷＝(0.2-10)：(1-20)：(10-30)：(30-70)的质量比称量原料并将原料混合，获得混合物；
步骤S104，将混合物熔融，获得玻璃液；
步骤S106，将玻璃液冷却成型，获得可溶性杀菌玻璃。
在本申请实施例的可溶性杀菌玻璃中，基于可溶性杀菌玻璃的总质量为100质量份(100wt％)，作为杀菌剂的氧化锌的含量为0.2wt％至10wt％，氧化硼的含量为1wt％至20wt％，氧化钙的含量为10wt％至30wt％，氧化磷的含量为30wt％至70wt％。
需要说明的是，本实施例以质量分数限定可溶性杀菌玻璃中各氧化物的比例关系。当直接以各元素的氧化物为原料，则本实施例可根据上述步骤S102中的比例关系直接对原料进行承重计量。当直接以各元素的盐类化合物为原料，则本实施例可根据各原料的摩尔质量与质量分数之间的换算关系确定原始称重比例。如采用液体原料，本实施例可根据体积浓度与质量分数之间的换算关系确定原始称重比例。本领域技术人员知晓上述换算与称重方式，本申请实施例对此不进行赘述。
此外，除包括氧化锌、氧化硼、氧化钙和氧化磷的主要原料之外，本实施例还可添加其它金属氧化物辅料。举例而言，本实施例可采用硝酸银(AgNO 3)、磷酸钙(Ca(H 2PO 4) 2)、磷酸钠(NaH 2PO 4)、磷酸铵(NH 4H 2PO 4)、硼酸(H 3BO 3)、氧化锌(ZnO)、氧化铜(CuO)、氧化钴(Co 2O 3)和氧化铈CeO 2为原料。其中，以全部原料的质量总和为100wt％计量，各原料在总原料中所占的质量比如下：硝酸银的占比为3wt％；磷酸钙的占比为78wt％；磷酸钠的占比为8.7wt％；磷酸铵的占比为0.9％；硼酸的占比为5.9wt％；氧化锌的占比为2.55wt％；氧化铜的占比为0.4wt％；氧化钴的占比为0.05wt％；氧化铈的占比为0.5wt％。
当制备较少的可溶性杀菌玻璃时，本申请实施例的称料过程可采用分析天平实现，通过玛瑙研钵或行星球磨机等小型混合设备实现原料的混合研磨，并通过电阻炉或马弗炉实现置于白金坩埚中的混合物的熔融，最终将白金坩埚中的玻璃液倾倒至铝板模具或铁板模具之上冷却成型。
当在实际生产中制备大量的可溶性杀菌玻璃时，本申请实施例的称料过程可采用大型磅秤实现，通过混炼机实现原料的混合研磨，并通过窑炉等大型设备实现混合物的熔融以及冷却。
需要说明的是，步骤S106的冷却成型工艺可为自然冷却，亦可为随炉冷却，还可为通过水淬方式冷却。
还需要说明的是，步骤S104的熔融工艺可在大气环境中进行，亦可在还原气氛或惰性气体中进行。
在冷却后，本实施方式还可实施退火工艺，以消除可溶性杀菌玻璃的内应力。退火工艺的温度范围为200摄氏度至500摄氏度，退火时长为2小时至4 小时。
本申请实施例的可溶性杀菌玻璃制备方法能够获得如本申请任一实施例的可溶性杀菌玻璃。本申请实施例的可溶性杀菌玻璃制备方法具有如本申请任一实施例的可溶性杀菌玻璃的全部有益效果，尤其需要说明的是，该可溶性杀菌玻璃中掺杂有缓释性能优异、缓释效率合理可控的锌离子杀菌剂。
在本申请实施例的部分实施方式中，将混合物熔融，获得玻璃液，包括：将混合物在950摄氏度至1350摄氏度的温度范围内进行时长为0.5小时至2小时的熔融，获得玻璃液。图2为本申请一个实施例的可溶性杀菌玻璃制备方法的步骤流程图之二。如图2所示，本实施方式的可溶性杀菌玻璃制备方法包括：
步骤S202，按氧化锌：氧化硼：氧化钙：氧化磷＝(0.2-10)：(1-20)：(10-30)：(30-70)的质量比称量原料并将原料混合，获得混合物；
步骤S204，将混合物在950摄氏度至1350摄氏度的温度范围内进行时长为0.5小时至2小时的熔融，获得玻璃液；
步骤S206，将玻璃液冷却成型，获得可溶性杀菌玻璃。
本实施方式步骤S204所采用的熔融工艺中的温度制度能够保证各金属氧化物的充分熔融，并保证本实施方式能够获得均质澄清的可溶性杀菌玻璃。
在本申请实施例的部分实施方式中，在将混合物熔融，获得玻璃液的处理前，制备方法还包括：对混合物进行预热。图3为本申请一个实施例的可溶性杀菌玻璃制备方法的步骤流程图之三。如图3所示，本实施方式的可溶性杀菌玻璃制备方法包括：
步骤S302，按氧化锌：氧化硼：氧化钙：氧化磷＝(0.2-10)：(1-20)：(10-30)：(30-70)的质量比称量原料并将原料混合，获得混合物；
步骤S304，对混合物进行预热；
步骤S306，将混合物熔融，获得玻璃液；
步骤S308，将玻璃液冷却成型，获得可溶性杀菌玻璃。
预热工艺的目的是进一步有效排出原料中的杂质和气体，避免玻璃液在熔融过程中过多地产生气泡，以保证可溶性杀菌玻璃的质地坚实致密。
在本申请实施例的部分实施方式中，对混合物进行预热，包括：在250 摄氏度至350摄氏度的温度范围内对混合物进行时长为0.5小时至1.5小时的预热。图4为本申请一个实施例的可溶性杀菌玻璃制备方法的步骤流程图之四。如图4所示，本实施方式的可溶性杀菌玻璃制备方法包括：
步骤S402，按氧化锌：氧化硼：氧化钙：氧化磷＝(0.2-10)：(1-20)：(10-30)：(30-70)的质量比称量原料并将原料混合，获得混合物；
步骤S404，在250摄氏度至350摄氏度的温度范围内对混合物进行时长为0.5小时至1.5小时的预热；
步骤S406，将混合物熔融，获得玻璃液；
步骤S408，将玻璃液冷却成型，获得可溶性杀菌玻璃。
本实施方式在250摄氏度至350摄氏度的温度范围内对混合物预热，预热的时长超过0.5小时，但不超过1.5小时。上述预热条件可有效去除原料中的杂质和气体。
在本申请实施例的部分实施方式中，将玻璃液冷却成型，获得玻璃液，包括：将金属模具进行预热；将玻璃液倒入金属模具并自然冷却成型，获得玻璃液。图5为本申请一个实施例的可溶性杀菌玻璃制备方法的步骤流程图之五。如图5所示，本实施方式的可溶性杀菌玻璃制备方法包括：
步骤S502，按氧化锌：氧化硼：氧化钙：氧化磷＝(0.2-10)：(1-20)：(10-30)：(30-70)的质量比称量原料并将原料混合，获得混合物；
步骤S504，将混合物熔融，获得玻璃液；
步骤S506，将金属模具进行预热；
步骤S508，将玻璃液倒入金属模具并自然冷却成型，获得可溶性杀菌玻璃。
本实施方式的金属模具可为铝制模具或铁制模具等耐热和导热性能较优的金属模具。在冷却成型前对金属模具进行预热的目的是避免玻璃液在倾倒和成型过程中炸裂。自然冷却成型是指将容纳有玻璃液的金属模具在室温环境(比如20摄氏度至30摄氏度之间)中放置并自然冷却，直至液态的玻璃液成为固态块状的玻璃体。
在本申请实施例的部分实施方式中，对金属模具进行预热，包括：将金属模具预热至200摄氏度至300摄氏度的温度范围。图6为本申请一个实施例的 可溶性杀菌玻璃制备方法的步骤流程图之六。如图6所示，本实施方式的可溶性杀菌玻璃制备方法包括：
步骤S602，按氧化锌：氧化硼：氧化钙：氧化磷＝(0.2-10)：(1-20)：(10-30)：(30-70)的质量比称量原料并将原料混合，获得混合物；
步骤S604，将混合物熔融，获得玻璃液；
步骤S606，将金属模具预热至200摄氏度至300摄氏度的温度范围；
步骤S608，将玻璃液倒入金属模具并自然冷却成型，获得可溶性杀菌玻璃。
本实施方式在200摄氏度至300摄氏度的温度范围内对金属模具进行预热，预热的时长可为1小时至2小时。举例而言，本实施方式可分别采用两个电阻炉分别实现对原料的熔融和对金属模具的预热。对原料加热的升温速率和对金属模具预热的升温速率可由本领域技术人员根据加热设备的性能进行选择和调整。其中，本实施方式可在原料接近或达到熔融温度后开启对于金属模具进行预热的电阻炉，以便在将混合物熔融并获得玻璃液后及时将完成预热且温度适宜的金属模具取出并使用。
在本申请实施例的部分实施方式中，原料包括锌源原料，锌源原料包括以下至少之一或其组合：硝酸锌(Zn(NO 3) 2)、氯化锌(ZnCl 2)、硫酸锌(ZnSO 4)、氧化锌(ZnO)。
在本申请实施例的部分实施方式中，原料包括硼源原料，硼源原料包括硼酸(H 3BO 3)。
在本申请实施例的部分实施方式中，原料包括钙源原料，钙源原料包括以下至少之一或其组合：碳酸钙(CaCO 3)、硝酸钙(Ca(NO 3) 2)、硫酸钙(CaSO 4)、磷酸钙(Ca(H 2PO 4) 2或CaHPO 4)、氯化钙(CaCl 2)、氧化钙(CaO)。
在本申请实施例的部分实施方式中，原料包括磷源原料，磷源原料包括以下至少之一或其组合：磷酸钙(Ca(H 2PO 4) 2或CaHPO 4)、磷酸铵((NH 4) 3PO 4)、氧化磷(P 2O 5)。
锌源原料为用于提供氧化锌的原料。相应地，硼源原料、钙源原料和磷源原料依次为用于提供氧化硼的原料、用于提供氧化钙的原料和用于提供氧化磷的原料。需要说明的是，包括锌、硼、钙和磷的原料可直接通过氧化物的形式 添加(即：直接以氧化锌、氧化硼、氧化钙和氧化磷作为原料)，亦可通过盐类化合物的形式添加(比如：氯化锌、硼酸、碳酸钙、各种磷酸盐、钙磷酸盐等物质作为原料)。其中，以盐类化合物作为原料，则含有锌、硼、钙和磷的各盐类化合物在高温条件下氧化成为氧化物，并在熔融后获得氧化物玻璃。相比于以金属氧化物为原料，以金属盐类化合物作为原料能够提高玻璃的均质程度和澄清度。
综上，本申请实施例的有益效果为：
1.本申请实施例通过对可溶性杀菌玻璃的选料和配比的调整，能够有效地控制可溶性杀菌玻璃中锌离子释放的浓度和速率，以保证可溶性杀菌玻璃长期且有效地实现杀菌作用。
2.本申请实施例通过对可溶性杀菌玻璃的加工工艺调整，可获得机械强度高、澄清度高，并且锌离子负载量大的可溶性杀菌玻璃。
在本说明书的描述中，术语“一个实施例”、“一些实施例”、“具体实施例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或特点包含于本申请的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不一定指的是相同的实施例或实例。而且，描述的具体特征、结构、材料或特点可以在任何的一个或多个实施例或示例中以合适的方式结合。
以上仅为本申请的优选实施例而已，并不用于限制本申请，对于本领域的技术人员来说，本申请可以有各种更改和变化。凡在本申请的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本申请的保护范围之内。

Claims (15)

  1. 一种可溶性杀菌玻璃，其中，所述可溶性杀菌玻璃的材料包括：
    氧化锌，0.2质量份至10质量份；
    氧化硼，1质量份至20质量份；
    氧化钙，10质量份至30质量份；
    氧化磷，30质量份至70质量份。
  2. 根据权利要求1所述的可溶性杀菌玻璃，其中，还包括：
    着色剂，0.0001质量份至0.0008质量份。
  3. 根据权利要求2所述的可溶性杀菌玻璃，其中，所述着色剂包括以下至少之一或其组合：氧化钴、氧化锰、氧化铁、氧化铜、硫化镉。
  4. 根据权利要求1所述的可溶性杀菌玻璃，其中，还包括：
    氧化铈，0.0001质量份至0.0006质量份。
  5. 根据权利要求1所述的可溶性杀菌玻璃，其中，所述可溶性杀菌玻璃中的锌离子包括四价态锌离子。
  6. 根据权利要求1所述的可溶性杀菌玻璃，其中，还包括以下至少之一或其组合：
    氧化锂、氧化钠、氧化钾、氧化镁、氧化硅、氧化铝。
  7. 根据权利要求1至6中任一项所述的可溶性杀菌玻璃，其中，所述可溶性杀菌玻璃中的锌离子的溶出量为1毫克锌离子/克水至500毫克锌离子/克水。
  8. 根据权利要求1至6中任一项所述的可溶性杀菌玻璃，其中，
    所述可溶性杀菌玻璃的厚度范围为3毫米至5毫米；和/或
    所述可溶性杀菌玻璃的长度范围为5毫米至8毫米。
  9. 一种可溶性杀菌玻璃的制备方法，其中，包括：
    按氧化锌：氧化硼：氧化钙：氧化磷＝(0.2-10)：(1-20)：(10-30)：(30-70)的质量比称量原料并将所述原料混合，获得混合物；
    将所述混合物熔融，获得玻璃液；
    将所述玻璃液冷却成型，获得所述可溶性杀菌玻璃。
  10. 根据权利要求9所述的可溶性杀菌玻璃的制备方法，其中，所述将所 述混合物熔融，获得玻璃液，包括：
    将所述混合物在950摄氏度至1350摄氏度的温度范围内进行时长为0.5小时至2小时的熔融，获得所述玻璃液。
  11. 根据权利要求9所述的可溶性杀菌玻璃的制备方法，其中，在所述将所述混合物熔融，获得玻璃液的处理前，所述制备方法还包括：
    对所述混合物进行预热。
  12. 根据权利要求11所述的可溶性杀菌玻璃的制备方法，其中，所述对所述混合物进行预热，包括：
    在250摄氏度至350摄氏度的温度范围内对所述混合物进行时长为0.5小时至1.5小时的预热。
  13. 根据权利要求9所述的可溶性杀菌玻璃的制备方法，其中，所述将所述玻璃液冷却成型，获得玻璃液，包括：
    将金属模具进行预热；
    将所述玻璃液倒入所述金属模具并自然冷却成型，获得可溶性杀菌玻璃。
  14. 根据权利要求13所述的可溶性杀菌玻璃的制备方法，其中，所述对金属模具进行预热，包括：
    将所述金属模具预热至200摄氏度至300摄氏度的温度范围。
  15. 根据权利要求9至14中任一项所述的可溶性杀菌玻璃的制备方法，其中，
    所述原料包括锌源原料，所述锌源原料包括以下至少之一或其组合：硝酸锌、氯化锌、硫酸锌、氧化锌；和/或
    所述原料包括硼源原料，所述硼源原料包括硼酸；和/或
    所述原料包括钙源原料，所述钙源原料包括以下至少之一或其组合：碳酸钙、硝酸钙、硫酸钙、磷酸钙、氯化钙、氧化钙；和/或
    所述原料包括磷源原料，所述磷源原料包括以下至少之一或其组合：磷酸钙、磷酸铵、氧化磷。
PCT/CN2021/094116 2020-12-31 2021-05-17 可溶性杀菌玻璃和可溶性杀菌玻璃的制备方法 WO2022142074A1 (zh)

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