CN111377608B - Deep sea glass floating ball and preparation method thereof - Google Patents
Deep sea glass floating ball and preparation method thereof Download PDFInfo
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- CN111377608B CN111377608B CN202010190325.6A CN202010190325A CN111377608B CN 111377608 B CN111377608 B CN 111377608B CN 202010190325 A CN202010190325 A CN 202010190325A CN 111377608 B CN111377608 B CN 111377608B
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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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
- B63B—SHIPS OR OTHER WATERBORNE VESSELS; EQUIPMENT FOR SHIPPING
- B63B22/00—Buoys
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
- C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
-
- 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
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
-
- 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
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
- C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
- B63B—SHIPS OR OTHER WATERBORNE VESSELS; EQUIPMENT FOR SHIPPING
- B63B22/00—Buoys
- B63B2022/006—Buoys specially adapted for measuring or watch purposes
Abstract
The invention provides a deep sea glass floating ball which is prepared from the following components in parts by mass: 55-65 wt% of silicon oxide; 18-25 wt% of alumina; 3-6 wt% of lithium oxide; 2-5 wt% of magnesium oxide; 2-6 wt% of sodium oxide; 0.5-2 wt% of potassium oxide; 0.5-1.5 wt% of boron oxide; 0-1 wt% of zirconium oxide; 0-1 wt% of titanium oxide; the mass fractions of zirconia and titania are not 0 at the same time. The invention uses Li as the main component2O‑Al2O3‑SiO2The prepared transparent glass ceramics have no phenomenon that the performance of the glass is obviously influenced by the equality, the components of the glass body are uniform, the performance can meet the use requirement of the deep sea floating ball, the cost is lower, the pressure resistance is higher, and the working depth of the deep sea glass floating ball prepared by the glass is more than 12000 m. The invention also provides a preparation method of the deep sea glass floating ball.
Description
Technical Field
The invention belongs to the technical field of ocean exploration, and particularly relates to a deep-sea glass floating ball and a preparation method thereof.
Background
The buoy and submerged buoy system is an important technical device for marine exploration, and can perform long-term, continuous, synchronous, automatic and comprehensive monitoring on various elements of marine hydrology and meteorology. The glass floating ball is an important component of a submerged buoy system, and can provide buoyancy for the system and serve as an instrument cabin.
The existing deep sea glass floating ball is mainly made of borosilicate glass material, and has the characteristics of low thermal expansion rate, high transparency, high compressive strength, light weight, no pollution, no magnetism, no electric conduction and the like. The preparation method generally has two methods: firstly, adopt the mould method to make glass hemisphere earlier, match glass hemisphere in pairs again, inside evacuation is to being less than 0.3 atmospheric pressure afterwards. After vacuumizing, the sealing agent is coated on the hemispherical joint and then the protective adhesive tape is wound on the hemispherical joint. And secondly, preparing the coated spheres by a template method, performing suction filtration, cleaning, drying at room temperature, and then sintering at a preset heat treatment temperature system to obtain the hollow glass microspheres.
Due to the presence of a large amount of B in borosilicate glass2O3，B2O3Has the characteristic of being volatile at high temperature. Alkali metal oxide (Na) in borosilicate glass2O and K2O) is insufficient, boron oxygen trigone (B-O)3) Is not enough to be converted into boron-oxygen tetrahedron (B-O)4) Boron oxygen trigones (B-O) present in the glass network3) Is large and further enrichment of certain regions is prone to phase separation in the formation of the glass, eventually forming a silica-rich phase and an alkali-boron-rich phase in the glass. Phase separation has an effect on the glass properties, and when phase separation causes the size of the alkali-rich boron phase to exceed that of visible light waves, the phase separation causes visible opacification, which affects the optical properties of the glass. Meanwhile, when the annealing process fluctuates, the alkali-rich boron phase and the silica-rich phase in the borosilicate glass form a mutually staggered three-dimensional network structure, so that the chemical stability of the glass is greatly reduced, and the glass is easy to corrode. Contamination by volatilization of boron also presents certain difficulties in its production.
Disclosure of Invention
The deep sea glass floating ball has no phase separation, and has high pressure resistance and deep submerging depth.
The invention provides a deep sea glass floating ball which is prepared from the following components in parts by mass:
the mass fractions of zirconia and titania are not 0 at the same time.
The invention provides a preparation method of a deep sea glass floating ball, which comprises the following steps:
A) according to mass fraction, 55-65 wt% of silicon oxide, 18-25 wt% of aluminum oxide and 3-6 wt% of lithium oxide are added; mixing and ball-milling 2-5 wt% of magnesium oxide, 2-6 wt% of sodium oxide, 0.5-2 wt% of potassium oxide, 0.5-1.5 wt% of boron oxide, 0-1 wt% of zirconium oxide and 0-1 wt% of titanium oxide, drying and sieving after ball-milling to obtain mixed powder;
B) melting the mixed powder at high temperature, clarifying and homogenizing to obtain glass liquid, and pouring the glass liquid into deionized water to obtain glass particles;
C) adding a binder into the glass particles, grinding and granulating, and then performing compression molding on the granulated glass particles to obtain a molded glass hemisphere;
D) calcining the formed glass hemisphere at 400-550 ℃, heating to 800-900 ℃ at the speed of 1-5 ℃/min, preserving heat for 0.5-1 hour, taking out and cooling to obtain a parent glass hemisphere;
E) heating the mother glass hemisphere to a nucleation temperature, then preserving heat for 0.5-2 hours, heating to a crystallization temperature, preserving heat for 1-2.5 hours, and finally performing chemical strengthening to obtain a deep sea glass floating ball hemisphere;
F) and matching every two hemispheres of the deep-sea glass floating ball, and assembling to obtain the deep-sea glass floating ball.
Preferably, the drying temperature in the step A) is 90-110 ℃;
the mesh number sieved in the step A) is 30-50 meshes.
Preferably, the temperature of the high-temperature melting in the step B) is 1500-1800 ℃;
and the time of high-temperature melting in the step B) is 3-5 hours.
Preferably, the binder in step C) is one or more of polyvinyl alcohol, an aqueous acrylic acid solution and carboxymethyl cellulose.
Preferably, the nucleation temperature in the step E) is 650-750 ℃.
Preferably, the crystallization temperature in the step E) is 750-850 ℃.
Preferably, the chemical strengthening is specifically:
dipping the crystallized glass floating ball in mixed molten salt to obtain a deep-sea glass floating ball hemisphere;
the mixed molten salt comprises the following components in percentage by mass:
KNO3：25～50％、NaNO3：49～70％、CsNO3：1～5％。
preferably, the dipping temperature is 450-750 ℃;
the dipping time is 45-90 min.
Preferably, in the step F), after the half spheres of the deep sea glass floating ball are matched with each other, vacuumizing is carried out until the pressure is lower than 0.3 atmospheric pressure, and then a sealant is coated on the joint of the two half spheres and a protective adhesive tape is wound on the joint to obtain the deep sea glass floating ball.
The invention provides a deep sea glass floating ball which is prepared from the following components in parts by mass: 55-65 wt% of silicon oxide; 18-25 wt% of alumina; 3-6 wt% of lithium oxide; 2-5 wt% of magnesium oxide; 2-6 wt% of sodium oxide; 0.5-2 wt% of potassium oxide; 0.5-1.5 wt% of boron oxide; 0-1 wt% of zirconium oxide; 0-1 wt% of titanium oxide; the mass fractions of zirconia and titania are not 0 at the same time. The invention provides a novel glass formula suitable for a deep sea floating ball, aiming at the problems of the existing borosilicate glass. The invention uses Li as the main component2O-Al2O3-SiO2The prepared transparent glass ceramics have no phenomenon that the performance of the glass is obviously influenced by the equality, the components of the glass body are uniform, the performance can meet the use requirement of the deep sea floating ball, the cost is lower, the pressure resistance is higher, and the working depth of the deep sea glass floating ball prepared by the glass is more than 12000 m.
Detailed Description
The invention provides a deep sea glass floating ball which is prepared from the following components in parts by mass:
the mass fractions of zirconia and titania are not 0 at the same time.
In the present invention, SiO2Mainly forms silicon-oxygen tetrahedrons and is connected to form a glass network structure, and the silicon-oxygen tetrahedrons are basic frameworks of glass. SiO 22The addition amount is preferably 55-65 wt%, more preferably 56-62 wt%, the grain size of the microcrystalline glass is easy to control, the size of the precipitated crystal is small, and transparent microcrystalline glass can be obtained. Specifically, in the embodiment of the present invention, it may be 56 wt%, 59 wt%, 62 wt%, or 65 wt%.
In the present invention, Al2O3Preferably 18 to 25 wt%, preferably 20 to 22 wt% in SiO2When the adding amount is 56-62 wt%, aluminum tetrahedron and silicon tetrahedron which can be formed in the glass are interpenetrated to form a network structure, so that the microcrystalline glass with lower thermal expansion coefficient and better transparency is obtained. Al (Al)2O3The content is increased to reduce the crystallization tendency of the glass and improve the thermal stability, chemical stability, mechanical strength, refractive index and hardness of the glass, but when the content exceeds 25 wt%, mullite is easily precipitated in the glass, so that the viscosity of the glass is increased, the melting temperature is increased, and the formability is deteriorated. Specifically, in the embodiment of the present invention, it may be 18 wt%, 20 wt%, 22 wt%, or 25 wt%.
In the present invention, the Li2O is one of important raw materials for forming the microcrystalline glass with a beta-quartz solid solution structure, and contributes to the preparation of the transparent microcrystalline glass with a low thermal expansion coefficient, and the content of the O is generally more than 3 wt%. Li2The increase of the O content can reduce the viscosity of the glass, accelerate the melting of the glass and improve the forming performance, but when the O content exceeds 6 wt%, the crystallization capacity of the glass is too high, and the stability of the glass is reduced. Thus, Li in the present application2The mass fraction of O is preferably 3 to 6 wt%, more preferably 4 to 5 wt%. Specifically, in the embodiment of the present invention, it may be 3 wt%, 4 wt%, 5 wt%, or 6 wt%.
In the present invention, Na2O and K2O is represented by R in the glass component in a total amount2And O. In the invention, R2The addition amount of O is 2.5-8 wt%, and Na is added2O can lower the melting temperature of the glass and greatly reduce the viscosity of the molten glassThe high-temperature fluidity of the glass is improved, the glass is a good fluxing agent, if the content is too large, the mechanical strength, the chemical stability and the thermal stability of the glass are reduced, the expansion coefficient of the glass is increased, the glass is brittle, the glass is easy to precipitate alkali and mildew, the production cost is increased, and therefore, the content cannot be too high. With small amounts of K2O is substituted, so that the double-alkali effect is achieved, the chemical stability of the glass can be improved, and the crystallization is obviously reduced. Introduction of K2O is mainly because it can greatly reduce the surface tension of the glass, is beneficial to flattening and polishing the glass liquid and improves the luster of the glass liquid.
Na in the invention2The mass fraction of O is preferably 2 to 6 wt%, more preferably 3 to 5.5 wt%, and specifically, in the embodiment of the present invention, may be 3 wt%, 4 wt%, 5 wt%, or 5.5 wt%; k2The mass fraction of O is preferably 0.5 to 2 wt%, more preferably 1 to 1.5 wt%, and specifically, may be 0.5 wt%, 1 wt%, or 2 wt% in the embodiment of the present invention.
In the invention, MgO can reduce the high-temperature viscosity, the crystallization tendency and the crystallization speed of glass, improve the mechanical strength, the chemical stability and the thermal stability, and when the temperature is higher than 1200 ℃, the addition of MgO can reduce the viscosity of the glass liquid, and the viscosity tends to be increased between 900 ℃ and 1200 ℃. The mass fraction of MgO in the present invention is preferably 2 to 5 wt%, more preferably 3 to 4 wt%, and specifically, in the embodiment of the present invention, it may be 2 wt%, 3 wt%, 4 wt%, or 5 wt%.
In the present invention, B2O3With boron-oxygen trigonal [ B-O ]3]And boron-oxygen tetrahedron [ B-O4]Are structural components. B is2O3Can reduce the expansion coefficient of the glass, improve the thermal stability, chemical stability and mechanical property of the glass, increase the refractive index of the glass and improve the gloss of the glass. Because it can reduce the viscosity of glass liquid at high temperature, it is favorable for melting and clarifying glass, and can improve the devitrification property of glass, and can also act as fluxing agent. But B2O3The volatility is strong, the melting temperature is higher, the time is longer, the volatilization amount is more, the surface of the molten glass is easy to peel, and the melting technology is not easy to master, so the formula B in the invention2O3Is addedThe amount is preferably 0.5 to 1.5 wt%, and specifically, in the embodiment of the present invention, may be 0.5 wt%, 1 wt%, or 1.5 wt%.
In the present invention, ZrO2、TiO2The nucleating agent is used as a nucleating agent to control the nucleation and crystallization processes of the microcrystalline glass. The nucleating agent has great influence on the performance of the transparent glass ceramics, and TiO2High solubility in glass melts, TiO in heat treatment2Can promote phase separation and form a titanium-rich phase, and can ensure that the glass is uniformly crystallized at a lower temperature. ZrO (ZrO)2As crystal nucleus agent and TiO in the crystallization process of microcrystalline glass2With similar behavior. But ZrO2Solubility in glass is small and cannot be made like TiO2Which can reduce the viscosity of the glass. Thus, the invention will ZrO2With TiO2Used as a mixed crystal nucleus agent. The mixed crystal nucleating agent can strongly influence the phase change kinetics of the glass, thereby influencing the final performance of the glass.
The content of the nucleating agent is increased, low-temperature crystallization is facilitated, if the content of the nucleating agent is insufficient, the number of crystal nuclei is small, the crystal grain growth of the beta quartz solid solution is overlarge, and the devitrification phenomenon of the microcrystalline glass occurs, so that the total content of the nucleating agent is preferably 0-2 wt%, and ZrO in the invention2Is preferably 0 to 1 wt%, more preferably 0.5 wt%, TiO2The mass fraction (b) is preferably 0 to 1 wt%, more preferably 0.5 wt%.
The invention also provides a preparation method of the deep sea glass floating ball, which comprises the following steps:
A) according to mass fraction, 55-65 wt% of silicon oxide, 18-25 wt% of aluminum oxide and 3-6 wt% of lithium oxide are added; mixing and ball-milling 2-5 wt% of magnesium oxide, 2-6 wt% of sodium oxide, 0.5-2 wt% of potassium oxide, 0.5-1.5 wt% of boron oxide, 0-1 wt% of zirconium oxide and 0-1 wt% of titanium oxide, drying and sieving after ball-milling to obtain mixed powder;
B) melting the mixed powder at high temperature, clarifying and homogenizing to obtain glass liquid, and pouring the glass liquid into deionized water to obtain glass particles;
C) adding a binder into the glass particles, grinding and granulating, and then performing compression molding on the granulated glass particles to obtain a molded glass hemisphere;
D) calcining the formed glass hemisphere at 400-6000 ℃, heating to 800-900 ℃ at the speed of 1-5 ℃/min, preserving heat for 0.5-1 hour, taking out and cooling to obtain a parent glass hemisphere;
E) heating the mother glass hemisphere to a nucleation temperature, then preserving heat for 0.5-2 hours, heating to a crystallization temperature, preserving heat for 1-2.5 hours, and finally performing chemical strengthening to obtain a deep sea glass floating ball hemisphere;
F) and matching every two hemispheres of the deep-sea glass floating ball, and assembling to obtain the deep-sea glass floating ball.
According to the formula of the deep sea glass floating ball, the raw materials are mixed, ball-milled, dried and sieved to obtain the powder with uniform particle size distribution.
In the present invention, the ball milling is a mixing means well known in the art, and is not described in detail herein. The drying temperature is preferably 90-110 ℃, and more preferably 100 ℃; in the present invention, the drying time is not particularly limited, and the drying may be performed in a forced air oven, preferably, after all the moisture in the powder slurry is evaporated. In the invention, the dried powder is preferably screened in a metal screen, and the mesh number of the screen is preferably 30-50 meshes, and more preferably 40 meshes.
In the invention, the mixed powder undergoes a series of chemical reactions in the high-temperature melting process, gas is discharged, and the glass liquid is obtained after the mixed powder is clarified and homogenized. The high-temperature melting temperature is preferably 1500-1800 ℃, and more preferably 1600-1700 ℃; the high-temperature melting time is preferably 3-5 hours, so that the molten glass is melted and clarified.
After the glass particles are obtained, the invention adds the binder into the glass particles, continuously grinds the glass particles and carries out granulation so as to reduce the surface activity of the surfaces of the particles, so that the contact between the glass particles is tighter, and the subsequent dry pressing molding is convenient.
In the present invention, the binder is preferably polyvinyl alcohol; in the invention, the grinding is preferably carried out by using an aqueous solution of a binder, and the molar concentration of the aqueous solution of the binder is preferably 40-60%. The invention grinds and granulates glass particles and binder in an agate bowl.
And placing the granulated glass particles under an oil press, and pressing the glass particles into glass hemispheres with uniform diameter and wall thickness by using a manufactured hemisphere die. The mold is preferably a graphite mold.
And after dry pressing forming, putting the formed glass hemisphere into an electric furnace, calcining to fully discharge the binder, then heating to 800-900 ℃, and preserving heat for 0.5-1 hour to obtain a parent glass hemisphere with smooth surface, good porcelain forming and compactness.
In the invention, the calcining temperature is preferably 400-600 ℃, and more preferably 450-550 ℃; the calcination time is preferably 0.5 to 3 hours, and more preferably 1 to 1.5 hours. After the calcination is finished, the temperature is preferably raised to 800-900 ℃ at the speed of 2-3 ℃/min, and the temperature is kept for 0.5-1 hour.
The obtained mother glass hemisphere is put into a muffle furnace, heated to the nucleation temperature, then kept warm for a certain time, heated to the crystallization temperature, kept warm for a certain time, cooled to the room temperature along with the furnace after the heat treatment is finished, and taken out.
In the invention, the nucleation temperature is preferably 650-750 ℃, and more preferably 700 ℃; the heating rate for heating to the nucleation temperature is preferably 1-10 ℃/min, more preferably 2-8 ℃/min, and most preferably 3-5 ℃/min, specifically, in the embodiment of the present invention, 3.5 ℃/min; after the temperature is raised to the nucleation temperature, the temperature is preferably kept for 0.5 to 2 hours, and more preferably for 0.5 to 1 hour.
In the invention, the crystallization temperature is preferably 750-850 ℃, and more preferably 800 ℃; the rate of raising the temperature to the crystallization temperature is preferably 1 to 10 ℃/min, more preferably 2 to 8 ℃/min, most preferably 3 to 5 ℃/min, and specifically, in the embodiment of the invention, 3.5 ℃/min; after the temperature is raised to the crystallization temperature, the temperature is preferably kept for 1 to 2.5 hours, and more preferably 1.5 to 2 hours.
After the crystallization treatment is finished, dipping the crystallized glass floating ball hemisphere in mixed molten salt to obtain a deep sea glass floating ball hemisphere;
the mixed molten salt comprises the following components in percentage by mass:
KNO3: 25-50%, more preferably 35-40%, specifically, in the embodiment of the present invention, 25%, 35%, 40%, 30%, 38%, and 50%;
NaNO3: 49-70%, more preferably 50-60%, specifically, in the embodiment of the present invention, 45%, 60%, 59%, 67%, 58%, or 70%;
CsNO3: 1-5%, more preferably 2-3%; specifically, in the embodiment of the present invention, it may be 5%, 2%, 3%, or 1%.
In the present invention, the temperature of the impregnation is preferably 450 to 750 ℃, more preferably 500 to 700 ℃, and most preferably 550 to 600 ℃, specifically, in the embodiment of the present invention, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, or 750 ℃; the dipping time is preferably 45-90 min, more preferably 50-80 min, most preferably 60-70 min, and specifically, in the embodiment of the present invention, the dipping time may be 50min, 60min, 75min or 80 min.
And finally, matching the deep sea glass floating ball hemispheres in pairs, vacuumizing the matched floating ball until the pressure is lower than 0.3 atmospheric pressure, coating a sealant at the joint of the two hemispheres, and winding a protective adhesive tape to obtain the deep sea glass floating ball.
The invention provides a deep sea glass floating ball which is prepared from the following components in parts by mass: 55-65 wt% of silicon oxide; 18-25 wt% of alumina; 3-6 wt% of lithium oxide; 2-5 wt% of magnesium oxide; 2-6 wt% of sodium oxide; 0.5-2 wt% of potassium oxide; 0.5-1.5 wt% of boron oxide; 0-1 wt% of zirconium oxide; 0-1 wt% of titanium oxide; the mass fractions of zirconia and titania are not 0 at the same time. The invention provides a novel glass formula suitable for a deep sea floating ball, aiming at the problems of the existing borosilicate glass. The invention uses Li as the main component2O-Al2O3-SiO2The prepared transparent microcrystalline glass has no phase separationThe glass has uniform components, the performance can meet the use requirement of the deep sea floating ball, the cost is lower, the pressure resistance is higher, and the working depth of the deep sea floating glass ball manufactured by the glass is more than 12000 m.
The invention also provides a preparation method of the deep sea glass floating ball, the lithium aluminum silicon glass ceramic prepared by the melting method has uniform glass body components, the mechanical property of the glass body can meet the use requirement, and the lithium aluminum silicon glass ceramic can adapt to more complex deep sea environment due to the characteristic of low thermal expansion (even zero expansion). The working depth of the deep-sea glass floating ball manufactured by the floating ball is more than 12000 m.
In order to further illustrate the present invention, the deep sea glass float ball and the preparation method thereof provided by the present invention are described in detail below with reference to the examples, but the present invention should not be construed as being limited to the scope of the present invention.
Example 1
According to the raw material formula in table 1, the raw materials are mixed, the batch is melted and clarified at 1600 ℃ by a melting method for 3 hours, then molten glass is poured into deionized water to obtain glass particles, and then a binder is added to granulate in an agate bowl. The granulated powder is placed under an oil press, and is pressed into glass hemispheres with uniform diameter and wall thickness by using a manufactured hemispheric grinding tool.
Putting the glass sample into a muffle furnace, calcining for 1 hour at 450 ℃ to fully discharge the binder, heating to a preset nucleation temperature (650 ℃) at a heating rate of 3.5 ℃/min, then preserving heat for half an hour, heating to a preset crystallization temperature (750 ℃) at a heating rate of 3.5 ℃/min, preserving heat for 1 hour, cooling to room temperature along with the furnace after heat treatment is finished, and taking out to obtain the glass hemisphere.
The glass hemisphere is put into the mixture ratio: KNO 3: 25%, NaNO 3: 70%, CsNO 3: 5 percent; the molten salt mixture of (1) was immersed at 750 ℃ for 75 minutes, taken out, cooled with water, washed and dried. The glass hemispheres are matched in pairs, and then the matched pair of hemispheres are internally vacuumized until the pressure is lower than 0.3 atmospheric pressure. The hemisphere joints were then coated with sealant and wrapped with protective tape.
Example 2
According to the raw material formula in table 1, the raw materials are mixed, the batch is melted and clarified for 3.5 hours at 1600 ℃ by using a melting method, then the mixture is poured into deionized water to obtain glass particles, and then the glass particles are added with a binder and granulated in an agate bowl. The granulated powder is placed under an oil press, and is pressed into glass hemispheres with uniform diameter and wall thickness by using a manufactured hemispheric grinding tool.
And (2) putting the annealed glass sample into a muffle furnace, calcining for 1 hour at 450 ℃ to fully discharge the binder, heating to a preset nucleation temperature (700 ℃) at a heating rate of 3.5 ℃/min, then preserving heat for half an hour, heating to a preset crystallization temperature (800 ℃) at a heating rate of 3.5 ℃/min, preserving heat for 1 hour, cooling to room temperature along with the furnace after the heat treatment is finished, and taking out to obtain the deep-sea glass hemisphere.
The glass hemisphere is put into the mixture ratio: KNO 3: 35%, NaNO 3: 60%, CsNO 3: 5 percent; the molten salt mixture of (3) was immersed at 750 ℃ for 60 minutes, taken out, cooled with water, washed and dried. The glass hemispheres are matched in pairs, and then the matched pair of hemispheres are internally vacuumized until the pressure is lower than 0.3 atmospheric pressure. The hemisphere joints were then coated with sealant and wrapped with protective tape.
Example 3
According to the raw material formula in table 1, the raw materials are mixed, the batch is melted and clarified for 4 hours at 1600 ℃ by using a melting method, then the mixture is poured into deionized water to obtain glass particles, and then a binder is added to granulate in an agate bowl. The granulated powder is placed under an oil press, and is pressed into glass hemispheres with uniform diameter and wall thickness by using a manufactured hemispheric grinding tool.
And (2) putting the annealed glass sample into a muffle furnace, calcining for 1.5 hours at 450 ℃ to fully discharge the binder, heating to a preset nucleation temperature (650 ℃) at a heating rate of 3.5 ℃/min, then preserving heat for half an hour, heating to a preset crystallization temperature (800 ℃) at a heating rate of 3.5 ℃/min, preserving heat for 1.5 hours, cooling to room temperature along with the furnace after heat treatment is finished, and taking out to obtain the deep-sea glass hemisphere.
The glass hemisphere is put into the mixture ratio: KNO 3: 35%, NaNO 3: 60%, CsNO 3: 5 percent; the molten salt mixture of (1) was immersed at 600 ℃ for 75 minutes, taken out, cooled with water, washed and dried. The glass hemispheres are matched in pairs, and then the matched pair of hemispheres are internally vacuumized until the pressure is lower than 0.3 atmospheric pressure. The hemisphere joints were then coated with sealant and wrapped with protective tape.
Example 4
According to the raw material formula in table 1, the raw materials are mixed, the batch is melted and clarified for 4 hours at 1600 ℃ by using a melting method, then the mixture is poured into deionized water to obtain glass particles, and then a binder is added to granulate in an agate bowl. The granulated powder is placed under an oil press, and is pressed into glass hemispheres with uniform diameter and wall thickness by using a manufactured hemispheric grinding tool.
And (2) putting the annealed glass sample into a muffle furnace, calcining for 1.5 hours at 450 ℃ to fully discharge the binder, heating to a preset nucleation temperature (700 ℃) at a heating rate of 3.5 ℃/min, then preserving heat for half an hour, heating to a preset crystallization temperature (800 ℃) at a heating rate of 3.5 ℃/min, preserving heat for 1.5 hours, cooling to room temperature along with the furnace after heat treatment is finished, and taking out to obtain the deep-sea glass hemisphere.
The glass hemisphere is put into the mixture ratio: KNO 3: 40%, NaNO 3: 58%, CsNO 3: 2 percent; the mixed molten salt of (3) was immersed at 600 ℃ for 60 minutes, taken out, cooled with water, washed and dried. The glass hemispheres are matched in pairs, and then the matched pair of hemispheres are internally vacuumized until the pressure is lower than 0.3 atmospheric pressure. The hemisphere joints were then coated with sealant and wrapped with protective tape.
Example 5
According to the raw material formula in table 1, the raw materials are mixed, the batch is melted and clarified for 4 hours at 1600 ℃ by using a melting method, then the mixture is poured into deionized water to obtain glass particles, and then a binder is added to granulate in an agate bowl. The granulated powder is placed under an oil press, and is pressed into glass hemispheres with uniform diameter and wall thickness by using a manufactured hemispheric grinding tool.
And (2) putting the annealed glass sample into a muffle furnace, calcining for 2 hours at 450 ℃ to fully discharge the binder, heating to a preset nucleation temperature (700 ℃) at a heating rate of 3.5 ℃/min, then preserving heat for half an hour, heating to a preset crystallization temperature (800 ℃) at a heating rate of 3.5 ℃/min, preserving heat for 2.5 hours, cooling to room temperature along with the furnace after heat treatment is finished, and taking out to obtain the deep-sea glass hemisphere.
The glass hemisphere is put into the mixture ratio: KNO 3: 30%, NaNO 3: 67%, CsNO 3: 3 percent; the molten salt mixture of (1) was immersed at 550 ℃ for 75 minutes, taken out, cooled with water, washed and dried. The glass hemispheres are matched in pairs, and then the matched pair of hemispheres are internally vacuumized until the pressure is lower than 0.3 atmospheric pressure. The hemisphere joints were then coated with sealant and wrapped with protective tape.
Example 6
According to the raw material formula in table 1, the raw materials are mixed, the batch is melted and clarified at 1600 ℃ for 4.5 hours by using a melting method, then the mixture is poured into deionized water to obtain glass particles, and then the glass particles are added with a binder and granulated in an agate bowl. The granulated powder is placed under an oil press, and is pressed into glass hemispheres with uniform diameter and wall thickness by using a manufactured hemispheric grinding tool.
And (2) putting the annealed glass sample into a muffle furnace, calcining for 2 hours at 450 ℃ to fully discharge the binder, heating to a preset nucleation temperature (750 ℃) at a heating rate of 3.5 ℃/min, then preserving heat for half an hour, heating to a preset crystallization temperature (850 ℃) at a heating rate of 3.5 ℃/min, preserving heat for 2 hours, cooling to room temperature along with the furnace after the heat treatment is finished, and taking out to obtain the deep-sea glass hemisphere.
The glass hemisphere is put into the mixture ratio: KNO 3: 40%, NaNO 3: 59%, CsNO 3: 1 percent; the molten salt mixture of (1) was immersed at 750 ℃ for 50 minutes, taken out, cooled with water, washed and dried. The glass hemispheres are matched in pairs, and then the matched pair of hemispheres are internally vacuumized until the pressure is lower than 0.3 atmospheric pressure. The hemisphere joints were then coated with sealant and wrapped with protective tape.
Example 7
According to the raw material formula in table 1, the raw materials are mixed, the batch is melted and clarified for 5 hours at 1600 ℃ by using a melting method, then the mixture is poured into deionized water to obtain glass particles, and then a binder is added to granulate in an agate bowl. The granulated powder is placed under an oil press, and is pressed into glass hemispheres with uniform diameter and wall thickness by using a manufactured hemispheric grinding tool.
And (2) putting the annealed glass sample into a muffle furnace, calcining for 2.5 hours at 450 ℃ to fully discharge the binder, heating to a preset nucleation temperature (650 ℃) at a heating rate of 3.5 ℃/min, then preserving heat for half an hour, heating to a preset crystallization temperature (850 ℃) at a heating rate of 3.5 ℃/min, preserving heat for 1 hour, cooling to room temperature along with the furnace after heat treatment is finished, and taking out to obtain the deep-sea glass hemisphere.
The glass hemisphere is put into the mixture ratio: KNO 3: 38%, NaNO 3: 60%, CsNO 3: 2 percent; the mixed molten salt of (3) was immersed at 500 ℃ for 80 minutes, taken out, cooled with water, washed and dried. The glass hemispheres are matched in pairs, and then the matched pair of hemispheres are internally vacuumized until the pressure is lower than 0.3 atmospheric pressure. The hemisphere joints were then coated with sealant and wrapped with protective tape.
Example 8
According to the raw material formula in table 1, the raw materials are mixed, the batch is melted and clarified for 5 hours at 1600 ℃ by using a melting method, then the mixture is poured into deionized water to obtain glass particles, and then a binder is added to granulate in an agate bowl. The granulated powder is placed under an oil press, and is pressed into glass hemispheres with uniform diameter and wall thickness by using a manufactured hemispheric grinding tool.
And (3) putting the annealed glass sample into a muffle furnace, calcining for 2.5 hours at 450 ℃ to fully discharge the binder, heating to a preset nucleation temperature (650 ℃) at a heating rate of 3.5 ℃/min, then preserving heat for half an hour, heating to a preset crystallization temperature (850 ℃) at a heating rate of 3.5 ℃/min, preserving heat for 2.5 hours, cooling to room temperature along with the furnace after heat treatment is finished, and taking out to obtain the deep-sea glass hemisphere.
The glass hemisphere is put into the mixture ratio: KNO 3: 50%, NaNO 3: 45%, CsNO 3: 5 percent; the molten salt mixture of (1) was immersed at 450 ℃ for 75 minutes, taken out, cooled with water, washed and dried. The glass hemispheres are matched in pairs, and then the matched pair of hemispheres are internally vacuumized until the pressure is lower than 0.3 atmospheric pressure. The hemisphere joints were then coated with sealant and wrapped with protective tape.
TABLE 1 raw material ratios in inventive examples 1 to 8
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | |
| Silicon oxide | 56 | 56 | 59 | 59 | 59 | 62 | 65 | 65 |
| Alumina oxide | 25 | 25 | 22 | 25 | 22 | 20 | 18 | 25 |
| Lithium oxide | 6 | 6 | 6 | 4 | 6 | 5 | 5 | 3 |
| Magnesium oxide | 5 | 5 | 5 | 4 | 2 | 4 | 3 | 2 |
| Sodium oxide | 5 | 5 | 5 | 5 | 5 | 4 | 5.5 | 3 |
| Potassium oxide | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 2 | 1 | 0.5 |
| Boron oxide | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1 | 0.5 | 0.5 |
| Zirconium oxide | 1 | 0 | 0.5 | 0.5 | 0.5 | 1 | 1 | 0.5 |
| Titanium oxide | 0 | 1 | 0.5 | 0.5 | 0.5 | 1 | 1 | 0.5 |
The deep sea glass floating ball obtained in the embodiment of the invention is subjected to performance test according to the following method, and the results are shown in table 2,
the coefficient of expansion is tested according to GB/T7962.16-2010;
the transmittance is tested according to GB/T7962.12-2010;
the moisture resistance stability is tested according to GB/T7962.15-2010;
the acid resistance stability is tested according to GB/T7962.14-2010;
flexural strength (mechanical properties): fixing the sintered strip microcrystalline glass sample on a CTM-6104 electronic universal testing machine, and applying pressure to the sample until the sample is broken, namely a three-point bending strength testing method;
insulation conductivity: the resistance value of the wafer sample after silver burning was measured by using an insulation resistance test instrument of model YD2681A under a dc voltage of 100V, and the conductivity was calculated.
Vickers hardness: the test was carried out under the conditions of an experimental load of 200gf and a retention time of 10S.
TABLE 2 Performance of deep sea glass float ball obtained in the example of the present invention
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A preparation method of a deep sea glass floating ball comprises the following steps:
A) according to mass fraction, 55-65 wt% of silicon oxide, 18-25 wt% of aluminum oxide and 3-6 wt% of lithium oxide are added; mixing and ball-milling 2-5 wt% of magnesium oxide, 2-6 wt% of sodium oxide, 0.5-2 wt% of potassium oxide, 0.5-1.5 wt% of boron oxide, 0-1 wt% of zirconium oxide and 0-1 wt% of titanium oxide, drying and sieving after ball-milling to obtain mixed powder; the mass fractions of the zirconium oxide and the titanium oxide are not 0 at the same time;
B) melting the mixed powder at high temperature, clarifying and homogenizing to obtain glass liquid, and pouring the glass liquid into deionized water to obtain glass particles;
C) adding a binder into the glass particles, grinding and granulating, and then performing compression molding on the granulated glass particles to obtain a molded glass hemisphere;
D) calcining the formed glass hemisphere at 400-550 ℃, heating to 800-900 ℃ at the speed of 1-5 ℃/min, preserving heat for 0.5-1 hour, and cooling to obtain a parent glass hemisphere;
E) heating the mother glass hemisphere to a nucleation temperature, then preserving heat for 0.5-2 hours, heating to a crystallization temperature, preserving heat for 1-2.5 hours, and finally performing chemical strengthening to obtain a deep sea glass floating ball hemisphere;
F) and matching every two hemispheres of the deep-sea glass floating ball, and assembling to obtain the deep-sea glass floating ball.
2. The preparation method according to claim 1, wherein the temperature for drying in the step A) is 90-110 ℃;
the mesh number sieved in the step A) is 30-50 meshes.
3. The preparation method according to claim 1, wherein the temperature of the high-temperature melting in the step B) is 1500-1800 ℃;
and the time of high-temperature melting in the step B) is 3-5 hours.
4. The preparation method of claim 1, wherein the binder in step C) is one or more of polyvinyl alcohol, an aqueous solution of acrylic acid and carboxymethyl cellulose.
5. The method according to claim 1, wherein the nucleation temperature in step E) is 650 to 750 ℃.
6. The method according to claim 1, wherein the crystallization temperature in step E) is 750-850 ℃.
7. The method according to claim 1, wherein the chemical strengthening is specifically:
dipping the crystallized glass floating ball in mixed molten salt to obtain a deep-sea glass floating ball hemisphere;
the mixed molten salt comprises the following components in percentage by mass:
KNO3：25～50％、NaNO3：49～70％、CsNO3：1～5％。
8. the preparation method according to claim 7, wherein the temperature of the impregnation is 450 to 750 ℃;
the dipping time is 45-90 min.
9. The preparation method according to claim 1, wherein the deep sea glass floating ball is obtained by performing vacuum pumping after the hemispheres of the deep sea glass floating ball are matched in pairs until the pressure is lower than 0.3 atmosphere, and then coating a sealant at the joint of the two hemispheres and winding a protective tape.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH076623A (en) * | 1993-04-20 | 1995-01-10 | Ishizuka Glass Co Ltd | Conductive paste additive |
| CN1495144A (en) * | 2002-08-20 | 2004-05-12 | 日本电气硝子株式会社 | Glass-ceramic |
| CN1886348A (en) * | 2003-10-24 | 2006-12-27 | Ppg工业俄亥俄公司 | Lithia-alumina-silica containing glass compositions and glasses suitable for chemical tempering and articles made using the chemically tempered glass |
| CN101823840A (en) * | 2009-03-05 | 2010-09-08 | 肖特公开股份有限公司 | The eco-friendly fusing and the method for refining of glass melt that is used for the crystallizable glass of lithium aluminosilicate (LAS) glass-ceramic |
| CN104364211A (en) * | 2012-03-20 | 2015-02-18 | 尤罗科拉公司 | Oven door |
| CN106517743A (en) * | 2016-12-28 | 2017-03-22 | 中国建材国际工程集团有限公司 | Preparation method of deep sea glass buoyage and moulding device thereof |
-
2020
- 2020-03-18 CN CN202010190325.6A patent/CN111377608B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH076623A (en) * | 1993-04-20 | 1995-01-10 | Ishizuka Glass Co Ltd | Conductive paste additive |
| CN1495144A (en) * | 2002-08-20 | 2004-05-12 | 日本电气硝子株式会社 | Glass-ceramic |
| CN1886348A (en) * | 2003-10-24 | 2006-12-27 | Ppg工业俄亥俄公司 | Lithia-alumina-silica containing glass compositions and glasses suitable for chemical tempering and articles made using the chemically tempered glass |
| CN101823840A (en) * | 2009-03-05 | 2010-09-08 | 肖特公开股份有限公司 | The eco-friendly fusing and the method for refining of glass melt that is used for the crystallizable glass of lithium aluminosilicate (LAS) glass-ceramic |
| CN104364211A (en) * | 2012-03-20 | 2015-02-18 | 尤罗科拉公司 | Oven door |
| CN106517743A (en) * | 2016-12-28 | 2017-03-22 | 中国建材国际工程集团有限公司 | Preparation method of deep sea glass buoyage and moulding device thereof |
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