CN115872623A - Crystallization-controllable boroaluminate microcrystalline glass and preparation method and application thereof - Google Patents
Crystallization-controllable boroaluminate microcrystalline glass and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of microcrystalline glass, and discloses crystallization-controllable boroaluminate microcrystalline glass as well as a preparation method and application thereof, wherein the preparation method comprises the following steps: respectively weighing and uniformly mixing the following preparation raw materials of the base glass by mass percent to obtain mixed powder: li 2 O9％～16％、Al 2 O 3 25％～42％、B 2 O 3 35％～55％、P 2 O 5 0％～3％、ZrO 2 0 to 3 percent; smelting the mixed powder to a molten state, quickly cooling to room temperature, and grinding to obtain base glass powder; to be provided withThe nano oxide is used as an induction seed crystal, and is uniformly mixed with the basic glass powder and then is smelted to a molten state to obtain a glass melt B; and (3) casting and molding the glass melt B by adopting a casting method, and then annealing to obtain the boron aluminate microcrystalline glass A. The microcrystalline glass prepared by the invention has the characteristics of low melting temperature, simple forming, convenience for ion exchange strengthening, high strength, high transparency and the like.
Description
Technical Field
The invention relates to the technical field of microcrystalline glass, in particular to crystallization-controllable boroaluminate microcrystalline glass and a preparation method and application thereof.
Background
A glass Cover plate (Cover glass) is an important component of modern smart terminal portable devices, and plays an important role in protecting display devices from external damage. The cover plate glass widely applied at present is mainly a high-alumina-silica glass system, although the falling resistance of the cover plate glass can be further improved by a chemical strengthening method, the sum of the contents of alumina and silica in the glass is close to or exceeds 80wt%, so that the high-temperature melting (more than 1600 ℃) and the forming of the cover plate glass are very difficult, and the corresponding preparation cost is high. Boron aluminate glass is a glass formed by B 2 O 3 And Al 2 O 3 Mainly composed of SiO-free 2 Compared with high-alumina silica glass, boron aluminate glass is caused by B 2 O 3 The content of (A) is higher (more than or equal to 50 wt%), so that the melting temperature is lower and the forming is easy, and meanwhile, the glass has excellent crack propagation resistance, but the lower hardness limits the further expansion application of the glass in the aspect of cover plate.
Microcrystallization is one of effective means for improving the glass hardness, so that the hardness of the glass can be improved by microcrystallizing the boroaluminate glass on the basis of not changing the glass formula and further improving the process difficulty. However, in the case of the component for the microcrystallization of aluminoborosilicate glass, it is often necessary to add TiO 2 As nucleating agents, but TiO 2 The glass is colored yellowish brown, which limits its further use in the field of cover glass. Furthermore, for cover glasses or transparent optical glass ceramics, high transparency to visible light is one of the use prerequisites that it must satisfy. The traditional boron aluminate glass is mainly subjected to microcrystallization through basic glass component regulation and optimization of a multi-section heat treatment crystallization system, and a crystal nucleating agent is directly added into a glass composition and forms basic glass through one-time high-temperature melting, and in the process, the crystal nucleating agent structure is easily damaged by high-temperature melting and participates in the formation of a glass network structure. Since the transmittance of the microcrystalline glass is generally closely related to the state of the crystal phase, e.g. the crystal phase has too large a size: (>800 nm) can rapidly reduce the transmittance of the microcrystalline glass and even lose the transmittance, so how to avoid TiO 2 On the premise of coloring effect, the preparation of the high-transmittance high-strength microcrystalline glass cover plate material has certain challenge.
Therefore, the invention provides a crystallization controllable boroaluminate microcrystalline glass and a preparation method and application thereof.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a crystallization-controllable boroaluminate microcrystalline glass and a preparation method and application thereof.
The crystallization controllable boroaluminate microcrystalline glass and the preparation method and the application thereof are realized by the following technical scheme:
a preparation method of crystallization-controllable boroaluminate microcrystalline glass comprises the following steps:
s1, respectively weighing corresponding preparation raw materials of the base glass according to the following mass percent ratio, and uniformly mixing to obtain mixed powder for later use:
Li 2 O 9％～16％、Al 2 O 3 25％～42％、B 2 O 3 35％～55％、P 2 O 5 0％～3％、ZrO 2 0 to 3%, and Li 2 O、Al 2 O 3 、B 2 O 3 、P 2 O 5 And ZrO 2 The sum of the total amount of (A) and (B) is 100%;
s2, carrying out primary smelting treatment on the mixed powder to a molten state to obtain a glass melt A; cooling the glass melt A to room temperature, and then grinding to obtain basic glass powder;
s3, taking the nano oxide as an induction seed crystal, uniformly mixing the induction seed crystal with the basic glass powder, and performing secondary smelting treatment to a molten state to obtain a glass melt B;
and S4, casting and molding the glass melt B by adopting a casting method, and annealing to obtain the boron aluminate microcrystalline glass A.
Further comprising S5, and crystallizing the boron aluminate microcrystalline glass A at the temperature of 650-750 ℃ to obtain the boron aluminate microcrystalline glass B.
Furthermore, the time of the crystallization treatment is 2-8 h.
Further, the nano oxide is Al 2 O 3 、SiO 2 、ZnO、ZrO 2 、Y 2 O 3 One or more of MgO and CaO;
and the dosage ratio of the nano oxide to the base glass powder is 1.
Further, in S2, the glass melt A is cooled to room temperature at a cooling rate of 10 to 60 ℃/S.
Further, the nano-oxide is added in any one state of a granular state, a plate state and a needle state; and the particle size of the nano oxide is 5-20 nm.
Further, the smelting temperature of the first smelting treatment is 1350-1500 ℃, and the smelting time is 2-8 h.
Further, the smelting temperature of the second smelting treatment is 1350-1500 ℃, and the smelting time is 2-4 h.
The second purpose of the invention is to provide the boron aluminate microcrystalline glass prepared by the preparation method.
The third purpose of the invention is to provide an application of the boroaluminate microcrystalline glass in preparing display cover plate glass and transparent optical microcrystalline glass of portable electronic equipment.
Compared with the prior art, the invention has the following beneficial effects:
the invention takes the nano oxide as the induced seed crystal, can greatly improve the crystallization capacity of the boron aluminate glass, and the invention adds the nano oxide of the nano crystalline phase after the glass is formed, can further play the induced crystallization function of the crystalline phase, and realizes the purpose of accurately controlling the size, the appearance, the type, the content, the distribution and the like of the precipitated crystalline phase in the microcrystalline glass by controlling the size, the appearance, the type, the content, the distribution and the like of the added nano crystalline phase, thereby leading the precipitation of the crystalline phase in the microcrystalline glass to present a controllable situation, being beneficial to the controllable precipitation of the nano crystalline phase in the microcrystalline glass, and achieving the purposes of strengthening the microcrystalline glass and not reducing the visible light transmittance of the base glass. Controllable microcrystal phase precipitation can not only greatly improve the surface hardness of the base glass, but also effectively prevent the further expansion of the surface cracks of the glass and prevent the large-area cracking of the glass. The hardness value of the prepared microcrystalline glass is 6.0-9.0 GPa, the size of a crystal phase precipitated in the microcrystalline glass is 15-40 nm, and the microcrystalline glass has small absorption and scattering effects on visible light, so that the transmittance of the prepared microcrystalline glass in a visible light wave band (400-800 nm) is more than 90%, and the microcrystalline glass has a good application prospect in the field of portable electronic equipment display cover plate glass.
The microcrystalline glass prepared by the invention has the characteristics of low melting temperature, simple forming, convenience for ion exchange reinforcement, high strength, high transparency and the like.
Drawings
Fig. 1 is an XRD pattern of the glass ceramic described in example 1.
Detailed Description
As described in the background art, the invention considers that the traditional crystal nucleating agent is mainly added with other preparation raw material components simultaneously when the glass is prepared, and the glass is formed by in-situ crystallization, but the method often has the defects of large size of precipitated crystal phase, difficult control of crystal phase content, uncontrollable morphology of the precipitated phase, difficult determination of precipitated phase distribution and the like, and difficult control of crystallization degree. Therefore, the nano oxide is used as the induction seed crystal and added after the glass is formed, so that the induction crystallization effect of the crystalline phase can be further exerted, and the purposes of accurately controlling the size, the shape, the type, the content, the distribution and the like of the precipitated crystalline phase in the microcrystalline glass can be realized by controlling the size, the shape, the type, the content, the distribution and the like of the added nano crystalline phase, so that the precipitation of the crystalline phase in the microcrystalline glass presents a controllable state, the controllable precipitation of the nano crystalline phase in the microcrystalline glass is facilitated, and the purposes of strengthening the microcrystalline glass and not reducing the visible light transmittance of the base glass are achieved. In addition, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
The invention provides boroaluminate microcrystalline glass, and a preparation method thereof is as follows:
s1, respectively weighing corresponding preparation raw materials of the base glass according to the following mass percent ratio, and uniformly mixing to obtain mixed powder for later use:
Li 2 O 9％～16％、Al 2 O 3 25％～42％、B 2 O 3 35％～55％、P 2 O 5 0％～3％、ZrO 2 0 to 3%, and Li 2 O、Al 2 O 3 、B 2 O 3 、P 2 O 5 And ZrO 2 The sum of the total amount of (A) is 100%;
the present invention is not limited to the mixing method of the respective production raw materials, as long as the raw materials can be sufficiently and uniformly mixed. Such as by ball milling or mechanical milling.
S2, carrying out primary smelting treatment on the mixed powder to a molten state to obtain a glass melt A; rapidly cooling the glass melt A to room temperature, and then grinding to obtain base glass powder;
in the present invention, in consideration of the specific composition range of the glass, in order to ensure complete melting and sufficient homogenization of the mixed powder, the mixed powder is melted to a molten state at a temperature of 1350 to 1500 ℃, and the invention does not limit the specific melting time, and the treatment is performed for a corresponding time according to the specifically selected temperature, as long as the mixed powder can be melted to a molten state, so that each component forms a glass melt a with uniform components, for example, the temperature is maintained at 1350 to 1500 ℃ for 2 to 8 hours.
In the invention, the glass melt A is rapidly cooled to form amorphous phase glass, and in order to ensure that the glass melt A can form a glass body, the glass melt A is preferably cooled to room temperature at a cooling speed of 10-60 ℃/s.
The present invention does not limit the specific process of the grinding treatment as long as it can be ground to obtain a base glass powder having a particle diameter of 10 to 30 μm.
S3, taking the nano oxide as an induction seed crystal, uniformly mixing the induction seed crystal with the basic glass powder, and carrying out secondary smelting treatment to obtain a glass melt B;
the specific components of the nano-oxide are not limited in the present invention, and the nano-oxide is selected as long as it does not cause glass coloring, and may be selected from Al, for example 2 O 3 、SiO 2 、ZnO、ZrO 2 、Y 2 O 3 One or more of MgO and CaO. The method takes the nano oxide of the nano crystalline phase as the induction seed crystal, adds the nano oxide after the base glass is formed, and then leads the nano oxide to fully play the induced crystallization function through smelting treatment, thereby leading the size, the appearance, the content, the distribution and the like of the crystalline phase precipitated in the base glass to be correspondingly influenced by the size, the appearance, the content, the distribution and the like of the induction seed crystal, leading the precipitation of the crystalline phase in the microcrystalline glass to present the controllable precipitation state, being beneficial to the controllable precipitation of the nano crystalline phase in the microcrystalline glass, and further achieving the purposes of strengthening the microcrystalline glass and not reducing the visible light transmittance of the base glass. Controlled precipitation of microcrystalline phasesThe surface hardness of the base glass can be greatly improved, the further expansion of the surface cracks of the glass can be effectively organized, and the phenomenon of large-area cracking of the glass is prevented. Therefore, the particle size of the nano-oxide preferably used in the present invention is 5 to 20nm.
And the nano oxide and the base glass powder are preferably mixed uniformly by a wet mixing method, and the invention is not limited to a specific mixing process as long as the nano oxide and the base glass powder can be fully and uniformly mixed. This can be done, for example, in the following manner: ethanol as medium solution, ball: material preparation: the ethanol proportion is 1. Since the material has residual medium solution after wet mixing, it is necessary to perform a drying process to remove the residual medium solution before the second melting process.
S4, casting and molding the glass melt B by adopting a casting method, and annealing to obtain the boron aluminate microcrystalline glass A;
it should be noted that, based on the glass composition and thermodynamic characteristics of the present invention, the preferred glass melt B is annealed at a temperature of 400 to 600 ℃ after being cast to ensure that the thermal stress generated during the casting process is slowly released and eliminated, thereby ensuring that the glass does not burst after being formed.
In order to improve the overall strength of the glass, the invention can also carry out crystallization treatment on the boron aluminate microcrystalline glass A at the temperature of 650-750 ℃ to obtain the boron aluminate microcrystalline glass B. The boroaluminate microcrystalline glass A is further deeply crystallized through crystallization treatment, and the added nano oxide is used as an induced seed crystal, so that the crystallization capacity of the glass is improved, the precipitation rate of the whole nano crystal of the glass is improved, and the whole strength of the glass is improved.
Example 1
The embodiment provides boroaluminate microcrystalline glass, and the preparation method thereof is as follows:
step one, according to the weight ratio of the following oxides: li 2 O(13％)、Al 2 O 3 (30％)、B 2 O 3 (53％)、P 2 O 5 (2％)、ZrO 2 (2%) accurately weighing, and uniformly mixing for later use;
step two, putting the uniformly mixed raw materials into a 1450 ℃ high-temperature furnace for melting, keeping the temperature for 4 hours to obtain a uniform glass melt, rapidly cooling the glass melt to obtain base glass, and then grinding the base glass to 10-30 mu m for later use;
step three, carrying out wet mixing on needle-shaped ZnO with the particle size of 5-20 nm and base glass micro powder according to the mass ratio of 1;
and step four, putting the dried mixed powder in the step three into a high-temperature furnace for melting, wherein the melting temperature is 1250 ℃, and the heat preservation time is 1h, so as to obtain a uniform glass melt.
And fifthly, rapidly forming the obtained glass melt by adopting a casting method, and annealing in an annealing furnace to eliminate thermal stress, wherein the set temperature of the annealing furnace is 520 ℃, and the annealing heat preservation time is 2 hours, so that the boron aluminate microcrystalline glass is obtained.
Example 2
The embodiment provides boroaluminate microcrystalline glass, and the preparation method thereof is as follows:
step one, according to the weight ratio of the following oxides: li 2 O(9％)、Al 2 O 3 (42％)、B 2 O 3 (46％)、、ZrO 2 (3%) accurately weighing, and uniformly mixing for later use;
step two, putting the uniformly mixed raw materials into a 1500 ℃ high-temperature furnace for melting, keeping the temperature for 6 hours to obtain a uniform glass melt, rapidly cooling the uniform glass melt to obtain base glass, and then grinding the base glass to 10-30 mu m for later use;
step three, preparing granular SiO with the grain size of 5-20 nm 2 And a plate-like Y having a particle size of 5 to 50nm 2 O 3 Mixing with the basic glass micro powder in a mass ratio of 1;
and step four, putting the dried mixed powder in the step three into a high-temperature furnace for melting, wherein the melting temperature is 1350 ℃, and the heat preservation time is 2.0 hours, so as to obtain a uniform glass melt.
And fifthly, rapidly forming the obtained glass melt by adopting a casting method, and putting the glass melt into an annealing furnace for annealing to eliminate thermal stress, wherein the set temperature of the annealing furnace is 600 ℃, and the annealing heat preservation time is 4 hours, so as to obtain the boron aluminate microcrystalline glass.
Example 3
The embodiment provides boroaluminate microcrystalline glass, and the preparation method thereof is as follows:
step one, according to the weight ratio of the following oxides: li 2 O(14％)、Al 2 O 3 (25％)、B 2 O 3 (55％)、P 2 O 5 (3％)、ZrO 2 (3%) accurately weighing, and uniformly mixing for later use;
step two, putting the uniformly mixed raw materials into a high-temperature furnace at 1350 ℃ for melting, keeping the temperature for 8 hours to obtain a uniform glass melt, rapidly cooling the uniform glass melt to obtain base glass, and then grinding the base glass to 10-30 microns for later use;
step three, preparing granular ZrO with the grain size of 5-20 nm 2 And granular Al having a particle size of 5 to 100nm 2 O 3 Mixing the glass powder with the basic glass micro powder in a mass ratio of 1;
and step four, putting the dried mixed powder in the step three into a high-temperature furnace for melting, wherein the melting temperature is 1100 ℃, and the heat preservation time is 1h, so as to obtain a uniform glass melt.
And fifthly, rapidly forming the obtained glass melt by adopting a casting method, and annealing in an annealing furnace to eliminate thermal stress, wherein the set temperature of the annealing furnace is 400 ℃, and the annealing heat preservation time is 3 hours, so that the boron aluminate microcrystalline glass is obtained.
And sixthly, placing the boron aluminate microcrystalline glass in a high-temperature furnace for crystallization heat treatment, setting the crystallization temperature at 650 ℃, setting the crystallization time at 3h, and then cooling along with the furnace to obtain the microcrystalline glass with enhanced performance.
Example 4
The embodiment provides boroaluminate microcrystalline glass, and the preparation method thereof is as follows:
step one, according to the weight ratio of the following oxides: li 2 O(16％)、Al 2 O 3 (32％)、B 2 O 3 (50％)、P 2 O 5 (2%) accurately weighing, and uniformly mixing for later use;
step two, putting the uniformly mixed raw materials into a 1500 ℃ high-temperature furnace for melting, keeping the temperature for 6 hours to obtain a uniform glass melt, rapidly cooling the uniform glass melt to obtain base glass, and then grinding the base glass to 10-30 mu m for later use;
step three, carrying out wet mixing on granular CaO with the particle size of 5-20 nm and the basic glass micro powder according to the mass ratio of 1;
and step four, putting the dried mixed powder in the step three into a high-temperature furnace for melting, wherein the melting temperature is 1300 ℃, and the heat preservation time is 1.0h, so as to obtain a uniform glass melt.
And fifthly, rapidly forming the obtained glass melt by adopting a casting method, and annealing in an annealing furnace to eliminate thermal stress, wherein the set temperature of the annealing furnace is 525 ℃, and the annealing heat preservation time is 3 hours, so that the boron aluminate microcrystalline glass is obtained.
Example 5
The embodiment provides boroaluminate microcrystalline glass, and the preparation method thereof is as follows:
step one, according to the weight ratio of the following oxides: li 2 O(12％)、Al 2 O 3 (32％)、B 2 O 3 (52％)、P 2 O 5 (2％)、ZrO 2 (2%) accurately weighing, and uniformly mixing for later use;
step two, putting the uniformly mixed raw materials into a high-temperature furnace at 1480 ℃ for melting, keeping the temperature for 2 hours to obtain a uniform glass melt, rapidly cooling the uniform glass melt to obtain base glass, and then grinding the base glass to 10-30 microns for later use;
step three, granular Al with the grain size of 5-20 nm 2 O 3 、SiO 2 The MgO, caO and the basic glass micropowder are subjected to wet mixing according to the mass ratio of 1;
and step four, putting the dried mixed powder in the step three into a high-temperature furnace for melting, wherein the melting temperature is 1280 ℃, and the heat preservation time is 0.5h, so as to obtain the uniform glass melt.
And fifthly, rapidly forming the obtained glass melt by adopting a casting method, and annealing in an annealing furnace to eliminate thermal stress, wherein the set temperature of the annealing furnace is 520 ℃, and the annealing heat preservation time is 2 hours, so that the boron aluminate microcrystalline glass is obtained.
And sixthly, placing the boron aluminate microcrystalline glass in a high-temperature furnace for crystallization heat treatment, setting the crystallization temperature to be 660 ℃, setting the crystallization time to be 2 hours, and then cooling along with the furnace to obtain the microcrystalline glass with enhanced performance.
Example 6
The embodiment provides boroaluminate microcrystalline glass, and the preparation method thereof is as follows:
step one, according to the weight ratio of the following oxides: li 2 O(16％)、Al 2 O 3 (28％)、B 2 O 3 (53％)、P 2 O 5 (1％)、ZrO 2 (2%) accurately weighing, and uniformly mixing for later use;
step two, putting the uniformly mixed raw materials into a 1460 ℃ high-temperature furnace for melting, keeping the temperature for 2 hours to obtain a uniform glass melt, rapidly cooling the uniform glass melt to obtain base glass, and then grinding the base glass to 10-30 mu m for later use;
step three, preparing granular ZrO with the grain size of 5-20 nm 2 、SiO 2 、Y 2 O 3 Mixing the glass powder with the basic glass micro powder in a mass ratio of 1;
and step four, putting the dried mixed powder in the step three into a high-temperature furnace for melting, wherein the melting temperature is 1260 ℃, and the heat preservation time is 1.5 hours, so as to obtain a uniform glass melt.
And fifthly, rapidly forming the obtained glass melt by adopting a casting method, and putting the glass melt into an annealing furnace for annealing to eliminate thermal stress, wherein the set temperature of the annealing furnace is 560 ℃, and the annealing heat preservation time is 2 hours, so that the boron aluminate microcrystalline glass is obtained.
And sixthly, placing the boron aluminate microcrystalline glass in a high-temperature furnace for crystallization heat treatment, setting the crystallization temperature at 750 ℃, setting the crystallization time at 3 hours, and then cooling along with the furnace to obtain the microcrystalline glass with enhanced performance.
Example 7
The embodiment provides boroaluminate microcrystalline glass, and the preparation method thereof is as follows:
step one, according to the weight ratio of the following oxides: li 2 O(10％)、Al 2 O 3 (40％)、B 2 O 3 (48％)、P 2 O 5 (1％)、ZrO 2 (1%) accurately weighing, and uniformly mixing for later use;
step two, putting the uniformly mixed raw materials into a high-temperature furnace at 1480 ℃ for melting, keeping the temperature for 5 hours to obtain a uniform glass melt, rapidly cooling the uniform glass melt to obtain basic glass, and then grinding the basic glass to 10-30 mu m for later use;
step three, granulating the granular Y with the grain size of 5-20 nm 2 O 3 Wet mixing with the base glass micro powder according to the mass ratio of 1;
and step four, putting the dried mixed powder in the step three into a high-temperature furnace for melting, wherein the melting temperature is 1300 ℃, and the heat preservation time is 1.5 hours, so as to obtain a uniform glass melt.
And fifthly, rapidly forming the obtained glass melt by adopting a casting method, and annealing the glass melt in an annealing furnace to eliminate thermal stress, wherein the set temperature of the annealing furnace is 550 ℃, and the annealing heat preservation time is 2 hours, so that the boron aluminate microcrystalline glass is obtained.
And step six, placing the boron aluminate microcrystalline glass in a high-temperature furnace for crystallization heat treatment, setting the crystallization temperature to be 650 ℃, setting the crystallization time to be 8 hours, and then cooling along with the furnace to obtain the microcrystalline glass with enhanced performance.
Example 8
The embodiment provides boroaluminate microcrystalline glass, and the preparation method thereof is as follows:
step one, according to the weight ratio of the following oxides: li 2 O(11％)、Al 2 O 3 (38％)、B 2 O 3 (49％)、P 2 O 5 (1％)、ZrO 2 (1%) accurately weighing, and uniformly mixing for later use;
step two, putting the uniformly mixed raw materials into a high-temperature furnace at 1480 ℃ for melting, keeping the temperature for 3 hours to obtain a uniform glass melt, rapidly cooling the uniform glass melt to obtain base glass, and then grinding the base glass to 10-30 microns for later use;
step three, preparing granular SiO with the grain size of 5-20 nm 2 And the ZnO and the base glass micropowder are subjected to wet mixing according to the mass ratio of 1;
and step four, putting the dried mixed powder in the step three into a high-temperature furnace for melting, wherein the melting temperature is 1300 ℃, and the heat preservation time is 0.5h, so as to obtain a uniform glass melt.
And fifthly, rapidly forming the obtained glass melt by adopting a casting method, and putting the glass melt into an annealing furnace for annealing to eliminate thermal stress, wherein the set temperature of the annealing furnace is 550 ℃, and the annealing heat preservation time is 2 hours, so as to obtain the boron aluminate microcrystalline glass.
And sixthly, placing the boron aluminate microcrystalline glass in a high-temperature furnace for crystallization heat treatment, setting the crystallization temperature to be 700 ℃, setting the crystallization time to be 6 hours, and then cooling along with the furnace to obtain the microcrystalline glass with enhanced performance.
Comparative example 1
The present comparative example provides a boroaluminate microcrystalline glass, and the manufacturing method thereof differs from example 1 only in that:
the nano oxide and other components of the glass are uniformly mixed and then are melted and poured at the same time to obtain base glass, and after the base glass is subjected to crystallization heat treatment, the obtained microcrystalline glass is in a semitransparent state, the visible light transmittance of the microcrystalline glass is 53 percent, and the grain size of the microcrystalline glass is 60-100 nm through testing the crystal phase size.
Comparative example 2
The present comparative example provides a boroaluminate microcrystalline glass, and the preparation method thereof differs from example 2 only in that:
the nano oxide and other components of the glass are uniformly mixed, then the mixture is melted and poured at the same time to obtain base glass, and after the base glass is subjected to crystallization heat treatment, the obtained microcrystalline glass is in a semitransparent state, the visible light transmittance of the microcrystalline glass is 40%, and the grain size of the microcrystalline glass is 80-120 nm through testing the crystal phase size.
Comparative example 3
This comparative example provides a boroaluminate microcrystalline glass, and the preparation method thereof differs from example 3 only in that:
the nano oxide and other components of the glass are uniformly mixed, then the mixture is melted and poured at the same time to obtain base glass, and after the base glass is subjected to crystallization heat treatment, the obtained microcrystalline glass is in a semitransparent state, the visible light transmittance of the microcrystalline glass is 20%, and the crystal grain size of the microcrystalline glass is 120-150 nm through testing the crystal phase size.
Comparative example 4
This comparative example provides a boroaluminate microcrystalline glass, and the preparation method thereof differs from example 4 only in that:
the nano oxide and other components of the glass are uniformly mixed, then the mixture is melted and poured at the same time to obtain base glass, and after the base glass is subjected to crystallization heat treatment, the obtained microcrystalline glass is in a semitransparent state, the visible light transmittance of the microcrystalline glass is 53%, and the grain size of the microcrystalline glass is 60-100 nm through testing the crystal phase size.
Comparative example 5
This comparative example provides a boroaluminate microcrystalline glass, and the preparation method thereof differs from that of example 5 only in that:
the nano oxide and other components of the glass are uniformly mixed, then the mixture is melted and poured at the same time to obtain base glass, and after the base glass is subjected to crystallization heat treatment, the obtained microcrystalline glass is in a semitransparent state, the visible light transmittance of the microcrystalline glass is 60%, and the crystal grain size of the microcrystalline glass is 60-80 nm through testing the crystal phase size.
Comparative example 6
The present comparative example provides a boroaluminate microcrystalline glass, and the production method thereof differs from example 6 only in that:
the nano oxide and other components of the glass are uniformly mixed and then are melted and poured at the same time to obtain base glass, and after the base glass is subjected to crystallization heat treatment, the obtained microcrystalline glass is in a semitransparent state, the visible light transmittance of the microcrystalline glass is 0%, and the grain size of the microcrystalline glass is 180-200 nm through testing the crystal phase size.
Comparative example 7
The present comparative example provides a boroaluminate microcrystalline glass, and the production method thereof differs from example 7 only in that:
the nano oxide and other components of the glass are uniformly mixed, then the mixture is melted and poured at the same time to obtain base glass, and after the base glass is subjected to crystallization heat treatment, the obtained microcrystalline glass is in a semitransparent state, the visible light transmittance of the microcrystalline glass is 39%, and the grain size of the microcrystalline glass is 80-120 nm through testing the crystal phase size.
Comparative example 8
This comparative example provides a boroaluminate microcrystalline glass, and the preparation method thereof differs from that of example 8 only in that:
the nano oxide and other components of the glass are uniformly mixed, then the mixture is melted and poured at the same time to obtain base glass, and after the base glass is subjected to crystallization heat treatment, the obtained microcrystalline glass is in a semitransparent state, the visible light transmittance of the microcrystalline glass is 46%, and the grain size of the microcrystalline glass is 70-110 nm by testing the crystal phase size.
In summary, the boroaluminate microcrystalline glasses of comparative examples 1-8 have a visible light transmittance of 0-60%, which is much lower than the method of the present invention. The crystal size of the crystal phase is measured and found to be 60-200 nm, which greatly limits the transmission of visible light. The reason is that the traditional adding mode of the nano oxide enables the nano oxide to be easily part of a glass melt and a glass network after being melted together with other glass components, and effective control on crystal phase precipitation is difficult to realize in the subsequent crystallization process, so that the size of precipitated crystal grains is overlarge, the transmission of visible light is seriously influenced, and the visible light transmittance of the microcrystalline glass is greatly reduced.
Test section
Hardness test
The hardness of the boroaluminate microcrystalline glasses prepared in examples 1-8 is respectively tested according to the test method of the GB/T16534-2009 fine ceramic room temperature hardness test method, and the test results are shown in Table 1.
Table 1 hardness test results
As can be seen from Table 1, the nano oxides with different sizes are doped in the base glass powder, so that the surface hardness of the base glass can be greatly improved, the further expansion of cracks on the surface of the glass can be effectively prevented, and the large-area cracking phenomenon of the glass can be prevented. And the adjustment of the surface hardness of the glass material can be realized by adjusting the size of the added nano oxide, so that the hardness value of the prepared microcrystalline glass is 6.0-9.0 GPa.
(II) analysis of precipitated phase Structure
The present invention separately tests the components and the sizes of precipitated phases of the boroaluminate microcrystalline glasses prepared in examples 1 to 8 by SEM (scanning electron microscope), and the test results are shown in table 2. And before the grain size test, the fresh microcrystalline glass section is soaked in 3% hydrofluoric acid solution by volume fraction for 60s so as to expose the microcrystalline phase.
TABLE 2 analysis of the precipitated phase structure
As can be seen from Table 2, the invention can realize the adjustment of the components and the sizes of the precipitated phase by doping the nano oxides with different sizes and components in the base glass powder, so that the precipitation of the crystalline phase in the microcrystalline glass presents a controllable state, the controllable precipitation of the nano crystalline phase in the microcrystalline glass is facilitated, the size of the crystalline phase precipitated in the microcrystalline glass is 15-40 nm, the absorption and scattering effects on visible light are small, and the aims of strengthening the microcrystalline glass and not reducing the visible light transmittance of the base glass are fulfilled.
(III) glass visible light transmittance test
The transmittance of the boroaluminate microcrystalline glass prepared in examples 1 to 8 in the visible light band (400 to 800 nm) was measured according to the method for measuring the luminous transmittance of the glass for daily use of GB/T5433 to 2008, and the measurement results are shown in table 3.
TABLE 3 test results of visible light transmittance test of glass
As can be seen from Table 3, the microcrystalline glass prepared by the method has a transmittance of more than 90% in a visible light band (400-800 nm), and has a good application prospect in the field of display cover plate glass of portable electronic equipment.
In summary, the invention firstly prepares the basic glass powder by a melting water quenching method, then dopes the nano crystal and mixes the nano crystal uniformly, and finally prepares the microcrystalline glass material by the mixed powder by a melting pouring method, wherein the separation control of the internal crystalline phase of the microcrystalline glass is mainly completed by the separation control of the doped nano crystalline phase. The size, shape, variety, distribution, content and the like of the externally doped crystalline phase can be accurately controlled before the glass is manufactured, after the externally doped crystalline phase is doped into the glass and is melted and cast with the glass again, the nano crystalline phase is difficult to be corroded and damaged by a melt due to lower temperature and shorter melting time compared with the first melting in the second melting process, the original shape, size and the like of the nano crystalline phase are completely stored, do not participate in the formation of a basic glass network structure, but are retained in the glass as a complete crystalline phase, so that the nano crystalline phase can be used as an accurately controllable nucleation site to control the precipitation of the crystalline phase in the microcrystalline glass, the precipitation of the nano crystalline phase is controllable, and the efficient preparation of the transparent optical microcrystalline glass is completed.
It is to be understood that the above-described embodiments are only some of the embodiments of the present invention, and not all of the 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.
Claims (10)
1. A preparation method of crystallization-controllable boroaluminate microcrystalline glass is characterized by comprising the following steps:
s1, respectively weighing corresponding preparation raw materials of the base glass according to the following mass percent ratio, and uniformly mixing to obtain mixed powder for later use:
Li 2 O 9％～16％、Al 2 O 3 25％～42％、B 2 O 3 35％～55％、P 2 O 5 0％～3％、ZrO 2 0 to 3%, and Li 2 O、Al 2 O 3 、B 2 O 3 、P 2 O 5 And ZrO 2 The sum of the total amount of (A) and (B) is 100%;
s2, carrying out primary smelting treatment on the mixed powder to a molten state to obtain a glass melt A; rapidly cooling the glass melt A to room temperature, and then grinding to obtain base glass powder;
s3, taking the nano oxide as an induction seed crystal, uniformly mixing the induction seed crystal with the basic glass powder, and performing secondary smelting treatment to a molten state to obtain a glass melt B;
and S4, casting and molding the glass melt B by adopting a casting method, and annealing to obtain the boron aluminate microcrystalline glass A.
2. The preparation method according to claim 1, further comprising S5, crystallizing the boron aluminate microcrystalline glass A at 650-750 ℃ for 2-8 h to obtain the boron aluminate microcrystalline glass B.
3. The method of claim 1, wherein the nano-oxide is Al 2 O 3 、SiO 2 、ZnO、ZrO 2 、Y 2 O 3 One or more of MgO and CaO;
and the mass ratio of the nano oxide to the base glass powder is 1.
4. The method according to claim 1, wherein the nano-oxide is added in any one state of a granular state, a plate state and a needle state; and the particle size of the nano oxide is 5-20 nm.
5. The production method according to claim 1, wherein in S2, the glass melt a is cooled to room temperature at a cooling rate of 10 to 60 ℃/S.
6. The preparation method of claim 1, wherein the melting temperature of the first melting treatment is 1350-1500 ℃, and the melting time is 2-8 h.
7. The preparation method of claim 1, wherein the smelting temperature of the second smelting treatment is 1100-1350 ℃ and the smelting time is 0.5-2 h.
8. The method according to claim 1, wherein the annealing temperature of the annealing treatment is 400 to 600 ℃. The annealing time is 2-4 h.
9. A boroaluminate glass-ceramic produced by the production method according to any one of claims 1 to 8.
10. Use of the boroaluminate microcrystalline glass of claim 9 in the preparation of display cover glass and transparent optical microcrystalline glass for portable electronic devices.
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