CN116143385A - Glass member manufacturing method, glass member and light-emitting device - Google Patents

Abstract

The application discloses a preparation method of a glass piece, the glass piece and a light-emitting device, wherein the preparation method comprises the following steps: preparing a dispersion liquid from at least two gas-phase silicon oxide particles with different particle diameters according to a preset proportion; adding alkoxy silane into the dispersion liquid, and hydrolyzing to form sol solution; the sol solution is made into gel, and the gel is sintered at 1000 ℃ to 1200 ℃ for a preset time to prepare the glass piece. By the mode, the glass piece can be prepared by mixing at least two gas-phase silicon oxide particles with different particle diameters according to a preset proportion and sintering at a low temperature of 1000-1200 ℃.

Description

Glass member manufacturing method, glass member and light-emitting device

Technical Field

The present disclosure relates to the field of glass manufacturing technology, and in particular, to a method for manufacturing a glass member, and a light emitting device.

Background

Silica glass has excellent properties such as transparency, chemical inertness, low thermal expansion coefficient, high strength, chemical stability and the like, and is widely used in various industries such as optical element lenses, optical fibers and the like.

In general, the conventional preparation of the optical element is completed by the procedures of grinding and polishing after the glass element is manufactured by a melting method, the sintering temperature of the glass manufactured by the conventional melting method is higher, the sintering temperature is generally higher than 1300 ℃, the edge deformation of a product is easy to generate in the high-temperature sintering process, the product is cracked, the transmittance is reduced and the energy consumption is high due to the local crystallization in the product, and the product with a micro fine structure has high requirement, is difficult to process, is difficult to copy the fine structure, is time-consuming and labor-consuming, and has high single product production cost.

Disclosure of Invention

A first aspect of embodiments of the present application provides a method for manufacturing a glass member, including: preparing a dispersion liquid from at least two gas-phase silicon oxide particles with different particle diameters according to a preset proportion; adding alkoxy silane into the dispersion liquid, and hydrolyzing to form sol solution; the sol solution is made into gel, and the gel is sintered at 1000 ℃ to 1200 ℃ for a preset time to prepare the glass piece.

A second aspect of embodiments of the present application provides a glazing produced by a method of manufacture comprising at least the first aspect of embodiments of the present application.

A third aspect of embodiments of the present application provides a light-emitting device comprising at least a glazing as made in accordance with the second aspect of embodiments of the present application.

The beneficial effects of this application are: the glass piece is prepared by mixing the gas phase silicon oxide particles with different particle diameters according to a preset proportion and sintering at a low temperature of 1000-1200 ℃, so that the edges of the product in the sintering process of the glass piece at a relatively low temperature are neat and smooth, the energy consumption is saved, and the production cost of a single product can be saved for a product with a tiny fine structure at a relatively low temperature.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.

FIG. 1 is a schematic flow chart of a first embodiment of a method of making a glazing of the present application;

FIG. 2 is a schematic flow chart of a second embodiment of a method of making a glazing of the present application;

FIG. 3 is a flowchart illustrating the step S12 of FIG. 1 according to an embodiment of the present application;

FIG. 4 is a flowchart illustrating the step S13 of FIG. 1 according to an embodiment of the present application;

fig. 5 is a flowchart of another embodiment of step S13 in fig. 1 of the present application.

Detailed Description

In the following description, for purposes of explanation and not limitation, specific details are set forth, such as particular system configurations, techniques, etc. in order to provide a thorough understanding of the embodiments of the present application. It will be apparent, however, to one skilled in the art that the present application may be practiced in other embodiments that depart from these specific details. In other instances, detailed descriptions of well-known systems, devices, circuits, and methods are omitted so as not to obscure the description of the present application with unnecessary detail.

It should be understood that the terms "comprises" and/or "comprising," when used in this specification and the appended claims, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.

It is also to be understood that the terminology used in the description of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in this specification and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.

It should be further understood that the term "and/or" as used in this specification and the appended claims refers to any and all possible combinations of one or more of the associated listed items, and includes such combinations.

As used in this specification and the appended claims, the term "if" may be interpreted as "when..once" or "in response to a determination" or "in response to detection" depending on the context. Similarly, the phrase "if a determination" or "if a [ described condition or event ] is detected" may be interpreted in the context of meaning "upon determination" or "in response to determination" or "upon detection of a [ described condition or event ]" or "in response to detection of a [ described condition or event ]".

In order to illustrate the technical solution of the present application, the following description is made by using specific embodiments, and referring to fig. 1, fig. 1 is a schematic flow chart of a first embodiment of a method for manufacturing a glass piece of the present application, where the method specifically includes the following steps:

s11: preparing a dispersion liquid from at least two gas-phase silicon oxide particles with different particle diameters according to a preset proportion;

in general, glass devices made using alkoxysilane alone, such as Tetraethoxysilane (TEOS), are prone to cracking when the silica sol formed after hydrolysis. Therefore, the solid content can be adjusted by adding the fumed silica particles, and the prepared sample has a wider size and is not easy to crack. The present application found that the different particle sizes of the vapor phase silica particles, which have a significant effect on the temperature of the process of sintering the finally prepared glass article, can reduce the sintering temperature by using two different particle sizes of vapor phase silica particles.

S12: adding alkoxy silane into the dispersion liquid, and hydrolyzing to form sol solution;

it is to be noted that the raw material of the alkoxysilane may be ethoxysilane such as TEOS, methoxysilane, propoxysilane, butoxysilane or the like, and is specifically selected according to the need without limitation. The alkoxysilane reacts with water to release the corresponding fatty alcohol to form the corresponding condensate, which is hydrolyzed to form silica sol, and mixed with the vapor phase silica to form a dispersion.

The alkoxysilane is added to the dispersion in a mass ratio of the alkoxysilane to the dispersion of 0.225 to 0.9, the alkoxysilane is hydrolyzed to form a sol solution, and the pH of the sol solution can be adjusted during the time in order to bring the sol solution to a gummy state, i.e., to gel.

Further, the mass ratio of alkoxysilane to dispersion may be 0.35 or more or 0.45 or more or 0.65 or more. The mass ratio of alkoxysilane to dispersion, if too large, may result in shrinkage that is too large to allow easy cracking or breakage of the glass part upon sintering, and must not be too small to allow formation of a sol solution, by setting the mass ratio such that the sintered glass part has both a large shrinkage and a high sample integrity.

S13: the sol solution is made into gel, and the gel is sintered at 1000 ℃ to 1200 ℃ for a preset time to prepare the glass piece.

The gel is prepared from the sol solution, the gel is dried and dehydrated, and the gel is sintered at a low temperature, so that the glass device with complete edge, high yield and high transmittance and large volume shrinkage is prepared, the temperature used for the low-temperature sintering is 1000-1200 ℃, the temperature can be about 1150 ℃, the used temperature is low, the energy consumption is low, and the cost is greatly saved. The sintering temperature may be 1150 ℃, 1100 ℃, 1050 ℃, or any combination thereof, and is selected according to the requirements, without limitation.

Therefore, by mixing the gas phase silicon oxide particles with different particle diameters in a preset proportion and sintering the mixture at a low temperature of 1000-1200 ℃ to prepare the glass piece, the edges of the product in the sintering process of the glass piece at a relatively low temperature are neat and smooth, the energy consumption is saved, and the production cost of a single product can be saved at a relatively low temperature for a product with a tiny fine structure.

With reference to fig. 2, fig. 2 is a schematic flow chart of a second embodiment of a method for preparing a glass article according to the present application, the step of preparing a dispersion from at least two kinds of vapor phase silicon oxide particles with different particle diameters according to a predetermined ratio includes:

s21: adding a preset amount of solvent into the first gas-phase silicon oxide particles and the second gas-phase silicon oxide particles according to a preset proportion to prepare a dispersion liquid with 20-45% of solid content;

wherein the predetermined ratio of the first vapor phase silicon oxide particles to the second vapor phase silicon oxide particles is 1:1 to 1:1000, wherein the predetermined ratio of the first vapor phase silicon oxide particles to the second vapor phase silicon oxide particles is preferably 1:3. it should be noted that the ratio herein specifically refers to a mass ratio, and the preset ratio of the first gas-phase silicon oxide particles to the second gas-phase silicon oxide particles may be 1:10, 1:20, 1:50, 1:100, 1:200, and other ratios, which may be selected according to the needs, and is not limited herein specifically. Wherein the first vapor phase silicon oxide particles have a larger particle diameter than the second vapor phase silicon oxide particles. For the ratio of the two gas phase silica particles, the applicant found that the more the content of large particle silica, the higher the sintering temperature, the higher the transmittance; and the more the content of the small-particle nano silica is, the lower the sintering temperature is, and the transmittance is slightly low, so that by making the ratio in the above range, the high transmittance is provided while the sintering temperature is low.

Further, the particle size of the first vapor phase silicon oxide particles is between 100nm and 150nm, such as 110nm, 130nm, 140nm, etc., and may be selected according to the needs, and is not particularly limited herein. The particle size of the second vapor phase silicon oxide particles is 10nm to 80nm, such as 20nm, 40nm, 60nm, etc., and may be selected according to the need, and is not particularly limited herein. The sintering temperature is reduced as much as possible by limiting the two gas-phase silicon oxide particles in the range, and the manufactured glass piece has high transmittance. Particle sizes in this application all refer to median particle size D50.

Wherein the first gas phase silicon oxide particles and the second gas phase silicon oxide particles in a predetermined ratio are added to a predetermined amount of the solvent. Specifically, a homogenizer may be used to uniformly disperse the first vapor phase silicon oxide particles and the second vapor phase silicon oxide particles in a solvent. The dispersion is prepared to have a solid content of 20% to 45%, preferably a dispersion having a solid content of 25%. And filtering the dispersion liquid through a filter element to remove impurities, agglomerated large particles and the like.

In addition, the solid content of the dispersion in the present application refers to the ratio of the total mass of the gas-phase silicon oxide particles added to the solvent to the total mass of the dispersion. The high solid content can make gas phase silicon oxide be difficult to disperse in the dispersion, and low solid content can lead to the volume shrinkage of glass spare too big, and easy fracture or damage when the solid content within this application is in the scope, when guaranteeing that gas phase silicon oxide can have good dispersibility in the dispersion, has great shrinkage again, and difficult fracture or damage.

The solvent may be selected as needed, and may be deionized water, dilute hydrochloric acid, or the like, without any particular limitation.

As shown in fig. 2, step S22 and step S23 in fig. 2 are similar to steps S12 and S13 in fig. 1, and are not described here again.

Still further, referring to fig. 3, fig. 3 is a schematic flow chart of an embodiment of step S12 in fig. 1 of the present application, wherein alkoxysilane is added to the dispersion and hydrolyzed to form a sol solution, and the method specifically includes the following steps:

s31: and regulating the pH value of the dispersion liquid to be 1.3-2.8 to obtain an acidification mixed liquid.

For example, the pH of the dispersion may be adjusted by using hydrochloric acid, and a dilute hydrochloric acid having a concentration of 0.1mol/L to 0.01mol/L may be prepared by first preparing dilute hydrochloric acid with deionized water, thereby adjusting the pH of the dispersion.

The diluted hydrochloric acid is added to the silica dispersion, and the pH of the dispersion is adjusted to 1.3 to 2.8, preferably 2.0, but the pH of the dispersion may be adjusted to 1.8, 2.5, or the like, and the dispersion is specifically selected according to the need and is not limited thereto. Thus, an acidified mixed solution was obtained. And stirring the acidified mixture for several minutes to several hours, preferably 30 minutes, to form a uniformly dispersed dispersion.

S32: the alkoxysilane is added to the acidified mixture to form a sol solution.

Specifically, the alkoxysilane may be added to the uniformly dispersed acidified mixture, and after stirring for a certain period of time, the alkoxysilane is hydrolyzed to form a sol solution. The stirring time is generally from 60 to 300 minutes, preferably 180 minutes. Of course, the stirring time can be adjusted to 90min, 150min, 250min, etc., and the stirring time is specifically selected according to the requirements, which is not limited herein.

Further, referring to fig. 4, fig. 4 is a flow chart illustrating an embodiment of step S13 in fig. 1 of the present application, in which the sol solution with the pH adjusted is prepared into a gel, and the method specifically includes the following steps:

s41: regulating the pH value of the sol solution to 2.5-5;

for example, ammonia water may be used to adjust the pH of the sol solution after the agitation, and deionized water may be used to prepare ammonia water having a concentration of 0.1mol/L, thereby adjusting the pH of the sol solution after the agitation. The pH of the sol solution is adjusted to a pH of between 2.5 and 5, preferably 4.0, by adding dilute aqueous ammonia. Of course, the pH of the sol solution may be adjusted to 3, 3.5, 4, etc., and is specifically selected according to the needs, which is not limited herein. In this way, the sol solution can be allowed to form a gel over a certain period of time.

S42: injecting the sol solution into a mold and aging to form a wet gel block;

since a large amount of bubbles are generated in the sol solution while the solution is stirred, the bubbles can be discharged by standing or vacuuming. The sol solution is allowed to stand for 0 to 200min, preferably 30min, but may be allowed to stand for 20min, 40min, 60min, etc., and is specifically selected according to the needs, and is not limited herein. Or vacuumizing for 0-10 min, preferably 2min, and the vacuumizing time can be regulated to be 1min, 3min, 5min and the like, and the vacuumizing time is specifically selected according to the requirements, and is not limited herein.

Injecting the foam-removed sol solution into a mold, aging and forming to obtain a wet gel block with certain strength. The mold may be of various shapes and sizes so that glass pieces of various shapes and sizes, such as optical element lenses, etc., may be obtained. The wet gel is released from the mold, and a wet gel block with a transferred fine structure can be obtained.

S43: pickling the wet gel block at pH of 4.0-7.0;

the wet gel pieces were acid washed at a pH. The ph=4.0 to 7.0, preferably ph=7.0, although the pH values of the pickling solution may be 5.0, 5.5, 6.0, etc., and the pH value is specifically selected according to the need, and is not limited thereto. The sample is circularly washed, so that the internal reaction of the gel block can be increased; secondly, surface impurities can be removed, and the transparency of the sample is improved.

S44: and drying the wet gel block after acid washing to obtain a xerogel block.

For example, the wet gel blocks after acid washing can be dried in a constant temperature and humidity box according to preset temperature and preset humidity, wherein the preset temperature is between 40 and 90 ℃, and the preset humidity is between 20 and 90 percent. Preferably, the drying is carried out at a preset temperature of 45℃and a preset humidity of 75%. The sample is easy to crack due to the fact that the preset temperature is too high, the preset humidity is too high, the drying time is long, and the preparation period is prolonged. Of course, the preset temperature may be 50 ℃, 60 ℃, 75 ℃ and the like, the preset humidity may be 30%, 40%, 60% and the like, and the preset humidity may be specifically selected according to the needs, which is not limited herein.

Further, referring to fig. 5, fig. 5 is a schematic flow chart of another embodiment of step S13 in fig. 1 of the present application, wherein the glass piece is sintered at 1000-1200 ℃ for a preset time, and the method specifically includes the following steps:

s51: placing the xerogel block in a sintering furnace;

for example, the xerogel blocks may be placed in a tube furnace or other sintering furnace, and the wet gel blocks may be sintered at a predetermined temperature.

S52: sintering the dry gel block in a sintering furnace at 1000-1200 ℃ for 4-20 h to prepare the glass piece.

In general, the sintering temperature of the sintering furnace may be preset for sintering the wet gel blocks for a predetermined time. Specifically, the wet gel block may be sintered at a preset temperature for 4 to 20 hours in a sintering furnace to manufacture a glass member.

It should be noted that, of course, the preset temperature may be 1050 ℃, 1100 ℃, 1150 ℃ and the like, and may be 5h, 7h, 9h and the like, which are specifically selected according to the requirement, and the present invention is not limited thereto.

Therefore, by using two kinds of nano silicon dioxide particles with different particle diameters, the sintering temperature can be reduced, and the sintering temperature can be further between 1050 ℃ and 1180 ℃, and the transmittance is more than 90%, so that a glass device meeting the requirements can be prepared according to the product requirement.

A second aspect of embodiments of the present application provides a glazing produced by at least a method comprising the first aspect of embodiments of the present application.

The glass piece can be prepared by the preparation method to obtain a silicon oxide glass sintered body. The glass piece has less cracking or breakage, the glass piece with the complete structure finally obtained accounts for more than 98 percent of the total sintered glass pieces, the glass piece can keep higher visible light transmittance which can reach more than 90 percent, and in addition, the volume shrinkage rate of the finally sintered glass piece relative to the dry gel block is 70-90 percent, so that the glass piece has higher shrinkage rate and can avoid cracking or breakage as much as possible.

A third aspect of embodiments of the present application provides a light-emitting device comprising at least a glazing as in the second aspect of embodiments of the present application.

The light emitting device can be applied to projection and display systems, such as a digital light path processor or a projector; but also to lighting systems such as car lights, stage lights, etc.

In addition, for better convenience of operation and understanding, according to the first aspect of the embodiments of the present application, two specific embodiments are presented, specifically, embodiment one and embodiment two:

example 1

Firstly, preparing dilute hydrochloric acid with pH=2.46, weighing 345g of fumed silica with the particle size of 10-80 nm and 345g of fumed silica with the particle size of 100-150 nm, mixing and stirring 2310g of dilute hydrochloric acid, and uniformly dispersing by using a homogenizer; after stirring for 30min, 1000g of ethyl orthosilicate is added, stirring is carried out for 150min to form a sol solution, then ammonia water is added to adjust the pH=4.0 of the sol, stirring is carried out for 5min, vacuum pumping is carried out for 2min, the sol is injected into a mould with a microstructure, gel is formed after 8h, demoulding is carried out after 48h, demoulding is easy, the gel hardness is hard, the breaking is difficult, and the sample integrity is as high as 98%.

And (3) putting the wet gel with the microstructure into pure deionized water, circularly washing, putting the wet gel into a constant temperature and humidity box with the temperature of 45 ℃ and the humidity of 75% for drying, and carrying out heat preservation at 1180 ℃ for 12 hours after drying the sample to obtain the optical element with the microstructure. The volume shrinkage of the whole was 80% and the transmittance was 91.90%.

Example two

Firstly, preparing dilute hydrochloric acid with pH=2.46, then weighing 627g of fumed silica with the particle size of 10-80 nm and 63g of fumed silica with the particle size of 100-150 nm, mixing and stirring 2310g of dilute hydrochloric acid, and uniformly dispersing by using a homogenizer; after stirring for 30min, 1000g of ethyl orthosilicate is added, stirring is carried out for 150min to form a sol solution, then ammonia water is added to adjust the pH=4.0 of the sol, stirring is carried out for 5min, vacuum pumping is carried out for 2min, the sol is injected into a mould with a microstructure, gel is formed after 8h, demoulding is carried out after 48h, demoulding is easy, the gel hardness is hard, the breaking is difficult, and the sample integrity is as high as 98%.

And (3) putting the wet gel with the microstructure into pure deionized water, circularly washing, putting the wet gel into a constant temperature and humidity box with the temperature of 45 ℃ and the humidity of 75% for drying, and carrying out heat preservation at 1130 ℃ for 12 hours after drying the sample to sinter the wet gel to obtain the optical element with the microstructure. The volume shrinkage of the whole was 80%, and the transmittance was 90.50%.

The foregoing description is only a partial embodiment of the present application, and is not intended to limit the scope of the present application, and all equivalent devices or equivalent process transformations made by using the descriptions and the drawings of the present application, or direct or indirect application to other related technical fields, are included in the patent protection scope of the present application.

Claims (10)

1. A method of making a glass article, the method comprising:

preparing a dispersion liquid from at least two gas-phase silicon oxide particles with different particle diameters according to a preset proportion;

adding alkoxy silane into the dispersion liquid, and hydrolyzing to form sol solution;

and preparing the sol solution into gel, and sintering the gel at 1000-1200 ℃ for a preset time to prepare the glass piece.

2. The production method according to claim 1, wherein the at least two kinds of vapor phase silicon oxide particles having different particle diameters include a first vapor phase silicon oxide particle and a second vapor phase silicon oxide particle;

the preset proportion of the first gas-phase silicon oxide particles and the second gas-phase silicon oxide particles is 1:1-1:1000 by weight, and the particle size of the first gas-phase silicon oxide particles is larger than that of the second gas-phase silicon oxide particles.

3. The method of claim 2, wherein the first vapor phase silica particles have a particle size of between 100nm and 150nm and the second vapor phase silica particles have a particle size of between 10nm and 80 nm.

4. The method according to claim 2, wherein the step of preparing the dispersion of at least two kinds of vapor phase silicon oxide particles having different particle diameters in a predetermined ratio comprises:

and adding a preset amount of solvent into the first gas-phase silicon oxide particles and the second gas-phase silicon oxide particles according to the preset proportion to prepare a dispersion liquid with the solid content of 20-45%.

5. The method according to claim 1, wherein in the step of adding an alkoxysilane to the dispersion, a mass ratio of the alkoxysilane to the dispersion is 0.225 to 0.9.

6. The method of claim 1, wherein said adding an alkoxysilane to said dispersion hydrolyzes to form a sol solution comprising:

regulating the pH value of the dispersion liquid to be 1.3-2.8 to obtain an acidified mixed liquid;

adding alkoxy silane into the acidified mixed solution to form the sol solution.

7. The method of claim 6, wherein forming the sol solution into a gel comprises:

regulating the pH value of the sol solution to 2.5-5;

injecting the sol solution into a mold and aging to form a wet gel mass;

pickling the wet gel block at pH of 4.0-7.0;

and drying the wet gel block after acid washing to obtain a xerogel block.

8. The method of claim 7, wherein sintering the gel at 1000 ℃ to 1200 ℃ for a predetermined time to form the glass part comprises:

placing the dried xerogel block into a sintering furnace;

sintering the wet gel block in the sintering furnace at 1000-1200 ℃ for 4-20 hours to obtain the glass piece.

9. A glazing produced by a process comprising at least one of the methods of any of claims 1 to 8.

10. A light-emitting device comprising at least the glass member according to claim 9.

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