CN113105105B

CN113105105B - Glass welding method and composite glass device

Info

Publication number: CN113105105B
Application number: CN202010031639.1A
Authority: CN
Inventors: 王伟; 许仁; 丁雄风; 王世军; 彭晓林
Original assignee: Weidali Industry Chibi Co ltd
Current assignee: Weidali Technology Co ltd
Priority date: 2020-01-13
Filing date: 2020-01-13
Publication date: 2022-10-14
Anticipated expiration: 2040-01-13
Also published as: CN113105105A

Abstract

The invention relates to the technical field of glass, in particular to a glass welding method and a composite glass product. The glass welding method disclosed by the invention comprises the following steps of: heating and jointing the surfaces to be welded between at least two glass pieces to obtain a heat jointing glass group; heating and welding the surfaces to be welded of the hot-adhered glass groups; and annealing the fused glass group. The glass group which is tightly attached without bubbles is realized through simple thermal attaching treatment, atoms on the surface to be welded of the glass are bonded again through heating, and the welding of the glass body can be realized without adding any flux. The glass product welded by the method has high strength at the joint and no bubble defect.

Description

Glass welding method and composite glass device

Technical Field

The invention relates to the technical field of glass, in particular to a glass welding method and a composite glass device.

Background

Glass is one of the most widely used materials in human production and life at present due to its advantages of excellent light transmittance, high hardness, low manufacturing cost, etc. With the development of the times, people have increasingly demanded multilayer glass structure products with more delicate appearances.

Conventional fusion bonding techniques typically require the use of a fusing agent such as a low melting point glass frit that softens at a relatively low temperature and acts like a glue to bond the two glass surfaces to be bonded together. However, the flux addition has high requirements on equipment and process, the uniformity of the coated flux is difficult to ensure, and the appearance of the product is very easily influenced. Furthermore, the joint of the combined glass material after the flux welding is not strong enough compared with the glass itself which is integrated. The more serious problem is that the thermal expansion coefficients of the fusing agent and the glass are different, which seriously restricts the overall thermal stability of the composite glass piece after welding and has great influence on the function of the product. The glass product is directly contacted and heated for welding, the glass is often required to be heated to a temperature higher than the softening temperature so that the glass has certain fluidity for processing, but the softening influences the shape of the glass, and bubbles at the contact part are often difficult to remove after welding, or the welding part is not welded locally because the welding part is not tightly attached. Therefore, it is necessary to develop a glass fusion technique that can achieve fusion without bubble defects without using a flux and without reaching the softening temperature of the glass.

Disclosure of Invention

In view of the above problems, it is an object of the present invention to provide a glass fusing method capable of achieving tight bubble defect-free fusing below the softening temperature of glass without requiring a flux, and a composite glass product manufactured according to the method.

A glass fusion process comprising the steps of:

1) Bonding the surfaces to be fused of at least two glass pieces, and controlling the temperature of the surfaces to be fused to be 70-120 ℃ to obtain a hot bonding glass group;

2) Heating the surfaces to be welded of the hot-adhered glass groups for welding;

3) And annealing the welded glass group.

In one embodiment, the glass piece may be a flat glass or a curved glass.

In one embodiment, the surfaces of the glass pieces to be fused

In one embodiment, the temperature of the attaching surface is 70-100 ℃ during the attaching and heating process.

In one embodiment, in the heating welding process in the step 2), the temperature of the surface to be welded of the glass group is controlled to be 600-800 ℃, and the welding time is 0.5-2 h.

In one embodiment, in step 3), the temperature of the annealing treatment is 500-900 ℃ and the time is 0.5-2 h.

In some of the above embodiments, the glass may be a soda-lime-silicate glass, a lead-silicate glass, an aluminosilicate glass, or a borosilicate glass.

In some of the above embodiments, the step 1) is followed by a step of defoaming the thermally bonded glass assembly. Optionally, the ambient pressure is 0.6MPa to 1.5MPa, the temperature is 45 ℃ to 65 ℃ and the time is 20min to 60min in the process of removing bubbles between interfaces to be welded of the heat bonding glass group.

In some embodiments, in the heating welding process in step 2), the temperature of the surface to be welded of the glass group is controlled to be 650-750 ℃, and the welding time is 1-2 h.

In some embodiments, in step 3), the temperature of the annealing treatment is 700 ℃ to 900 ℃ and the time is 1h to 2h.

The invention also provides a composite glass device prepared according to the glass welding method in any one of the above embodiments.

The inventors of the present invention have discovered that, in an attempt to achieve fusion bonding of glass without bubble defects, fusion bonding of glass at a certain temperature is performed to eliminate bubble defects that are difficult to eliminate. After further experiments and analysis, the glass welding method is used for bonding glass in a hot state, so that bubbles between interfaces can be effectively removed, and bubble defects in a final glass finished product are eliminated; the surface activity of the glass can be enhanced, so that atoms with higher surface free energy are bonded and tightly attached; the glass group can be cooled to generate negative pressure on the surface to be welded, so that the glass group is difficult to separate and is more convenient for subsequent welding operation. After the tight bonding is realized, the interface to be welded of the glass is heated, the diffusion of atoms between the glass interfaces in tight bonding is promoted, the bonding of the atoms between the two glasses is realized, and the effect of welding can be achieved without heating to the softening temperature of the glass.

The glass welding method does not need a flux, the obtained finished products are firmly combined, no obvious air bubbles or deformation exists between welding surfaces, the integration of the glass products after welding is realized, and the glass welding method can be used for occasions with higher requirements on welding effects, such as mobile phone cover plates and the like, and has good application prospects.

Drawings

FIG. 1 is a schematic flow chart of a glass fusing method according to the present invention.

FIG. 2 is a photograph of two glass sheets of example 1 attached together before fusion bonding.

FIG. 3 is a photograph of a glass product after welding two glass plates according to example 1.

FIG. 4 is a laser microscopic image of a cross section of a glass product obtained by fusing two glass sheets in example 1, after the glass product has been artificially broken.

Fig. 5 is a picture of a glass product after two flat glasses in comparative example 1 are fused, in which a portion circled by a black circle is a bubble defect between the glasses.

Detailed Description

In order that the invention may be more fully understood, reference will now be made to the following more particular description of the invention, examples of which are given by way of illustration only. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

Referring to fig. 1, the present invention provides a glass fusing method including the following steps.

Step S1, adhering surfaces to be welded of at least two glass pieces, and controlling the temperature of the surfaces to be welded to be 70-120 ℃ to obtain a heat-adhered glass group;

the glass piece can be flat glass or curved glass, as a specific example, the glass pieces to be welded are all flat glass, and the flat glass is glass with a wide application range in daily life. It should be understood that the glass welding method provided by the invention can also be used for glass with different shapes, as long as the glass piece to be welded is provided with a surface to be welded which can be jointed with another glass piece, and the flat glass or the curved glass is only a common implementation object. In addition, the surface to be welded can be totally-enclosed solid glass or ring glass with a hole in the middle, as long as the subsequent bonding can be realized.

As a specific example, the glass material to be fused may be soda-lime-silicate glass, lead-silicate glass, aluminosilicate glass, or borosilicate glass. More specifically, it may be aluminosilicate glass. It is noted that depending on the oxide components of the glass material, the glass may have different softening temperatures. The softening temperature of aluminosilicate glasses will generally be above 900 c, significantly higher than the temperatures used in the glass fusion process provided by the present invention. That is, the fusing process of the glass fusing method may be performed below the softening temperature.

As a specific example, before the surfaces to be welded of the glass pieces are bonded, the surfaces of the glass pieces to be welded may be cleaned, and the surface attachments may be removed and dried. The attachments on the surface specifically refer to dust, glass dust, grease and the like adsorbed on the surface of the glass. The glass is cleaned to prevent impurities on the surface of the glass from influencing subsequent close fitting and further influencing the effect of a final glass finished product. The roughness of the surface to be welded of the glass to be welded should not be higher than

The smooth surface is conducive to achieving a tight fit.

Further, the temperature of the surface to be welded can be controlled to be 70-100 ℃ in the bonding process in the step S1. In practical tests, the invention finds that bubbles which are difficult to remove originally between the two glass welding surfaces can be effectively removed by properly heating the glass in the laminating process, so that no bubbles exist between the welding surfaces of the welded glass finished product, and the appearance is attractive; the temperature should not be too high, otherwise the glass may be slightly deformed at high temperature, and warp may occur, which affects the shape of the final product. The other effect of heating and laminating is that the glass slightly shrinks in the process of cooling the heated glass, negative pressure can be generated at the interface, the laminating effect between the glass is enhanced, and the further operation is convenient; the heating can also improve the kinetic energy of atoms on the surface of the glass and promote the primary bonding of atoms on the surface in a higher energy state.

Optionally, a further bubble removal step may be added after application and heating. The environmental pressure is 0.6MPa to 1.5MPa, the temperature is 45 ℃ to 65 ℃ and the time is 20min to 60min in the defoaming process.

And S2, heating the surfaces to be welded of the hot-adhered glass groups for welding.

As a specific example, in the process of heating welding, the temperature of the surface to be welded of the glass group is required to be controlled to be 600-800 ℃, and the welding time is required to be 0.5-2 h. At this temperature, the glass will partially be fluid and some of the weakly bonded atoms on the surface will be easily broken. After the bond breaking of part of the atoms on one surface of the glass, the atoms on the other surface of the glass are bonded again. Because the bonds between the atoms are formed, the resulting fused glass product bonds strongly. It should be clear from the above description that the fusion of the present invention is to make atoms on the original glass surface disconnected by heating and reconnect to form new chemical bonds under the condition of close adhesion, so that the fusion can be performed at a temperature not higher than the softening point of the glass, and the shape of the glass is not affected significantly.

Specifically, the softening temperature of aluminosilicate glass is usually above 900 ℃, while the temperature used in the welding process in the welding method provided by the present invention is only 600 ℃ to 800 ℃. Generally, the higher the temperature, the shorter the time it takes to complete the weld. Further, because of the wide variety of specific glass sub-divisions, the softening temperatures vary from glass to glass depending on the silica content or other additives commonly used in the art. Therefore, other glasses mentioned in the present invention may also include some glass products having a higher heat resistance and a softening temperature higher than the fusion temperature. And for some products with lower softening temperature, the welding temperature can be properly reduced.

And S3, annealing the welded glass group to obtain the composite glass device.

As a specific example, the temperature of the annealing treatment in the step 3 is 500-900 ℃ and the time is 0.5-2 h. Further, the temperature of the annealing treatment can be 700-900 ℃ and the time is 1-2 h. The annealing treatment can ensure that atoms in the glass are rearranged to a certain degree in the processes of heat preservation and slow temperature reduction to reach a state with lower energy, eliminate residual stress or defects in the glass and prolong the service life of the glass. It should be noted that annealing and the aforementioned welding are actually two distinct operating steps. The annealing process is much less difficult than the fusion process. Generally, annealing requires only that the glass device be subjected to a temperature environment for heat preservation, regardless of the location or accuracy of the applied temperature.

The glass welding method can realize the welding between the glasses without a flux. Specifically, the fusion welding method is characterized in that bubbles between surfaces to be fused of glass pieces are effectively removed in a heating and laminating mode, and tight adhesion is achieved. And then negative pressure appears between the interface of waiting to weld after the cooling, and the laminating is more inseparable. And subsequently, through one-step heating welding, the broken bonds and the re-bonding of atoms on the interface to be welded are promoted, so that the fusion without bubble defects below the softening point temperature of the glass can be realized, and the fused composite glass product has firm combination of bubbles or defects.

The low temperature glass fusing method of the present invention will be described in further detail with reference to specific examples, and the glass fusing method provided by the present invention will be apparent from the following specific steps and effect tests. In the following examples, the raw materials used are all commercially available without specific reference.

The plate glasses used in the following examples and comparative examples are all Corning GG3 glasses with a specification of 75mm 150mm.

Example 1:

1) Cleaning two pre-processed and molded plate glasses, heating and laminating under a vacuum condition, wherein the temperature of a glass piece is 70 ℃ in the laminating process, and then placing the glass piece in a bubble removing machine for removing bubbles, wherein the temperature in the bubble removing machine is 65 ℃, the air pressure is 0.6MPa, and the time is 50min;

2) Placing the glass group subjected to the defoaming treatment on a bracket, heating the interface part to be welded, controlling the temperature of the part to be welded to be 650 ℃, and setting the welding time to be 2 hours;

3) And (3) placing the welded glass group in a resistance furnace, and annealing for 2h at the temperature of 900 ℃.

Example 2:

1) Cleaning two pre-processed and molded plate glasses, heating and laminating under a vacuum condition, wherein the temperature of a glass piece is 85 ℃ in the laminating process, and then placing the glass piece in a bubble removing machine for removing bubbles, wherein the temperature in the bubble removing machine is 55 ℃, the air pressure is 0.8MPa, and the time is 40min;

2) Placing the glass group subjected to the defoaming treatment on a bracket, heating an interface part to be welded, controlling the temperature of the part to be welded to be 700 ℃, and setting the welding time to be 1.5h;

3) And (3) placing the welded glass group in a resistance furnace, and annealing for 2h at the temperature of 800 ℃.

Example 3:

1) Cleaning two pre-processed and molded plate glasses, heating and laminating the two pre-processed and molded plate glasses under the air condition, wherein the temperature of a glass piece in the laminating process is 100 ℃, and then placing the glass piece in a bubble removing machine for removing bubbles, wherein the temperature in the bubble removing machine is 50 ℃, the air pressure is 1MPa, and the time is 30min;

2) Placing the glass group subjected to defoaming treatment on a bracket, heating an interface part to be welded, controlling the temperature of the part to be welded to be 750 ℃, and setting the welding time to be 1h;

3) And (3) placing the welded glass group in a resistance furnace, and annealing for 2h at the temperature of 700 ℃.

Comparative example 1:

1) Cleaning at least two pieces of plate glass which are processed and formed in advance, then attaching the plate glass under a vacuum condition, wherein the temperature of the plate glass in the attaching process is 25 ℃, then placing the plate glass in a bubble removing machine to remove bubbles, the temperature in the bubble removing machine is 65 ℃, the air pressure is 0.6MPa, and the time is 50min;

2) Placing the glass group subjected to defoaming treatment on a bracket, heating an interface part to be welded, controlling the temperature of the part to be welded to be 650 ℃, and setting the welding time to be 2 hours;

3) And (3) placing the welded glass group in a resistance furnace, and annealing for 2h at the temperature of 750 ℃.

Comparative example 2:

1) Cleaning at least two pieces of plate glass which are processed and formed in advance, then attaching the plate glass under a vacuum condition, wherein the temperature of the plate glass in the attaching process is 50 ℃, then placing the plate glass in a bubble removing machine to remove bubbles, the temperature in the bubble removing machine is 65 ℃, the air pressure is 0.6MPa, and the time is 50min;

Comparative example 3:

1) Cleaning at least two pieces of plate glass which are processed and formed in advance, then attaching the plate glass under the air condition, wherein the temperature of the plate glass is 150 ℃ in the attaching process, then placing the plate glass in a bubble removing machine to remove bubbles, wherein the temperature in the bubble removing machine is 65 ℃, the air pressure is 0.6MPa, and the time is 50min;

Effect test

The effects of the fusion surfaces of the fusion-bonded glasses obtained in examples 1 to 3 and comparative examples 1 to 3 are shown in the following Table 1:

as can be seen from Table 1, in examples 1 to 3, the bonding was performed by heating at 70 to 120 ℃ and the final welded product had a tight bond with no bubble on the welding surface. In contrast, in comparative example 1, the bonding is performed at normal temperature, and the welded surface of the finally welded product has large bubbles, which are particularly seen in the black circle marked part in fig. 5, and have a large influence on the appearance. Comparative example 2 when the lamination is carried out at 50 ℃, the interior of the laminated product still has fewer bubbles distributed in a single point. Comparative example 3 the lamination was carried out at 150 c, and the product after lamination was slightly warped although no air bubbles were present in the product.

Fig. 2 is a photograph showing two flat glasses before welding in example 1 after they are bonded. The two flat glasses are tightly attached together by themselves after hot attaching and removing bubbles between the interfaces, and the gap in the middle is the interface to be attached, which is very obvious in the photo, so that the obvious interface still exists between the two flat glasses.

FIG. 3 is a photograph of two glass sheets after fusion-bonding in example 1. The two flat glasses are welded at high temperature, atoms on the surfaces to be welded of the glasses are subjected to bond breaking and bonding again, and the atoms between the two glass sheets are bonded together through covalent bonds, which is equivalent to forming an integrated glass device. So that no significant gap between the two panes is visible in fig. 3.

Further, fig. 4 shows the result of characterization of the fused surface under a laser microscope after the glass sample shown in fig. 3 is artificially fractured. The section in fig. 4 is a relatively flat section, and no gap or trace of the welding interface can be found in the microscope picture of the section, which indicates that the two pieces of flat glass welded by the welding method provided in example 1 have no interface, and the original welding surface has uniform components, firm combination, and is comparable to the integrated glass, thus proving the superiority and practicability of the welding method provided by the present invention. Meanwhile, the glass after welding basically has no deformation compared with the glass before welding, and the fact that the glass is not softened in the welding process is also shown.

The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims

1. A glass fusion bonding method, comprising the steps of:

1) Cleaning the surface of a glass piece to be welded, removing surface attachments and drying; attaching surfaces to be welded of at least two glass pieces at a temperature of 55-120 ℃, wherein the roughness of the surfaces to be welded of the glass pieces is less than or equal to 30 angstroms to promote primary bonding of atoms with higher energy states on the surfaces of the glass pieces to obtain a thermally attached glass group, and performing bubble removal treatment on the thermally attached glass group, wherein in the step of bubble removal, the ambient air pressure is 0.6-1.5 MPa, the temperature is 50-65 ℃, the time in the step of bubble removal is 2-60min, and the glass is aluminosilicate glass or borosilicate glass;

2) Heating the surfaces to be welded of the heat-adhered glass groups to weld, controlling the temperature of the surfaces to be welded of the glass groups to be 650-750 ℃, and welding under the condition that the temperature is lower than the softening point of the glass piece, wherein the welding time is 1h-2h;

3) And annealing the fused glass group.

2. The glass fusing method of claim 1, wherein the glass pieces to be fused are sheet glass.

3. The glass fusing method of claim 1, wherein the temperature of the surface to be fused is controlled to be 70-100 ℃ during the attaching process.