阅读说明：本技术 一种兼具紫外吸收与低表面张力的碱铝硅酸盐柔性玻璃 (Alkali aluminosilicate flexible glass with ultraviolet absorption and low surface tension ) 是由 田英良 侯延升 徐正本 徐强 于 2020-04-07 设计创作，主要内容包括：本发明属于柔性玻璃技术领域,提出了一种兼具紫外吸收与低表面张力的碱铝硅酸盐柔性玻璃,包括按质量百分比计,包括玻璃熔体活性物质组合物3-5％、紫外吸收剂组合物3-5％、碱铝硅酸盐玻璃配合料90-94％；按质量份数计,所述的玻璃熔体活性物质组合物包括五氧化二铌1-2份、三氧化二锑20-30份、硝酸钾35-40份；紫外吸收剂组合物包括三氧化二铁1～3份、三氧化钼10～20份、氧化铒4～8份、硝酸钾35～40份。通过上述技术方案,解决了现有技术中玻璃熔体表面张力大,不利于柔性玻璃成形、皮秒紫外激光加工质量不高的问题。(The invention belongs to the technical field of flexible glass, and provides alkali aluminosilicate flexible glass with ultraviolet absorption and low surface tension, which comprises 3-5% of glass melt active substance composition, 3-5% of ultraviolet absorbent composition and 90-94% of alkali aluminosilicate glass batch material by mass percent; the glass melt active substance composition comprises, by mass, 1-2 parts of niobium pentoxide, 20-30 parts of antimony trioxide and 35-40 parts of potassium nitrate; the ultraviolet absorbent composition comprises 1-3 parts of ferric oxide, 10-20 parts of molybdenum trioxide, 4-8 parts of erbium oxide and 35-40 parts of potassium nitrate. Through the technical scheme, the problems that in the prior art, the surface tension of glass melt is large, the flexible glass is not easy to form, and the picosecond ultraviolet laser processing quality is not high are solved.)

1. An alkali aluminosilicate flexible glass with ultraviolet absorption and low surface tension is characterized by comprising 3-5% of glass melt active substance composition, 3-5% of ultraviolet absorbent composition and 90-94% of alkali aluminosilicate glass batch by mass percentage.

2. The alkali aluminosilicate flexible glass having both ultraviolet absorption and low surface tension according to claim 1, comprising, by mass, 5% of glass melt active composition, 5% of ultraviolet absorber composition, and 90% of alkali aluminosilicate glass batch.

3. The alkali aluminosilicate flexible glass having both ultraviolet absorption and low surface tension according to claim 1, comprising, by mass, 4% of glass melt active composition, 4% of ultraviolet absorber composition, and 92% of alkali aluminosilicate glass batch.

4. The alkali aluminosilicate flexible glass having both ultraviolet absorption and low surface tension according to claim 1, comprising, by mass, 3% of glass melt active composition, 3% of ultraviolet absorber composition, and 94% of alkali aluminosilicate glass batch.

5. The alkali aluminosilicate flexible glass having both ultraviolet absorption and low surface tension according to claim 1, wherein the glass melt active material composition comprises, by mass, 1-2 parts of niobium pentoxide, 20-30 parts of antimony trioxide, and 35-40 parts of potassium nitrate.

6. The alkali aluminosilicate flexible glass having both ultraviolet absorption and low surface tension according to claim 1, wherein the ultraviolet absorber composition comprises, by mass, 1 to 3 parts of ferric oxide, 10 to 20 parts of molybdenum trioxide, 4 to 8 parts of erbium oxide, and 35 to 40 parts of potassium nitrate.

7. The alkali aluminosilicate flexible glass having both ultraviolet absorption and low surface tension according to claim 1, wherein the glass melt active composition comprises, by mass, 1.5 parts of niobium pentoxide, 25 parts of antimony trioxide, and 37.5 parts of potassium nitrate.

8. The alkali aluminosilicate flexible glass having both ultraviolet absorption and low surface tension according to claim 1, wherein the ultraviolet absorber composition comprises the following components in parts by weight: 2 parts of ferric oxide, 15 parts of molybdenum oxide, 6 parts of erbium oxide and 37.5 parts of potassium nitrate.

9. The alkali aluminosilicate flexible glass having both ultraviolet absorption and low surface tension according to claim 1, wherein the alkali aluminosilicate glass batch comprises, by mass: 54.0-69.0% of silicon oxide, 5.0-24.0% of aluminum oxide, 0-3.5% of lithium oxide, 12.8-16.0% of sodium oxide, 0-3.5% of potassium oxide, 0-4.0% of calcium oxide, 4.0-6.0% of magnesium oxide, 0-3.0% of zinc oxide and 0-1.0% of zirconium dioxide.

10. The alkali aluminosilicate flexible glass having both ultraviolet absorption and low surface tension according to claim 1, wherein the flexible glass comprises, in mass percent: 51.15-66.96% of silicon oxide, 4.74-23.29% of aluminum oxide, 0-3.88% of lithium oxide, 12.79-15.53% of sodium oxide, 1.02-5.28% of potassium oxide, 0-3.88% of calcium oxide, 2.84-5.82% of magnesium oxide, 0-2.91% of zinc oxide, 0-0.93% of zirconium dioxide, 0.09-0.16% of ferric oxide, 0.62-1.06% of molybdenum trioxide, 0.25-0.42% of erbium oxide, 0.06-0.11% of niobium pentoxide and 0.42-1.58% of antimony trioxide.

Technical Field

The invention belongs to the technical field of flexible glass, and relates to alkali aluminosilicate flexible glass with ultraviolet absorption and low surface tension.

Background

With the development of electronic information display products in the directions of light weight, thinness, large size, flexibility, high resolution, high contrast and the like, under the traction action of requirements, electronic glass also develops in the directions of light weight, thinness, large size and flexibility, and when the thickness of the glass reaches below 0.1mm (100 micrometers), the glass can show excellent flexibility, so that flexible glass varieties are produced.

The flexible glass changes the storage mode of the plate glass, can meet the requirement of bending and winding, and realizes the roll-to-roll process in the aspect of processing and use. Technologists propose many application scenarios for flexible glass, including flexible displays, flexible photovoltaic products, wearable products, roll-to-roll capacitors, and the like.

Flexible ultra-thin glass has entered into the preliminary stage of industrialization, in which technologies development and industrial production have been conducted in flexible ultra-thin glass by the united states corning company, asahi glass, electric glass company and german schottky company. In recent years, the four companies mentioned above have made new breakthroughs in the thickness of flexible glass, and a plurality of flexible ultrathin glass products have been successively introduced.

At present, the production method of flexible glass mainly comprises an overflow method, a float method, a slit downdraw method, a redraw method, a chemical thinning method and the like, and for the ultra-thin glass and the flexible glass which are formed in one step, after batch materials are melted into uniform, bubble-free and stone-free high-quality glass melt, no matter the overflow method, the float method or the slit downdraw method is adopted to produce and form the glass, the glass must be in a glass forming temperature range (namely viscosity is 10)^4～11.5Poise corresponding temperature), longitudinal stretching (consistent with the production advancing direction) and transverse stretching (perpendicular to the production advancing direction) are required, if only longitudinal stretching is carried out, the molten glass strip can generate obvious retraction effect under the action of surface tension, so that the molten glass strip is gathered towards the center, the plate width of the formed glass strip is only 1/3 of the initial glass melt width, even smaller, the thickness distribution along the plate width direction is extremely uneven, the thicknesses of two sides are larger, the thickness of the center is smaller, the thickness of the edge part is almost about 3 times of the center thickness of the plate surface, the part of unqualified edge part almost occupies 1/3 of the whole plate width, even more, the utilization rate of qualified glass liquid is greatly wasted, and the raw material or the production efficiency of the flexible glass is greatly reduced. To overcome the deleterious effects of the retraction of the glass sheet surface due to surface tension of the glass melt during forming, it is necessary to apply a force to the molten glass ribbonThe transverse stretching effect is added, a common mechanical device is an edge roller or a pair roller clamping mechanism, more than 20 pairs of transverse edge rollers are needed in the float process for producing ultrathin glass with the thickness of 0.2-0.4 mm, and 2-4 pairs of transverse edge rollers or pair roller clamping mechanisms are also needed in the overflow method and the slit downdraw method, so that the surface tension of the glass melt is a very harmful factor for the ultrathin and flexible glass forming.

The surface tension of the glass melt depends on the chemical components and the composition of the glass to a great extent, and at present, the flexible glass for displaying electronic information mainly comprises alkali-free aluminoborosilicate base glass and alkali aluminosilicate glass, and the two types of glass have excellent mechanical property, thermal property, electrical property and chemical stability and have the functions of mechanical support, semiconductor circuit bearing body, transparency and light transmission and screen protection. Because the two kinds of glass are rich in a large amount of alumina (Al)₂O₃) Aluminum oxide (Al)₂O₃) Can impart excellent physical and chemical properties to glass, but alumina (Al)₂O₃) The surface tension of the glass melt is greatly increased, for alkali aluminosilicate glass, the surface tension of the glass melt reaches 350 mN/m-410 mN/m (milli-newton per meter), while the surface tension of common soda-lime glass is only 310 mN/m-330 mN/m, for the ultra-thin forming of the glass, especially for producing and preparing flexible glass with the thickness of less than 100 microns, the larger surface tension is a great difficulty for the ultra-thin forming of the glass melt, and the thickness uniformity and the surface flatness of a glass plate surface can be seriously influenced.

Chemical substances are important technical means for improving and reducing the surface tension of glass melt, and a surfactant is disclosed in Chinese patent CN106495468A (mass percentage): MoO₃1～4％，V₂O₅0～2％，WO₃0 to 3% and MoO₃+V₂O₅+WO₃1-5%; CN1041176932B discloses a surfactant which comprises the following components in percentage by mass: MoO₃0.6～0.8％，Bi₂O₃1.1～1.5％，GeO₂1.2 to 1.3%, and MoO₃+Bi₂O₃+GeO₂3 to 3.5 percent; CN1058859128B discloses a surfactant which is (mole percentage): WO₃0.001～0.5％，CaF₂And/or SrCl₂0.3 to 1.5 percent. The above surfactants have three main problems: 1) toxic, e.g. V₂O₅，CaF₂And/or SrCl₂Volatile matter of (2); 2) colouring, e.g. MoO₃、V₂O₅、WO₃Coloration, yellow or brown due to valence-change characteristics or color center; 3) and crystallization, namely MoO3 and WO3 belong to oxides with high atomic numbers, are easy to accumulate to cause crystallization, and the three points seriously influence the glass forming characteristics, the product quality and the product application.

In addition to the surface tension effects encountered during the manufacturing process, flexible glass products are also subject to the cutting and severing challenges of the manufacturing process.

The traditional flat glass cutting and processing mainly utilizes the brittleness of glass and the extension of a Graves crack to form a fracture, a diamond cutter wheel scratch breaking method is generally adopted, in the last decade, high-pressure water jet cutting and processing appear, and the method is mainly suitable for glass plates with the thickness of more than 4 mm; in addition, infrared (10.6 microns and 1.06 microns) CO₂The laser cutting is also applied and popularized, and the applicable thickness is 1-20 mm. However, in the cutting method, for the processing of the flexible glass, radioactive damage occurs at the action point of the flexible glass plate surface, and the processing of the flexible glass can hardly be completed.

And picosecond ultraviolet laser is relatively excellent in flexible glass cutting efficiency and cutting section quality. The common wavelength range of ultraviolet laser is 325-352nm, and conventional articles of aluminoborosilicate glass and alkali aluminoborosilicate glass have good ultraviolet transmittance and do not have ultraviolet absorption capacity, so that the processing efficiency and the cross section processing quality of the ultraviolet laser are poor, and therefore the problem of developing flexible glass with the ultraviolet absorption capacity is urgently solved, and meanwhile, ultraviolet absorption substances cannot damage other functions of the flexible glass, such as visible light transparency and imaging quality effect.

At present, it is known that the ultraviolet absorbing substances usable for colorless transparent glass are mainly cerium oxide and titanium dioxide, and the effect of both is better, but the greatest problem of cerium oxide and titanium dioxide as ultraviolet absorbers is that: 1) the crystallization is easy, the liquidus of the glass is improved, titanium dioxide is a common crystal nucleating agent, the total mass content of 3-4 percent has higher risk, and the glass forming is not favorable; 2) the glass is yellowed and even amber, the appearance color of the glass product is influenced, and the visible light transmittance is reduced by 3-5%; 3) cerium dioxide is a rare earth element, generates a strong fluorescence effect under the ultraviolet excitation of LED backlight, and has a destructive effect on the actual color of a screen image, so that the traditional cerium dioxide and titanium dioxide ultraviolet absorbers cannot be used in flexible glass for information display products. Therefore, it is highly desirable to invent an alkali aluminosilicate flexible glass suitable for ultraviolet laser processing (cutting, slotting, drilling, etc.).

Based on the harm and influence of the surface tension of the glass melt on the forming of the flexible glass, the urgent need of realizing an ultraviolet absorption function in the flexible glass, the promotion of precise high-quality and high-efficiency processing of the flexible glass by ultraviolet laser, and the search for a novel composition of a glass melt active substance and the ultraviolet absorption function becomes a problem which needs to be solved urgently in the industry.

Disclosure of Invention

The invention provides alkali aluminosilicate flexible glass with ultraviolet absorption and low surface tension, and solves the problems that in the prior art, the surface tension of glass melt is high, the flexible glass is not easy to form, and the picosecond ultraviolet laser processing quality is not high.

The technical scheme of the invention is realized as follows: an alkali aluminosilicate flexible glass with ultraviolet absorption and low surface tension comprises, by mass, 3-5% of a glass melt active substance composition, 3-5% of an ultraviolet absorbent composition, and 90-94% of an alkali aluminosilicate glass batch.

Further, the glass melt comprises 5% of glass melt active substance composition, 5% of ultraviolet absorbent composition and 90% of alkali aluminosilicate glass batch by mass percentage.

Further, the glass melt active material composition comprises 4% of glass melt active material composition, 4% of ultraviolet absorbent composition and 92% of alkali aluminosilicate glass batch by mass percentage.

Further, the glass melt comprises 3% of glass melt active substance composition, 3% of ultraviolet absorbent composition and 94% of alkali aluminosilicate glass batch by mass percentage.

Furthermore, the glass melt active substance composition comprises, by mass, 1-2 parts of niobium pentoxide, 20-30 parts of antimony trioxide and 35-40 parts of potassium nitrate.

Further, the ultraviolet absorbent composition comprises, by mass, 1-3 parts of ferric oxide, 10-20 parts of molybdenum trioxide, 4-8 parts of erbium oxide and 35-40 parts of potassium nitrate.

Further, the glass melt active substance composition comprises 1.5 parts of niobium pentoxide, 25 parts of antimony trioxide and 37.5 parts of potassium nitrate by mass.

Further, the ultraviolet absorbent composition comprises the following components in parts by weight: 2 parts of ferric oxide, 15 parts of molybdenum oxide, 6 parts of erbium oxide and 37.5 parts of potassium nitrate.

Further, the alkali aluminosilicate glass batch comprises the following components in percentage by mass: 54.0-69.0% of silicon oxide, 5.0-24.0% of aluminum oxide, 0-3.5% of lithium oxide, 12.8-16.0% of sodium oxide, 0-3.5% of potassium oxide, 0-4.0% of calcium oxide, 4.0-6.0% of magnesium oxide, 0-3.0% of zinc oxide and 0-1.0% of zirconium dioxide.

Further, the flexible glass comprises, in mass percent: 51.15-66.96% of silicon oxide, 4.74-23.29% of aluminum oxide, 0-3.88% of lithium oxide, 12.79-15.53% of sodium oxide, 1.02-5.28% of potassium oxide, 0-3.88% of calcium oxide, 2.84-5.82% of magnesium oxide, 0-2.91% of zinc oxide, 0-0.93% of zirconium dioxide, 0.09-0.16% of ferric oxide, 0.62-1.06% of molybdenum trioxide, 0.25-0.42% of erbium oxide, 0.06-0.11% of niobium pentoxide and 0.42-1.58% of antimony trioxide.

The working principle and the beneficial effects of the invention are as follows: the ultraviolet absorbent composition, the glass melt surface active substance composition and the alkali aluminosilicate glass batch are combined, so that the high-quality melting of glass is met, the aim of reducing the surface tension of the glass melt is effectively fulfilled, the phenomenon of uneven wrinkles caused by surface tension retraction in the spreading and unfolding process of the glass melt is greatly improved, the plate surface unfolding efficiency is greatly improved, the effective width of a plate surface is increased, the plate surface flatness is better, and the application of an information display product can be met; the high ultraviolet absorption and high visible light transmission of the alkali aluminosilicate flexible glass are realized, the picosecond ultraviolet laser processing problem of the flexible glass is effectively solved, and the technical conditions for the flexible glass in folding mobile phones and flexible photovoltaic products are laid.

According to the flexible glass prepared by the invention, the surface tension of the glass melt can be reduced by about 30-41mN/m (milli-newton per meter), and is reduced by 8-10% compared with the glass without using surface active substances, so that the phenomenon of uneven wrinkles caused by surface tension retraction in the spreading and unfolding process of the glass melt is greatly improved, the roughness is less than 2 micrometers, the thickness difference is less than 5 micrometers, the width of the plate surface is increased by 30%, the effective width of the plate surface is increased, the flatness of the plate surface is better, and the application of information display products is better met.

The spectrum transmittance of the flexible glass prepared by the invention in the 325-352nm ultraviolet region is less than 30%, and the absorption of several typical ultraviolet lasers can be realized, thereby effectively meeting the ultraviolet laser processing of the flexible glass. And the average value of the visible light transmittance for the glass sheet with the thickness of 50 mu m is more than 89 percent; for the formed and prepared flexible glass with the thickness of 50 mu m, 343nm picosecond ultraviolet laser is adopted for cutting processing, the linear velocity can reach 160mm/s, the section is smooth and has no burr, and the cutting efficiency is improved by 60 percent.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part 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.