阅读说明：本技术 适用紫外激光加工的碱铝硅酸盐柔性玻璃 (Alkali aluminosilicate flexible glass suitable for ultraviolet laser processing ) 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：本发明公开了适用紫外激光加工的碱铝硅酸盐柔性玻璃,属于柔性玻璃技术领域,包括紫外吸收剂组合物3.0-5.0％和碱铝硅酸盐玻璃配合料的氧化物95.0-97.0％,紫外吸收剂组合物包括三氧化二铁、氧化钼、氧化铒和硝酸钾,按照重量份数比,三氧化二铁∶氧化钼∶氧化铒∶硝酸钾的比值为(1-3)∶(10-20)∶(4-8)∶(70-80)；碱铝硅酸盐玻璃配合料的氧化物包括以下组分：氧化硅54.0-69.0％、氧化铝5.0-24.0％、一价氧化物13.5-18.0％和二价氧化物4-6％,其中,一价氧化物包括氧化锂0-3.5％、氧化钠13.5-16.0％和氧化钾0-3.5％,二价氧化物包括氧化钙0-4.0％、氧化镁3.0-6.0％和氧化锌0-3.0％,实现了高紫外吸收和高可见光透过,为柔性玻璃在折叠手机和柔性光伏产品中的应用奠定了基础。(The invention discloses alkali aluminosilicate flexible glass suitable for ultraviolet laser processing, which belongs to the technical field of flexible glass and comprises 3.0-5.0% of an ultraviolet absorbent composition and 95.0-97.0% of oxides of alkali aluminosilicate glass batch, wherein the ultraviolet absorbent composition comprises ferric oxide, molybdenum oxide, erbium oxide and potassium nitrate, and the ratio of the ferric oxide to the molybdenum oxide to the erbium oxide to the potassium nitrate is (1-3) to (10-20) to (4-8) to (70-80) according to the weight part ratio; the oxides of the alkali aluminosilicate glass batch materials comprise the following components: 54.0-69.0% of silicon oxide, 5.0-24.0% of aluminum oxide, 13.5-18.0% of monovalent oxide and 4-6% of divalent oxide, wherein the monovalent oxide comprises 0-3.5% of lithium oxide, 13.5-16.0% of sodium oxide and 0-3.5% of potassium oxide, and the divalent oxide comprises 0-4.0% of calcium oxide, 3.0-6.0% of magnesium oxide and 0-3.0% of zinc oxide, so that high ultraviolet absorption and high visible light transmission are realized, and a foundation is laid for the application of the flexible glass in folding mobile phones and flexible photovoltaic products.)

1. The alkali aluminosilicate flexible glass suitable for ultraviolet laser processing is characterized by comprising 3.0-5.0% of ultraviolet absorbent composition and 95.0-97.0% of oxide of alkali aluminosilicate glass batch according to mass percentage.

2. The alkali aluminosilicate flexible glass suitable for UV laser processing according to claim 1, wherein the UV absorber composition comprises, in parts by weight, iron sesquioxide, molybdenum oxide, erbium oxide, and potassium nitrate in a ratio of (1-3) to (10-20) to (4-8) to (70-80).

3. The alkali aluminosilicate flexible glass suitable for ultraviolet laser processing according to claim 1, wherein the oxides of the alkali aluminosilicate glass batch materials comprise, by mass, 54.0-69.0% of silicon oxide, 5.0-24.0% of aluminum oxide, 0-3.5% of lithium oxide, 13.5-16.0% of sodium oxide, 0-3.5% of potassium oxide, 0-4.0% of calcium oxide, 3.0-6.0% of magnesium oxide, and 0-3.0% of zinc oxide.

4. The alkali aluminosilicate flexible glass suitable for ultraviolet laser processing according to claim 1, wherein the flexible glass oxide comprises, by mass, 0.03 to 0.15% of ferric oxide, 0.30 to 1.02% of molybdenum oxide, 0.12 to 0.41% of erbium oxide, 52.13 to 68.0% of silicon oxide, 4.83 to 23.65% of aluminum oxide, 0 to 3.45% of lithium oxide, 13.03 to 15.77% of sodium oxide, 0.99 to 5.27% of potassium oxide, 0 to 3.94% of calcium oxide, 2.90 to 5.91% of magnesium oxide, and 0 to 2.96% of zinc oxide.

5. The alkali aluminosilicate flexible glass suitable for ultraviolet laser processing according to claim 3, wherein the oxides of the alkali aluminosilicate glass batch material comprise the following components in percentage by mass: 54.0% of silicon oxide, 24.0% of aluminum oxide, 2.5% of lithium oxide, 13.5% of sodium oxide, 4.5% of magnesium oxide and 1.5% of zinc oxide.

6. The alkali aluminosilicate flexible glass suitable for ultraviolet laser processing according to claim 3, wherein the oxides of the alkali aluminosilicate glass batch material comprise the following components in percentage by mass: 62.0 percent of silicon oxide, 15.0 percent of aluminum oxide, 15.5 percent of sodium oxide, 1.5 percent of potassium oxide, 3.0 percent of magnesium oxide and 3.0 percent of zinc oxide.

7. The alkali aluminosilicate flexible glass suitable for ultraviolet laser processing according to claim 3, wherein the oxides of the alkali aluminosilicate glass batch material comprise the following components in percentage by mass: 61.0% of silicon oxide, 16.0% of aluminum oxide, 13.5% of sodium oxide, 3.5% of lithium oxide and 6.0% of magnesium oxide.

8. The alkali aluminosilicate flexible glass suitable for ultraviolet laser processing according to claim 3, wherein the oxides of the alkali aluminosilicate glass batch material comprise the following components in percentage by mass: 66.0 percent of silicon oxide, 11.0 percent of aluminum oxide, 16.0 percent of sodium oxide, 1.0 percent of potassium oxide, 1.0 percent of calcium oxide and 5.0 percent of magnesium oxide.

9. The alkali aluminosilicate flexible glass suitable for ultraviolet laser processing according to claim 3, wherein the oxides of the alkali aluminosilicate glass batch material comprise the following components in percentage by mass: 59.0% of silicon oxide, 18.0% of aluminum oxide, 1.5% of lithium oxide, 14.5% of sodium oxide, 1.0% of potassium oxide, 5.0% of magnesium oxide and 1.0% of zinc oxide.

10. The alkali aluminosilicate flexible glass suitable for ultraviolet laser processing according to claim 2, wherein the ratio of ferric oxide, molybdenum oxide, erbium oxide and potassium nitrate is 2: 15: 6: 77 in parts by weight.

Technical Field

The invention belongs to the technical field of flexible glass, and relates to alkali aluminosilicate flexible glass, in particular to alkali aluminosilicate flexible glass suitable for ultraviolet laser processing.

Background

With the development of electronic information display products in the directions of light weight, thinness, large size, flexibility, high resolution and high contrast, 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 the flexible glass is produced.

The flexible glass changes the storage mode of the plate glass, can meet the requirement of a bending winding mode, and realizes a 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 glass has entered into the primary stage of industrialization, in which technologies development and industrial production attempts have been made in flexible glass by corning, asahi glass company, japan electric glass company and german schottky company. In recent years, the four companies mentioned above have made breakthroughs in the thickness of flexible glass, and a plurality of flexible ultrathin glass products are successively released, such as:

1) the 2012 corning company introduced ultra-thin flexible Glass, named Willow Glass, at boston international counseling display society, with a thickness of 100 μm.

2) "SPOOL" flexible glass, which is produced by Asahi glass company of Japan in 2014 by the float process, has a thickness of 40 μm, a width of 1150mm and a length of 100m and can be rolled up into a roll, is a soda-lime silicate glass.

3) The flexible glass technology of Japan electric glass company mastered two technologies of a reintroduction method and an overflow downdraw method, the company has been researched very early, a glass ribbon sample with the thickness of 10 mu m is prepared in a laboratory in 2009, and a G-Leaf product is newly pushed out by FPD China exhibition in 2014, the plate thickness is 35 mu m, and the flexible glass has quite good flexibility.

4) German Schottky company Flexible glass products haveAS87eco, the product thickness is 35-75 μm.

At present, the production method of the flexible glass mainly comprises an overflow method, a slit downdraw method, a redraw method, a chemical thinning method and the like, and for the flexible glass product, the production has great difficulty and the cutting and truncation problem of the product processing process is also faced.

The traditional flat glass cutting and processing mainly utilizes the brittleness of glass and the ductile fracture of a Graves crack, a diamond cutter wheel scratch breaking method is generally adopted, and no matter the cutting and processing are carried out by a high-pressure water jet cutter or infrared CO in the last two decades₂The laser is widely applied and popularized in the aspect of glass cutting. However, in the cutting method for the flexible glass cutting, radioactive damage is likely to occur at the force application point of the flexible glass plate, and a glass processed product with a predetermined shape can hardly be obtained.

The laser processing method has more adjustability and advantages compared with a cutter wheel cutting method and a water jet cutting method, and CO is respectively applied to AdamR₂Laser, nanosecond ultraviolet laser and femtosecond infrared laser were used to perform cutting tests on alkali-free thin glass with a thickness of 110 μm. The results show that CO is affected by thermal stress₂Lasers are not suitable for cutting thin glass; the nanosecond ultraviolet laser can cut the alkali-free glass more accurately, but the cutting speed is lower (8mm/s), and the cutting quality is poorer (edge breakage phenomenon exists); the femtosecond infrared laser processed glass has no heat affected zone and heat diffusion phenomenon, so that the processing has certainty and accuracy, no crack is generated at the cutting edge, the femtosecond infrared laser processed glass is more suitable for scribing on thin glass, and the processing speed is lower (3 mm/s). KrystianL Wlodarczyk et al used picosecond lasers with different wavelengths (1030nm, 515nm, 343nm) to cut very thin glass (flexible glass) with thicknesses of 50 μm and 100 μm, and analyzed the influence of the wavelength, pulse energy, repetition frequency, scanning speed and number of pulses of the laser on the cutting quality. The result shows that the maximum effective speed for cutting 50 mu m glass by 1030nm picosecond laser is 80mm/s, and the maximum effective speed for cutting 100 mu m glass is 74 mm/s; the best cutting quality can be obtained by 343nm picosecond laser; the 515nm picosecond laser can obtain relatively good cutting quality, and simultaneously, 50 mu m glass can be cut at the speed of 100mm/s, and the heat affected zone is ensured to be less than 25 mu m. Through the background information, the cutting efficiency and cutting of picosecond ultraviolet laser on flexible glass are provedThe cross section quality is relatively excellent.

As the flexible OLED (organic light emitting display) industry matured, curved display products began to appear in large numbers. In the foldable mobile phone with Galaxy Fold released in san Tsung 4 in 2019, the flexible OLED is fully developed, and a market opportunity is created for competing organic materials and flexible glass for a cover plate protection material on the surface of a screen of the foldable mobile phone.

Alkali aluminosilicate cover glasses are the most promising glass materials for screen protection glasses. At present, alkali aluminosilicate glass is not rich in components with ultraviolet absorption characteristics, and the ultraviolet absorbing substances for colorless transparent glass are mainly cerium dioxide and titanium dioxide, which are better when used together, but the biggest problems of cerium dioxide and titanium dioxide as ultraviolet absorbers are 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 yellow 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.).

Disclosure of Invention

In order to overcome the defects of the prior art, the invention designs the alkali aluminosilicate flexible glass suitable for ultraviolet laser processing, realizes high ultraviolet absorption and high visible light transmission of the alkali aluminosilicate flexible glass, effectively solves the problem of ultraviolet picosecond laser processing of the flexible glass, and lays a foundation for the application of the flexible glass in folding mobile phones and flexible photovoltaic products.

The invention adopts the specific technical scheme that: the alkali aluminosilicate flexible glass suitable for ultraviolet laser processing comprises, by mass, 3.0-5.0% of an ultraviolet absorbent composition and 95.0-97.0% of an oxide of an alkali aluminosilicate glass batch.

Furthermore, the ultraviolet absorbent composition comprises, by weight, ferric oxide, molybdenum oxide, erbium oxide and potassium nitrate in a ratio of (1-3) to (10-20) to (4-8) to (70-80).

Further, according to the mass percentage, the oxide of the alkali aluminosilicate glass batch comprises 54.0-69.0% of silicon oxide, 5.0-24.0% of aluminum oxide, 0-3.5% of lithium oxide, 13.5-16.0% of sodium oxide, 0-3.5% of potassium oxide, 0-4.0% of calcium oxide, 3.0-6.0% of magnesium oxide and 0-3.0% of zinc oxide.

Further, the flexible glass oxide comprises, by mass, 0.03 to 0.15% of ferric oxide, 0.30 to 1.02% of molybdenum oxide, 0.12 to 0.41% of erbium oxide, 52.13 to 68.0% of silicon oxide, 4.83 to 23.65% of aluminum oxide, 0 to 3.45% of lithium oxide, 13.03 to 15.77% of sodium oxide, 0.99 to 5.27% of potassium oxide, 0 to 3.94% of calcium oxide, 2.90 to 5.91% of magnesium oxide and 0 to 2.96% of zinc oxide.

Further, the oxides of the alkali aluminosilicate glass batch comprise the following components in percentage by mass: 54.0% of silicon oxide, 24.0% of aluminum oxide, 2.5% of lithium oxide, 13.5% of sodium oxide, 4.5% of magnesium oxide and 1.5% of zinc oxide.

Further, the oxides of the alkali aluminosilicate glass batch comprise the following components in percentage by mass: 62.0 percent of silicon oxide, 15.0 percent of aluminum oxide, 15.5 percent of sodium oxide, 1.5 percent of potassium oxide, 3.0 percent of magnesium oxide and 3.0 percent of zinc oxide.

Further, the oxides of the alkali aluminosilicate glass batch comprise the following components in percentage by mass: 61.0% of silicon oxide, 16.0% of aluminum oxide, 13.5% of sodium oxide, 3.5% of lithium oxide and 6.0% of magnesium oxide.

Further, the oxides of the alkali aluminosilicate glass batch comprise the following components in percentage by mass: 66.0 percent of silicon oxide, 11.0 percent of aluminum oxide, 16.0 percent of sodium oxide, 1.0 percent of potassium oxide, 1.0 percent of calcium oxide and 5.0 percent of magnesium oxide.

Further, the oxides of the alkali aluminosilicate glass batch comprise the following components in percentage by mass: 59.0% of silicon oxide, 18.0% of aluminum oxide, 1.5% of lithium oxide, 14.5% of sodium oxide, 1.0% of potassium oxide, 5.0% of magnesium oxide and 1.0% of zinc oxide.

Furthermore, the ratio of ferric oxide to molybdenum oxide to erbium oxide to potassium nitrate is 2: 15: 6: 77 according to the weight portion ratio.

The invention has the beneficial effects that: the ultraviolet absorbent composition is combined with the oxide of the alkali aluminosilicate glass batch, the spectral transmittance is less than or equal to 30 percent and even as low as 15.7 percent, which indicates that about 70 percent and even as high as 84.3 percent of ultraviolet light is absorbed, and the visible light transmittance is more than or equal to 89.5 percent and even as high as 92.6 percent, so that the ultraviolet laser processing can be effectively met, the high-quality melting of the glass can be met, the coloring of the glass can be reduced to the maximum extent, the reduction of the average visible light transmittance can be avoided, the ultraviolet region spectral absorption in the range of 300-.

The ferric oxide is the highest valence state of iron element and has a chemical formula of Fe₂O₃Reddish brown powder with a melting point of 1565 deg.C, iron sesquioxide easily melted in alkali aluminosilicate glass, and when it enters into the glass melt, it is regarded as a glass network outer body and uniformly distributed in the glass, and the iron sesquioxide added into the alkali aluminosilicate glass can coexist with ions with valence +2 and valence +3, i.e. Fe²⁺And Fe³⁺Ion, Fe⁺³The ions appear yellowish green in color in alkali aluminosilicate glass, Fe⁺²The ions exhibit a blue phase, Fe, in alkali aluminosilicate glasses⁺³The ions have strong absorption capacity in the ultraviolet region, so Fe²⁺The glass has a reduced spectral transmittance in the visible range, and Fe²⁺The tinting strength being Fe³⁺More than 10 times of coloring power, so to improve Fe³⁺In alkali aluminosilicate glasses, the proportion of Fe is reduced²⁺In glassThe formation ratio must be maintained under oxidizing conditions, i.e., the REDOX value (REDOX value) of the glass melt is controlled to a positive value.

The UV absorber composition functions as follows:

the molybdenum oxide is transition metal oxide with a chemical formula of MoO₃White crystal with the melting point of 795 ℃ and is easy to melt in alkali aluminosilicate glass, and no coloring harm is caused to the glass. Because the molybdenum element in the molybdenum oxide is in a +6 valence state, the molybdenum oxide has a six-coordination octahedron structure, high electric field intensity and an accumulation effect, can not be tightly connected with non-bridging oxygen in a glass network, can not effectively enter the glass network, and can only form short chain connection by means of self accumulation, in order to enable the molybdenum oxide to exist stably, redundant oxygen needs to be absorbed to form the octahedron which tends to be in a stable ordered structure, therefore, the molybdenum oxide moves to the surface of a glass melt through ion migration in the melting forming process, the molybdenum oxide tends to be more stable, and the surface energy of the molybdenum oxide is reduced. The valence state of the molybdenum oxide in the alkali aluminosilicate glass is relatively stable, and the molybdenum oxide is influenced by the unsaturated state of the electronic outer layer and has certain ultraviolet absorption capacity.

Erbium oxide is a rare earth oxide with the chemical formula of Er₂O₃The erbium oxide is pink powder at normal temperature, is commonly used as a coloring agent and a decoloring agent of optical glass, but has general coloring capability, so that the erbium oxide is widely used as a glass decoloring agent, and the erbium oxide presents a blue color phase in alkali aluminosilicate glass. The 4f orbital of erbium is unsaturated and has ultraviolet absorption ability.

Potassium nitrate is a strong oxidant, with a melting point of 334 deg.C, and above 670 deg.C it will decompose and release oxygen (O)₂) The high oxidation state of ferric oxide, molybdenum oxide and erbium oxide provided to the iron trioxide, molybdenum oxide and erbium oxide avoids the effect of reducing species (carbon or organic carbon) in the glass batch on the valence state of the iron, molybdenum and erbium ions, and thus potassium nitrate is an essential species for maintaining the uv absorber composition in the glass melt in an oxidized state.

The oxidation in the oxides of the alkali aluminosilicate glass batch materials is as follows:

the silicon oxide is a glass network forming body, maintains the necessary substances of the glass network, gives consideration to the physical and chemical properties and the technological properties of the glass, and has the preferred range of 54.0-69.0 percent of mass composition;

the aluminum oxide is a network intermediate, endows the glass with better mechanical property, provides the glass with better toughness, is beneficial to improving the bending fatigue property of the flexible glass, gives consideration to the physical and chemical properties and the process property of the glass, and has the preferred range of 5.0-24.0 percent of mass composition.

The lithium oxide, the sodium oxide and the potassium oxide are external bodies of the glass network, play a role in breaking the network, promote the melting of the glass, reduce the melting forming temperature, have obvious fluxing effect of the lithium oxide, can reduce about 100 ℃, can promote the realization of ion exchange, enable the surface of the glass to generate compressive stress, avoid the expansion of surface micro cracks caused by the bending of the flexible glass, improve the flexibility of the glass, reduce the minimum critical radius of minimum bending, and have the optimal range of mass composition: 0-3.5% of lithium oxide, 13.5-16.0% of sodium oxide and 0-3.5% of potassium oxide.

The calcium oxide, the magnesium oxide and the zinc oxide are beneficial to promoting the melting of the glass, reducing the high-temperature melting temperature, improving and increasing the strain point of the glass, and improving the chemical stability of the glass compared with alkali metal oxides. Preferred ranges of mass composition: 0 to 4.0 percent of calcium oxide, 3.0 to 6.0 percent of magnesium oxide and 0 to 3.0 percent of zinc oxide.

Detailed Description

The present invention will be described in detail with reference to the following specific examples: