阅读说明：本技术 一种高钛高折射率超白玻璃微珠及其制备方法 (High-titanium high-refractive index ultra-white glass bead and preparation method thereof ) 是由 郭宏伟 刘帅 党梦阳 刘磊 李荣悦 王翠翠 白赟 张维祥 于 2020-12-29 设计创作，主要内容包括：本发明公开了一种高钛高折射率超白玻璃微珠及其制备方法,目的在于,克服现有生产技术在熔制玻璃时由于侵蚀耐火材料而引入杂质的缺点,减少了Fe杂质引入量,通过预制钛钡固溶体粉末,然后再高温熔制的工艺,提前让钡和钛形成稳定的化合物,避免高温下钡对窑炉耐火材料的侵蚀,降低50～80％氧化铁对玻璃微珠的影响,按照本发明制备方法得到的高钛高折射率超白玻璃微珠折射率高,色散小,透光率高,白度高,亮度好,玻璃析晶倾向小,化学稳定性优良,且制备工艺操作过程简单,成本低廉,适于工业化生产。(The invention discloses a high-titanium high-refractive index ultra-white glass bead and a preparation method thereof, and aims to overcome the defect that impurities are introduced due to corrosion of refractory materials in the process of melting glass in the prior art, reduce the introduction amount of Fe impurities, lead barium and titanium to form stable compounds in advance by a process of prefabricating titanium barium solid solution powder and then melting at high temperature, avoid corrosion of barium to kiln refractory materials at high temperature, and reduce the influence of 50-80% of ferric oxide on the glass bead.)

1. The preparation method of the high-titanium high-refractive index ultra-white glass bead is characterized by comprising the following steps of:

the method comprises the following steps: preparing titanium barium compound powder:

firstly, mixing 20-50 wt% of titanium dioxide, 25-60 wt% of barium carbonate, 5-20 wt% of barium nitrate and 0.5-10 wt% of aluminum hydroxide to form a mixture;

then, sintering the mixture at 1300-1400 ℃ for 2-4 h, and then cooling in a furnace to obtain a sintered solid;

finally, crushing the cooled sintered solid, and then screening the crushed sintered solid through a standard sieve of 180-100 meshes to obtain barium titanium compound powder;

step two: preparation of glass particles:

firstly, mixing 65-85 wt% of barium titanium compound powder, 8-15 wt% of silicon dioxide, 0.5-5 wt% of strontium carbonate, 1-5 wt% of zinc oxide, 0.1-2 wt% of antimony oxide and 5-10 wt% of calcium carbonate to form a batch;

then melting the batch at 1350-1380 ℃ for 3-5 h, and stirring to obtain glass liquid;

secondly, performing water quenching on the molten glass at room temperature to obtain water-quenched glass particles;

finally, taking out the water-quenched glass particles and drying to obtain glass particles;

step three: preparing glass beads:

firstly, crushing glass particles into powder of 10-100 mu m;

then, balling the powder at 1200-1250 ℃, grading and collecting glass beads after balling;

and finally, adding the collected glass beads into a rotary furnace at 650-660 ℃ for annealing, collecting the glass beads discharged from the rotary furnace and cooling to obtain the high-titanium high-refractive-index ultra-white glass beads.

2. The method for preparing high titanium high refractive index ultra white glass micro beads according to claim 1, wherein the content of ferric oxide in the titanium dioxide, barium carbonate, barium nitrate, aluminum hydroxide, silicon dioxide, strontium carbonate, zinc oxide, antimony oxide and calcium carbonate is less than 50 ppm.

3. The method for preparing high titanium high refractive index ultra white glass microspheres of claim 2, wherein the silica comprises silica sand, and the particle size of the silica sand is less than 150 mesh.

4. The preparation method of the high-titanium high-refractive index ultra-white glass beads according to claim 1, wherein in the first step, titanium dioxide, barium carbonate, barium nitrate and aluminum hydroxide are placed into a V-shaped mixer to be mixed for 40-60 min, and the mixture is placed into a mullite sagger to be sintered.

5. The method for preparing high-titanium high-refractive index ultra-white glass beads according to claim 1, wherein in the second step, the barium titanium compound powder, the silicon dioxide, the strontium carbonate, the zinc oxide, the antimony oxide and the calcium carbonate are put into a QH type mixer to be mixed for 3-5 min, the batch is melted in a kiln and is stirred for 20-40 min at 1350-1380 ℃ by a stirring paddle, and a rotary air dryer is adopted for drying.

6. The method for preparing high titanium high refractive index ultra white glass micro beads according to claim 1, wherein in the third step, the glass particles are crushed in a jet mill, and the powder is treated by balling in a well type gas balling furnace.

7. The method for preparing high titanium high refractive index ultra white glass microspheres of claim 1, wherein the classification treatment in the third step adopts a cyclone separator and a bag dust collector.

8. The method for preparing high titanium high refractive index ultra white glass micro beads according to claim 1, wherein the feeding speed of the rotary furnace in the third step is controlled to be 10Kg/h, and the rotation number of the rotary tube is controlled to be 25-35 circles/min.

9. The method for preparing high titanium high refractive index ultra white glass micro beads according to claim 1, wherein the lining material of the rotary furnace is 310S stainless steel, and the glass micro beads are collected by a heat-resistant stainless steel barrel.

10. A high titanium high refractive index ultra-white glass bead, characterized in that, it is prepared by the method of any one of claims 1 to 9.

Technical Field

The invention relates to a preparation method of glass, in particular to high-titanium high-refractive index ultra-white glass beads and a preparation method thereof.

Background

The glass beads mean solid or hollow glass beads having a diameter of several micrometers to several hundred micrometers. The beads are divided into small beads with the diameter of more than 0.8 mm; beads having a diameter of 0.8mm or less are referred to as microbeads. The glass bead is a novel silicate material and has the characteristics of transparency, adjustable refractive index, directional retro-reflection, smooth surface, good fluidity, electric insulation, stable chemical performance, heat resistance, high mechanical strength and the like.

The high-strength solid micro-beads are mainly used as grinding media, grinding materials for machining, reinforcing fillers and the like, the reflective solid micro-beads are mainly used for traffic signs, art and propaganda advertisements, marine life-saving equipment, performance clothing, directional projection screens and the like, and the hollow micro-beads are mainly used for solid buoyancy materials, ultralow-temperature heat-insulating materials, engineering plastics, solid rocket fuel fillers and the like. The method is widely applied to the industries of light industry, chemical industry, textile, traffic, shipping, precision machining and the like.

The high-refractive-index glass beads are important raw materials for manufacturing the reflective material, have the advantages of transparency, high mechanical strength and the like, can realize the reflective marking effect when being coated on road paint, and particularly can still have good reflective effect in a rainy night environment. The reflective glass beads applied to traffic signs, art propaganda and the like in the market at present are commonly used glass beads with common refractive indexes, and are used as reflective signs or road pavement signs in highway roads and traffic, so that the reflective glass beads with the common refractive indexes have insufficient reflective performance or insufficient reflective distance, especially the visibility in the road traffic at rainy night is greatly reduced, the reflective effect of reflective ground marks on the highway surface is greatly reduced after the reflective ground marks are wet or soaked by rainwater, and the traffic signs on the road surface are difficult to be formed at a distance of twenty-ten meters, so that traffic accidents are easily caused. The all-weather high-refractive-index glass beads have stronger light reflecting effect and light reflecting function, so that the glass beads are more and more paid attention to the market, and the glass beads with high refraction, which need to use all-weather high-refractive-index glass beads, are more and more widely applied. It is difficult to meet the actual needs in the market. Therefore, how to provide the high-refraction glass bead and the preparation method thereof is a practical need of the current glass bead preparation enterprises.

In the existing production of high-refraction glass beads, the corrosion of the bead glass to refractory materials of a kiln is too strong, the production is only suitable for the production in the environment of noble metals such as platinum and the like, the production investment is large, and the energy consumption is high. However, inevitable refractory material erosion can occur in the production of the large melting furnace, and moreover, the erosion effect is more serious because the high-titanium high-refractive-index ultra-white glass beads contain 25-45 wt% of barium carbonate, and the service life of the furnace does not exceed 3 months when the furnace is produced by adopting a tank furnace. After the glass is corroded, Fe in the refractory enters molten glass to generate refractory defects, so that the precursor glass water quenching material is colored.

The role and hazard of iron in glass production mentions that the mineral raw materials (quartz sand, feldspar, dolomite, limestone, etc.) used in glass production usually account for about 80% of the total weight of the batch. Because of different formation reasons, the raw mineral materials contain some mineral impurities such as iron and the like, and on one hand, the impurities and iron impurities brought into the glass through other ways (such as some iron impurities brought when a certain proportion of cullet is added in the glass production and iron impurities falling into the glass after refractory materials are corroded by the molten glass) can pollute the molten glass. Also in high titanium glasses, coloration of the Fe-Ti combination occurs, which gives the glass a dark brown color. It has been demonstrated that: TiO 2₂Has no influence on the coordination number of Fe, and the color tone of the Fe-Fe alloy is Fe³⁺The absorption shifts to the long wave region. Compared with glass beads, if Fe impurities are mixed in the production, the whiteness of the glass beads is affected, the subsequent application is greatly reduced, and the surface color of the reflecting material is not bright white enough.

The discussion of the method for improving the permeability of ceramic tiles mentions that the purity of the raw materials of the transparent ceramics is required to be very high (more than 99.5%).However, it is difficult to obtain this purity from ceramic tile raw materials, which may contain colored metal oxides such as iron oxide, titanium oxide (whiteness), and the like. Conventional glasses generally exhibit a green color in early production because of a small amount of Fe in the glass²⁺Selectively absorbing light of green wave bands by ions; when Fe²⁺When the content of (A) is sufficient, the light transmittance of the glass is also affected. Experiments show that when the transmittance is required to be more than 30%, the content of the ferric oxide in the porcelain blank should not exceed 0.6%, and when the transmittance is required to be more than 40%, the content of the ferric oxide should not exceed 0.35%. It is seen that the coexistence of Fe ions and titanium ions has a great influence on the whiteness and transmittance of ceramics and glass.

Disclosure of Invention

In order to solve the problems in the prior art, the invention provides the high-titanium high-refractive-index ultra-white glass bead and the preparation method thereof, which overcome the defect that impurities are introduced due to corrosion of refractory materials when glass is melted in the prior art, reduce the introduction amount of Fe impurities, and obtain the high-titanium high-refractive-index ultra-white glass bead with high refractive index, small dispersion, high light transmittance, high whiteness, good brightness, small glass crystallization tendency, excellent chemical stability, simple preparation process and operation process and low cost, and is suitable for industrial production.

In order to achieve the above object, the present invention provides a method for preparing high titanium high refractive index ultra-white glass beads, comprising the steps of:

the method comprises the following steps: preparing titanium barium compound powder:

firstly, mixing 20-50 wt% of titanium dioxide, 25-60 wt% of barium carbonate, 5-20 wt% of barium nitrate and 0.5-10 wt% of aluminum hydroxide to form a mixture;

then, sintering the mixture at 1300-1400 ℃ for 2-4 h, and then cooling in a furnace to obtain a sintered solid;

finally, crushing the cooled sintered solid, and then screening the crushed sintered solid through a standard sieve of 180-100 meshes to obtain barium titanium compound powder;

step two: preparation of glass particles:

firstly, mixing 65-85 wt% of barium titanium compound powder, 8-15 wt% of silicon dioxide, 0.5-5 wt% of strontium carbonate, 1-5 wt% of zinc oxide, 0.1-2 wt% of antimony oxide and 5-10 wt% of calcium carbonate to form a batch;

then melting the batch at 1350-1380 ℃ for 3-5 h, and stirring to obtain glass liquid;

secondly, performing water quenching on the molten glass at room temperature to obtain water-quenched glass particles;

finally, taking out the water-quenched glass particles and drying to obtain glass particles;

step three: preparing glass beads:

firstly, crushing glass particles into powder of 10-100 mu m;

then, balling the powder at 1200-1250 ℃, grading and collecting glass beads after balling;

and finally, adding the collected glass beads into a rotary furnace at 650-660 ℃ for annealing, collecting the glass beads discharged from the rotary furnace and cooling to obtain the high-titanium high-refractive-index ultra-white glass beads.

Preferably, the content of ferric oxide in the titanium dioxide, barium carbonate, barium nitrate, aluminum hydroxide, silicon dioxide, strontium carbonate, zinc oxide, antimony oxide and calcium carbonate is less than 50 ppm.

Preferably, the silica comprises quartz sand, and the particle size of the quartz sand is less than 150 meshes.

Preferably, in the first step, titanium dioxide, barium carbonate, barium nitrate and aluminum hydroxide are placed into a V-shaped mixer to be mixed for 40-60 min, and the mixture is placed into a mullite sagger to be sintered.

Preferably, in the second step, the barium titanium compound powder, the silicon dioxide, the strontium carbonate, the zinc oxide, the antimony oxide and the calcium carbonate are placed into a QH type mixer to be mixed for 3-5 min, the batch materials are melted in a kiln and are stirred for 20-40 min at 1350-1380 ℃ by a stirring paddle, and a rotary air dryer is adopted for drying.

Preferably, in the third step, the glass particles are crushed in a jet mill, and the powder is pelletized in a well-type gas pelletizing furnace.

Preferably, the classification treatment in the third step adopts a cyclone separator and a bag dust collector.

Preferably, the feeding speed of the rotary furnace in the third step is controlled to be 10Kg/h, and the revolution of the rotary pipe is controlled to be 25-35 circles/min.

Preferably, the lining material of the rotary furnace is 310S stainless steel, and the glass beads are collected by a barrel made of heat-resistant stainless steel.

The invention also provides the high-titanium high-refractive index ultra-white glass bead prepared by the preparation method.

Compared with the prior art, the preparation method has the advantages that the barium and the titanium form stable compounds in advance through the process of prefabricating the titanium barium solid solution powder and then melting at high temperature, the corrosion of the barium to a kiln refractory material at high temperature is avoided, and the influence of 50-80% of ferric oxide on the glass beads is reduced.

Drawings

FIG. 1 is a morphology under an electron microscope of a high titanium high refractive index ultra-white glass bead prepared in example 1 of the present invention;

FIG. 2 is a graph of differential thermal data measured by a simultaneous integrated thermal analyzer of the high titanium high refractive index ultra-white glass microspheres prepared in example 1 of the present invention;

FIG. 3 is an XRD diffraction data graph of the high titanium high refractive index ultra-white glass microspheres prepared in example 1 of the present invention crystallized for 1 hour at a crystallization temperature.

Detailed Description

The present invention will be further explained with reference to specific examples, which are intended to form part of the present application, but not all of the present application. 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 application.

The invention provides a preparation method of high-titanium high-refractive index ultra-white glass beads, which comprises the following steps:

the method comprises the following steps: preparing titanium barium compound powder:

firstly, mixing 20-50 wt% of titanium dioxide, 25-60 wt% of barium carbonate, 5-20 wt% of barium nitrate and 0.5-10 wt% of aluminum hydroxide to form a mixture; preferably, the titanium dioxide, the barium carbonate, the barium nitrate and the aluminum hydroxide are placed into a V-shaped mixer to be mixed for 40-60 min;

then, sintering the mixture at 1300-1400 ℃ for 2-4 h, and then cooling in a furnace to obtain a sintered solid; preferably, the mixture is placed into a mullite sagger for sintering;

finally, crushing the cooled sintered solid, and then screening the crushed sintered solid through a standard sieve of 180-100 meshes to obtain barium titanium compound powder;

step two: preparation of glass particles:

firstly, mixing 65-85 wt% of barium titanium compound powder, 8-15 wt% of silicon dioxide, 0.5-5 wt% of strontium carbonate, 1-5 wt% of zinc oxide, 0.1-2 wt% of antimony oxide and 5-10 wt% of calcium carbonate to form a batch; preferably, the titanium barium compound powder, the silicon dioxide, the strontium carbonate, the zinc oxide, the antimony oxide and the calcium carbonate are put into a QH type mixer to be mixed for 3-5 min;

then melting the batch at 1350-1380 ℃ for 3-5 h, and stirring to obtain glass liquid; preferably, the batch materials are melted in a kiln and stirred for 20-40 min at 1350-1380 ℃ by a stirring paddle;

secondly, performing water quenching on the molten glass at room temperature to obtain water-quenched glass particles; preferably, the water quenching is performed in deionized water;

finally, taking out the water-quenched glass particles and drying to obtain glass particles; preferably, the drying adopts a rotary air dryer;

step three: preparing glass beads:

firstly, crushing glass particles into powder of 10-100 mu m; preferably, the glass particles are comminuted in a jet mill;

then, balling the powder at 1200-1250 ℃, grading and collecting glass beads after balling; preferably, the powder is pelletized in a well type gas pelletizing furnace; the grading treatment adopts a cyclone separator and a bag dust collector;

and finally, adding the collected glass beads into a rotary furnace at 650-660 ℃ for annealing, collecting the glass beads discharged from the rotary furnace and cooling to obtain the high-titanium high-refractive-index ultra-white glass beads. Preferably, the feeding speed of the rotary furnace is controlled to be 10Kg/h, and the revolution of the rotary pipe is controlled to be 25-35 circles/min; the lining material of the rotary furnace is 310S stainless steel, and the glass beads are collected by a barrel made of heat-resistant stainless steel.

Preferably, the contents of ferric oxide in titanium dioxide, barium carbonate, barium nitrate, aluminum hydroxide, silicon dioxide, strontium carbonate, zinc oxide, antimony oxide and calcium carbonate are all less than 50ppm, the silicon dioxide comprises quartz sand, and the particle size of the quartz sand is less than 150 meshes, namely, the quartz sand can completely pass through a 150-mesh standard sieve.

Example 1:

step one, preparing titanium barium compound powder:

(1) respectively weighing 35.5 wt% of titanium dioxide, 50.4 wt% of barium carbonate, 13.1 wt% of barium nitrate and 1 wt% of aluminum hydroxide according to mass percentage;

(2) putting weighed titanium dioxide, barium carbonate, barium nitrate and aluminum hydroxide into a V-shaped mixer to be mixed for 60min to form a mixture;

(3) placing the mixture into a mullite sagger, sintering at 1400 ℃ for 4h, and then placing into a furnace for cooling;

(4) crushing the cooled sintered solid, and sieving the crushed solid through a 150-mesh standard sieve to obtain barium titanium compound powder;

step two, preparing high-titanium high-refractive-index glass particles:

(1) 79.09 wt% of the prepared barium titanium compound powder, 10.8 wt% of silicon dioxide, 0.71 wt% of strontium carbonate, 2.93 wt% of zinc oxide, 0.12 wt% of antimony oxide and 6.35 wt% of calcium carbonate are weighed according to mass percentage respectively;

(2) putting the weighed raw materials into a QH type mixer, and mixing for 5min to form a batch;

(3) adding the uniformly mixed batch materials into a kiln, melting for 5h at 1380 ℃, then dropping a stirring paddle, and stirring for 40min at 1380 ℃;

(4) pouring the molten glass liquid into water at room temperature to obtain water-quenched glass particles;

(5) fishing out the water quenching material, and drying by using a rotary air dryer to obtain high-titanium high-refractive-index glass particles;

thirdly, preparing the high-titanium high-refractive index ultra-white glass beads:

(1) putting the obtained high-titanium high-refractive-index glass particles into a jet mill to be milled into powder of 10-100 mu m;

(2) putting the prepared powder into a 1200 ℃ well type gas balling furnace for balling;

(3) grading the prepared glass beads by using a cyclone separator and a bag dust collector, and collecting to obtain the high-titanium high-refractive-index glass beads;

(4) adding the obtained high-titanium high-refractive-index glass beads into an electric heating rotary furnace at 650 ℃, wherein the feeding speed is controlled to be 10 Kg/h; the revolution of the rotary tube is 34.4 circles/min, the glass beads coming out of the rotary furnace are collected and barreled and cooled to obtain the high-titanium high-refractive index ultra-white glass beads.

The brightness of the sample was measured by NFZ-6 retroreflective marker measuring apparatus at a light source voltage of 5.78V to obtain a brightness of 65cd 1x^-1m^-2(ii) a The refractive index of the resulting glass microspheres was measured to be 1.932 using an WYV-S digital V-prism refractometer.

The appearance of the high-titanium high-refractive index ultra-white glass bead prepared in example 1 under an electron microscope is shown in fig. 1, and the glass bead prepared in fig. 1 has no impurities on the surface and is bright.

The refractive data of the high titanium and high refractive index ultra-white glass beads prepared in example 1 were measured by a simultaneous comprehensive thermal analyzer, and the results are shown in fig. 2. fig. 2 shows that the glass beads have a small crystallization behavior, a crystallization peak at 858 ℃ but a small tendency, and a melting point of 1200 ℃.

The high titanium high refractive index ultra-white glass microspheres prepared in example 1 were crystallized at about 850 ℃ as determined by differential thermal data, and XRD diffraction tests were performed after crystallization was performed at the 850 ℃ crystallization temperature for 1 hour, the XRD diffraction data are shown in FIG. 3, and Ba could be generated from FIG. 3 if the Ba is retained at this temperature for too long₂(Ti0)Si₂O₇。

Example 2:

step one, preparing titanium barium compound powder:

(1) respectively weighing 35.5 wt% of titanium dioxide, 50.5 wt% of barium carbonate, 13 wt% of barium nitrate and 1 wt% of aluminum hydroxide according to mass percentage;

(2) putting weighed titanium dioxide, barium carbonate, barium nitrate and aluminum hydroxide into a V-shaped mixer to be mixed for 60min to form a mixture;

(3) placing the mixture into a mullite sagger, sintering at 1400 ℃ for 4h, and then placing into a furnace for cooling;

(4) crushing the cooled sintered solid, and sieving the crushed solid through a 150-mesh standard sieve to obtain barium titanium compound powder;

step two, preparing high-titanium high-refractive-index glass particles:

(1) 79.13 wt% of the prepared barium titanium compound powder, 10.8 wt% of silicon dioxide, 0.71 wt% of strontium carbonate, 2.9 wt% of zinc oxide, 0.12 t% of antimony oxide and 6.34 wt% of calcium carbonate are weighed according to mass percentage respectively;

(2) putting the weighed raw materials into a QH type mixer, and mixing for 5min to form a batch;

(3) adding the uniformly mixed batch materials into a kiln, melting for 5h at 1380 ℃, then dropping a stirring paddle, and stirring for 40min at 1380 ℃;

(4) pouring the molten glass liquid into water at room temperature to obtain water-quenched glass particles;

(5) fishing out the water quenching material, and drying by using a rotary air dryer to obtain high-titanium high-refractive-index glass particles;

thirdly, preparing the high-titanium high-refractive index ultra-white glass beads:

(1) putting the obtained high-titanium high-refractive-index glass particles into a jet mill to be milled into powder of 10-100 mu m;

(2) putting the prepared powder into a 1200 ℃ well type gas balling furnace for balling;

(3) and grading the prepared glass beads by using a cyclone separator and a bag dust collector, and collecting to obtain the high-titanium high-refractive-index glass beads.

(4) Adding the obtained high-titanium high-refractive-index glass beads into an electric heating rotary furnace at 650 ℃, wherein the feeding speed is controlled to be 10 Kg/h; the revolution of the rotary tube is 34.8 circles/min, the glass beads coming out of the rotary furnace are collected and barreled and cooled to obtain the high-titanium high-refractive index ultra-white glass beads.

The brightness of the sample was measured by NFZ-6 retroreflective marker measuring apparatus at a light source voltage of 5.78V and was measured to be 66cd 1x^-1m^-2(ii) a The refractive index of the resulting glass microspheres was measured to be 1.934 using an WYV-S digital V-prism refractometer.

Example 3:

step one, preparing titanium barium compound powder:

(1) respectively weighing 35.4 wt% of titanium dioxide, 50.5 wt% of barium carbonate, 13 wt% of barium nitrate and 1.1 wt% of aluminum hydroxide according to mass percentage;

(2) putting weighed titanium dioxide, barium carbonate, barium nitrate and aluminum hydroxide into a V-shaped mixer to be mixed for 50min to form a mixture;

(3) placing the mixture into a mullite sagger, sintering at 1400 ℃ for 3h, and then placing into a furnace for cooling;

(4) crushing the cooled sintered solid, and sieving the crushed solid through a 150-mesh standard sieve to obtain barium titanium compound powder;

step two, preparing high-titanium high-refractive-index glass particles:

(1) 79.09 wt% of the prepared barium titanium compound powder, 10.8 wt% of silicon dioxide, 0.71 wt% of strontium carbonate, 2.91 wt% of zinc oxide, 0.12 wt% of antimony oxide and 6.35 wt% of calcium carbonate are weighed according to mass percentage;

(2) putting the weighed raw materials into a QH type mixer to mix for 4min to form a batch;

(3) adding the uniformly mixed batch materials into a kiln, melting for 4h at 1380 ℃, then dropping a stirring paddle, and stirring for 30min at 1380 ℃;

(4) pouring the molten glass liquid into water at room temperature to obtain water-quenched glass particles;

(5) fishing out the water quenching material, and drying by using a rotary air dryer to obtain high-titanium high-refractive-index glass particles;

thirdly, preparing the high-titanium high-refractive index ultra-white glass beads:

(1) putting the obtained high-titanium high-refractive-index glass particles into a jet mill to be milled into powder of 10-100 mu m;

(2) putting the prepared powder into a 1200 ℃ well type gas balling furnace for balling;

(3) grading the prepared glass beads by using a cyclone separator and a bag dust collector, and collecting to obtain the high-titanium high-refractive-index glass beads;

(4) adding the obtained high-titanium high-refractive-index glass beads into an electric heating rotary furnace at 650 ℃, wherein the feeding speed is controlled to be 10 Kg/h; the revolution of the rotary tube is 35.2 circles/min, the glass beads coming out of the rotary furnace are collected and barreled and cooled to obtain the high-titanium high-refractive index ultra-white glass beads.

The brightness of the sample was measured by NFZ-6 retroreflective marker measuring apparatus at a light source voltage of 5.78V and was measured to be 64cd x 1x^-1m^-2(ii) a The refractive index of the resulting glass microspheres was measured to be 1.932 using an WYV-S digital V-prism refractometer.

Example 4:

step one, preparing titanium barium compound powder:

(1) respectively weighing 35.4 wt% of titanium dioxide, 50.5 wt% of barium carbonate, 13.1 wt% of barium nitrate and 1.1 wt% of aluminum hydroxide according to mass percentage;

(2) putting weighed titanium dioxide, barium carbonate, barium nitrate and aluminum hydroxide into a V-shaped mixer to be mixed for 40min to form a mixture;

(3) placing the mixture into a mullite sagger, sintering at 1400 ℃ for 2, and then placing into a furnace for cooling;

(4) crushing the cooled sintered solid, and sieving the crushed solid through a 150-mesh standard sieve to obtain barium titanium compound powder;

step two, preparing high-titanium high-refractive-index glass particles:

(1) 79.13 wt% of the prepared barium titanium compound powder, 10.8 wt% of silicon dioxide, 0.72 wt% of strontium carbonate, 2.91 wt% of zinc oxide, 0.12 wt% of antimony oxide and 6.34 wt% of calcium carbonate are weighed according to mass percentage respectively;

(2) putting the weighed raw materials into a QH type mixer, and mixing for 5min to form a batch;

(3) adding the uniformly mixed batch materials into a kiln, melting at 1380 ℃ for 3h, dropping a stirring paddle, and stirring at 1380 ℃ for 20 min;

(4) pouring the molten glass liquid into water at room temperature to obtain water-quenched glass particles;

(5) fishing out the water quenching material, and drying by using a rotary air dryer to obtain high-titanium high-refractive-index glass particles;

thirdly, preparing the high-titanium high-refractive index ultra-white glass beads:

(1) putting the obtained high-titanium high-refractive-index glass particles into a jet mill to be milled into powder of 10-100 mu m;

(2) putting the prepared powder into a 1200 ℃ well type gas balling furnace for balling;

(3) grading the prepared glass beads by using a cyclone separator and a bag dust collector, and collecting to obtain the high-titanium high-refractive-index glass beads;

(4) adding the obtained high-titanium high-refractive-index glass beads into an electric heating rotary furnace at 650 ℃, wherein the feeding speed is controlled to be 10 Kg/h; the revolution of the rotary tube is 34.3 circles/min, the glass beads coming out of the rotary furnace are collected and barreled and cooled to obtain the high-titanium high-refractive index ultra-white glass beads.

The brightness of the sample was measured by NFZ-6 retroreflective marker measuring apparatus at a light source voltage of 5.78V and was measured to be 66cd 1x^-1m^-2(ii) a The refractive index of the resulting glass microspheres was measured to be 1.931 using an WYV-S digital V-prism refractometer.

Example 5:

step one, preparing titanium barium compound powder:

(1) respectively weighing 35.5 wt% of titanium dioxide, 50.5 wt% of barium carbonate, 12.9 wt% of barium nitrate and 1.1 wt% of aluminum hydroxide according to mass percentage;

(2) putting weighed titanium dioxide, barium carbonate, barium nitrate and aluminum hydroxide into a V-shaped mixer to be mixed for 40min to form a mixture;

(3) placing the mixture into a mullite sagger, sintering at 1400 ℃ for 2h, and then placing into a furnace for cooling;

(4) crushing the cooled sintered solid, and sieving the crushed solid through a 150-mesh standard sieve to obtain barium titanium compound powder;

step two, preparing high-titanium high-refractive-index glass particles:

(1) 79.1 weight percent of prepared barium titanium compound powder, 10.8 weight percent of silicon dioxide, 0.72 weight percent of strontium carbonate, 2.92 weight percent of zinc oxide, 0.12 weight percent of antimony oxide and 6.34 weight percent of calcium carbonate are respectively weighed according to the mass percentage;

(2) putting the weighed raw materials into a QH type mixer, and mixing for 3min to form a batch;

(3) adding the uniformly mixed batch materials into a kiln, melting at 1380 ℃ for 3h, dropping a stirring paddle, and stirring at 1380 ℃ for 20 min;

(4) pouring the molten glass liquid into water at room temperature to obtain water-quenched glass particles;

(5) fishing out the water quenching material, and drying by using a rotary air dryer to obtain high-titanium high-refractive-index glass particles;

thirdly, preparing the high-titanium high-refractive index ultra-white glass beads:

(1) putting the obtained high-titanium high-refractive-index glass particles into a jet mill to be milled into powder of 10-100 mu m;

(2) putting the prepared powder into a 1200 ℃ well type gas balling furnace for balling;

(3) grading the prepared glass beads by using a cyclone separator and a bag dust collector, and collecting to obtain the high-titanium high-refractive-index glass beads;

(4) adding the obtained high-titanium high-refractive-index glass beads into an electric heating rotary furnace at 650 ℃, wherein the feeding speed is controlled to be 10 Kg/h; the revolution of the rotary tube is 34.5 circles/min, the glass beads coming out of the rotary furnace are collected and barreled and cooled to obtain the high-titanium high-refractive index ultra-white glass beads.

The brightness of the sample was measured by NFZ-6 retroreflective marker measuring apparatus at a light source voltage of 5.78V and was measured to be 66cd 1x^-1m^-2(ii) a The refractive index of the resulting glass microspheres was measured to be 1.929 using an WYV-S digital V-prism refractometer.

Example 6:

step one, preparing titanium barium compound powder:

(1) firstly, respectively weighing 35.4 wt% of titanium dioxide, 50.5 wt% of barium carbonate, 12.9 wt% of barium nitrate and 1.1 wt% of aluminum hydroxide according to mass percentage;

(2) putting weighed titanium dioxide, barium carbonate, barium nitrate and aluminum hydroxide into a V-shaped mixer to be mixed for 50min to form a mixture;

(3) placing the mixture into a mullite sagger, sintering at 1400 ℃ for 3h, and then placing into a furnace for cooling;

(4) crushing the cooled sintered solid, and sieving the crushed solid through a 150-mesh standard sieve to obtain barium titanium compound powder;

step two, preparing high-titanium high-refractive-index glass particles:

(1) 79.11 weight percent of prepared barium titanium compound powder, 10.8 weight percent of silicon dioxide, 0.72 weight percent of strontium carbonate, 2.92 weight percent of zinc oxide, 0.12 weight percent of antimony oxide and 6.34 weight percent of calcium carbonate are respectively weighed according to the mass percentage;

(2) putting the weighed raw materials into a QH type mixer to mix for 4min to form a batch;

(3) adding the uniformly mixed batch materials into a kiln, melting for 4h at 1380 ℃, then dropping a stirring paddle, and stirring for 30min at 1380 ℃;

(4) pouring the molten glass liquid into water at room temperature to obtain water-quenched glass particles;

(5) fishing out the water quenching material, and drying by using a rotary air dryer to obtain high-titanium high-refractive-index glass particles;

thirdly, preparing the high-titanium high-refractive index ultra-white glass beads:

(1) putting the obtained high-titanium high-refractive-index glass particles into a jet mill to be milled into powder of 10-100 mu m;

(2) putting the prepared powder into a 1200 ℃ well type gas balling furnace for balling;

(3) grading the prepared glass beads by using a cyclone separator and a bag dust collector, and collecting to obtain the high-titanium high-refractive-index glass beads;

(4) adding the obtained high-titanium high-refractive-index glass beads into an electric heating rotary furnace at 650 ℃, wherein the feeding speed is controlled to be 10 Kg/h; the revolution of the rotary tube is 35.5 circles/min, the glass beads coming out of the rotary furnace are collected and barreled and cooled to obtain the high-titanium high-refractive index ultra-white glass beads.

The brightness of the sample was measured by NFZ-6 retroreflective marker measuring apparatus at a light source voltage of 5.78V and was measured to be 67cd 1x^-1m^-2(ii) a The refractive index of the resulting glass microspheres was measured to be 1.934 using an WYV-S digital V-prism refractometer.

Example 7:

step one, preparing titanium barium compound powder:

(1) firstly, respectively weighing 20 wt% of titanium dioxide, 60 wt% of barium carbonate, 10 wt% of barium nitrate and 10 wt% of aluminum hydroxide according to mass percentage;

(2) putting weighed titanium dioxide, barium carbonate, barium nitrate and aluminum hydroxide into a V-shaped mixer to be mixed for 40min to form a mixture;

(3) placing the mixture into a mullite sagger, sintering at 1300 ℃ for 2 hours, and then putting into a furnace for cooling;

(4) crushing the cooled sintered solid, and sieving the crushed solid through a 100-mesh standard sieve to obtain barium titanium compound powder;

step two, preparing high-titanium high-refractive-index glass particles:

(1) respectively weighing 65 wt% of the prepared barium titanium compound powder, 15 wt% of silicon dioxide, 5 wt% of strontium carbonate, 5 wt% of zinc oxide, 2 wt% of antimony oxide and 8 wt% of calcium carbonate according to mass percentage;

(2) putting the weighed raw materials into a QH type mixer, and mixing for 3min to form a batch;

(3) adding the uniformly mixed batch materials into a kiln, melting at 1350 ℃ for 3h, dropping a stirring paddle, and stirring at 1350 ℃ for 20 min;

(4) pouring the molten glass liquid into water at room temperature to obtain water-quenched glass particles;

(5) fishing out the water quenching material, and drying by using a rotary air dryer to obtain high-titanium high-refractive-index glass particles;

thirdly, preparing the high-titanium high-refractive index ultra-white glass beads:

(1) putting the obtained high-titanium high-refractive-index glass particles into a jet mill to be milled into powder of 10-100 mu m;

(2) putting the prepared powder into a 1250 ℃ well type gas balling furnace for balling;

(3) grading the prepared glass beads by using a cyclone separator and a bag dust collector, and collecting to obtain the high-titanium high-refractive-index glass beads;

(4) adding the obtained high-titanium high-refractive-index glass microspheres into an electric heating rotary furnace at 660 ℃, wherein the feeding speed is controlled to be 10 Kg/h; and (4) rotating the rotary tube at the speed of 25 circles/min, collecting the glass microspheres discharged from the rotary furnace, barreling and cooling to obtain the high-titanium high-refractive-index ultra-white glass microspheres.

Example 8:

step one, preparing titanium barium compound powder:

(1) firstly, respectively weighing 50 wt% of titanium dioxide, 25 wt% of barium carbonate, 20 wt% of barium nitrate and 5 wt% of aluminum hydroxide according to mass percentage;

(2) putting weighed titanium dioxide, barium carbonate, barium nitrate and aluminum hydroxide into a V-shaped mixer to be mixed for 60min to form a mixture;

(3) placing the mixture into a mullite sagger, sintering at 1350 ℃ for 2.5h, and then placing into a furnace for cooling;

(4) crushing the cooled sintered solid, and sieving the crushed solid through a 180-mesh standard sieve to obtain barium titanium compound powder;

step two, preparing high-titanium high-refractive-index glass particles:

(1) respectively weighing 85 wt% of prepared barium titanium compound powder, 8 wt% of silicon dioxide, 0.5 wt% of strontium carbonate, 1 wt% of zinc oxide, 0.1 wt% of antimony oxide and 5.4 wt% of calcium carbonate according to mass percentage;

(2) putting the weighed raw materials into a QH type mixer, and mixing for 5min to form a batch;

(3) adding the uniformly mixed batch materials into a kiln, melting at 1370 ℃ for 4.5h, dropping a stirring paddle, and stirring at 1370 ℃ for 40 min;

(4) pouring the molten glass liquid into water at room temperature to obtain water-quenched glass particles;

(5) fishing out the water quenching material, and drying by using a rotary air dryer to obtain high-titanium high-refractive-index glass particles;

thirdly, preparing the high-titanium high-refractive index ultra-white glass beads:

(1) putting the obtained high-titanium high-refractive-index glass particles into a jet mill to be milled into powder of 10-100 mu m;

(2) putting the prepared powder into a 1250 ℃ well type gas balling furnace for balling;

(3) grading the prepared glass beads by using a cyclone separator and a bag dust collector, and collecting to obtain the high-titanium high-refractive-index glass beads;

(4) adding the obtained high-titanium high-refractive-index glass microspheres into an electric heating rotary furnace at 660 ℃, wherein the feeding speed is controlled to be 10 Kg/h; and (4) rotating the rotary tube at 35 circles/min, collecting the glass microspheres discharged from the rotary furnace, barreling and cooling to obtain the high-titanium high-refractive-index ultra-white glass microspheres.

Example 9:

step one, preparing titanium barium compound powder:

(1) firstly, 39.5 wt% of titanium dioxide, 55 wt% of barium carbonate, 5 wt% of barium nitrate and 0.5 wt% of aluminum hydroxide are respectively weighed according to the mass percentage;

(2) putting weighed titanium dioxide, barium carbonate, barium nitrate and aluminum hydroxide into a V-shaped mixer to be mixed for 45min to form a mixture;

(3) placing the mixture into a mullite sagger, sintering at 1360 ℃ for 3h, and then cooling in a furnace;

(4) crushing the cooled sintered solid, and sieving the crushed solid through a standard sieve of 140 meshes to obtain titanium-barium compound powder;

step two, preparing high-titanium high-refractive-index glass particles:

(1) respectively weighing 71 wt% of prepared barium titanium compound powder, 10 wt% of silicon dioxide, 3 wt% of strontium carbonate, 4 wt% of zinc oxide, 2 wt% of antimony oxide and 10 wt% of calcium carbonate according to mass percentage;

(2) putting the weighed raw materials into a QH type mixer to mix for 4min to form a batch;

(3) adding the uniformly mixed batch materials into a kiln, melting at 1370 ℃ for 3.5h, dropping a stirring paddle, and stirring at 1370 ℃ for 30 min;

(4) pouring the molten glass liquid into water at room temperature to obtain water-quenched glass particles;

(5) fishing out the water quenching material, and drying by using a rotary air dryer to obtain high-titanium high-refractive-index glass particles;

thirdly, preparing the high-titanium high-refractive index ultra-white glass beads:

(1) putting the obtained high-titanium high-refractive-index glass particles into a jet mill to be milled into powder of 10-100 mu m;

(2) putting the prepared powder into a 1230 ℃ well type gas balling furnace for balling;

(3) grading the prepared glass beads by using a cyclone separator and a bag dust collector, and collecting to obtain the high-titanium high-refractive-index glass beads;

(4) adding the obtained high-titanium high-refractive-index glass beads into an electric heating rotary furnace at 655 ℃, wherein the feeding speed is controlled to be 10 Kg/h; and (4) rotating the rotary tube at the speed of 25 circles/min, collecting the glass microspheres discharged from the rotary furnace, barreling and cooling to obtain the high-titanium high-refractive-index ultra-white glass microspheres.

The high-titanium high-refractive index ultra-white glass bead prepared by the invention has the advantages of high refractive index, small dispersion, high light transmittance, high whiteness, good brightness, small glass crystallization tendency and the like. And the preparation process has simple operation process and low cost and is suitable for industrial production. The high-titanium high-refractive index ultra-white glass microspheres prepared by the preparation method can be used for reflective cloth, reflective films, traffic signs and the like.

Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.