阅读说明：本技术 低共熔点玻璃粉及其制备方法和应用 (Eutectic point glass powder and preparation method and application thereof ) 是由 毛智勇 徐达 陈静静 王达健 王伟 于 2020-06-02 设计创作，主要内容包括：本发明公开了一种低共熔点玻璃粉及其制备方法和应用,低共熔点玻璃粉按质量百分比计,包括：20～70wt％的Bi-(2)O-(3)、20～70wt％的B-(2)O-(3)、5～20wt％的ZnO和0～10wt％的调节组分,所述调节组分为BaO、SiO-(2)、Al-(2)O-(3)、MgO、Na-(2)O、Li-(2)O和CaO中的一种或一种以上任意比例的混合物。本发明的低共熔点玻璃粉具有较低的玻璃共熔温度,且与远红光荧光粉混合后,可以在600～700℃范围内共熔,大大降低实际应用中熔融难度,减少能耗。(The invention discloses a eutectic point glass powder and a preparation method and application thereof, wherein the eutectic point glass powder comprises the following components in percentage by mass: 20 to 70 wt% of Bi 2 O 3 20 to 70 wt% of B 2 O 3 5-20 wt% of ZnO and 0-10 wt% of regulating component, wherein the regulating component is BaO and SiO 2 、Al 2 O 3 、MgO、Na 2 O、Li 2 One or a mixture of more than one of O and CaO in any proportion. The eutectic point glass powder has lower glass eutectic temperature, and can be mixed with far-infrared fluorescent powderThe eutectic melting is carried out within the range of 600-700 ℃, so that the melting difficulty in practical application is greatly reduced, and the energy consumption is reduced.)

1. The eutectic point glass powder is characterized by comprising the following components in percentage by mass: 20 to 70 wt% of Bi₂O₃20 to 70 wt% of B₂O₃5-20 wt% of ZnO and 0-10 wt% of regulating component, wherein the regulating component is BaO and SiO₂、Al₂O₃、MgO、Na₂O、Li₂One or a mixture of more than one of O and CaO in any proportion.

2. The eutectic glass frit of claim 1, wherein the Bi is present in mass percent₂O₃21 to 63 wt%, of the component B₂O₃21-63 wt%, ZnO 8-12 wt%, and the adjusting component 4-6 wt%.

3. The eutectic glass powder according to claim 2, wherein the raw materials of the eutectic glass powder are one of the following:

the regulating components are BaO and Li₂O and Al₂O₃The mixture of (A) and (B), in parts by mass, the BaO and Li₂O and Al₂O₃The ratio of (4-5): (0.01-0.1): (0.01 to 0.1) of the above Bi₂O₃And B₂O₃The ratio of (1.9-2.1): 1;

the adjusting components are BaO and SiO₂And Na₂A mixture of O, the BaO and the SiO are calculated according to the mass portion₂And Na₂The ratio of O is (4-5): (0.01-0.1): (0.01 to 0.1) of the above Bi₂O₃And B₂O₃The ratio of (1.9-2.1): 1;

the regulating component is a mixture of BaO, MgO and CaOThe composition comprises the following components in parts by weight, wherein the ratio of BaO to MgO to CaO is (4-5): (0.01-0.1): (0.01 to 0.1) of the above Bi₂O₃And B₂O₃The ratio of (1.9-2.1): 1;

the adjusting component is a mixture of BaO, MgO and CaO, and the ratio of BaO, MgO and CaO is (4-5) in parts by mass: (0.01-0.1): (0.01 to 0.1) of the above Bi₂O₃And B₂O₃The ratio of (1) to (0.9): 1;

the adjusting component is a mixture of BaO, MgO and CaO, and the ratio of BaO, MgO and CaO is (4-5) in parts by mass: (0.01-0.1): (0.01 to 0.1) of the above Bi₂O₃And B₂O₃The ratio of (1): (1.9-2.1).

4. The method for preparing the eutectic glass powder according to any one of claims 1 to 3, comprising the steps of:

1) grinding and mixing the raw materials uniformly, and melting at 800-1200 ℃ for 60-180 minutes to obtain glass liquid;

2) and performing water quenching on the glass liquid, naturally cooling to room temperature of 20-25 ℃, performing suction filtration to obtain a precipitate, drying the precipitate to obtain a glass block, and crushing and grinding the glass block to obtain the eutectic point glass powder.

5. The preparation method according to claim 4, wherein in the step 1), the melting temperature is 900 to 1100 ℃ and the time is 90 to 150 minutes.

6. The method according to claim 4, wherein in the step 1), the starting material is Bi₂O₃、B₂O₃ZnO, ZnO and regulating components, wherein BaO, CaO and Na in the regulating components₂O and Li₂O is prepared from carbonate, SiO in said regulating component₂、Al₂O₃MgO is produced from the oxide itself.

7. The preparation method according to claim 4, wherein in the step 2), the water quenching method comprises the following steps: pouring the glass liquid into deionized water;

in the step 2), the drying time is 12-36 hours, and the drying temperature is 50-120 ℃;

in the step 2), the grain size of the eutectic point glass powder is 10-15 microns.

8. The method for preparing far-red light boron bismuthate luminescent glass ceramic based on the eutectic point glass powder is characterized in that the eutectic point glass powder in claim 1 is uniformly mixed with far-red light fluorescent powder, and the mixture is calcined at 600-700 ℃ for 30-180 minutes to obtain the far-red light boron bismuthate luminescent glass ceramic.

9. The method as claimed in claim 8, wherein the far-red phosphor is far-red ZnGa₂O₄And (3) fluorescent powder.

10. The method according to claim 9, wherein the ratio of the eutectic point glass powder to the far-red fluorescent powder is (9-11) in parts by mass: (0.1-0.3).

Technical Field

The invention belongs to the technical field of special glass production and manufacturing, and particularly relates to eutectic point glass powder and a preparation method and application thereof.

Background

The traditional commercial eutectic point glass system contains lead, hexavalent chromium, cadmium, mercury and the like, seriously harms the natural environment and the human health and does not meet the national environmental protection requirement; secondly, during the heat treatment process, the glass should not react with the fluorescent powder; finally, for ease of processing, glass systems with lower softening temperatures should be selected. Research shows that in a lead-free low-softening-temperature glass system, phosphate system and stannous system eutectic point glass is not suitable for outdoor use due to the factors of poor water resistance, difficulty in preparation and the like; bismuth (Bi) oxide only₂O₃) A few systems such as glass have application potential. However, bismuth oxide glass generally requires a high melting temperature and a large thermal expansion coefficient.

Far-red light (700-740 nm) is of great importance to plants because it can induce or inhibit photomorphogenesis (light-mediated development) by photosensitizing pigments, and also can optimize photosynthesis by balancing the energy distribution among photosystems with different spectra. In particular, far-red light is very important for growing high-value vegetables because it can prevent deterioration in eating quality and bitterness caused by excessive growth of vegetables. However, there are few reports on the current lighting source special for plant growth, and the current agricultural lighting source is also a non-far-red light source, so that there is no more positive gain effect on plant growth, and a certain influence is caused on agriculture and production, therefore, the luminescent glass ceramic material capable of emitting far-red light is the main development direction of the LED light source special for plant growth.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide the eutectic point glass powder, which adjusts the glass process and performance by introducing different oxide components.

The invention also aims to provide a preparation method of the eutectic point glass powder.

The invention also aims to provide a method for preparing far-red light boron bismuthate luminescent glass ceramic based on the eutectic point glass powder, the far-red light boron bismuthate luminescent glass ceramic has excellent thermal stability, and can obtain far-infrared fluorescence emission with a strong peak value and favorable for plant growth under the excitation of the wavelength of a visible light region.

The purpose of the invention is realized by the following technical scheme.

The eutectic point glass powder comprises the following components in percentage by mass: 20 to 70 wt% of Bi₂O₃20 to 70 wt% of B₂O₃5-20 wt% of ZnO and 0-10 wt% of regulating component, wherein the regulating component is BaO and SiO₂、Al₂O₃、MgO、Na₂O、Li₂One or a mixture of more than one of O and CaO in any proportion.

In the above technical scheme, the Bi is calculated by mass percentage₂O₃21 to 63 wt%, of the component B₂O₃21-63 wt%, ZnO 8-12 wt%, and the adjusting component 4-6 wt%.

In the above technical scheme, the raw material of the eutectic point glass powder is one of the following cases:

the regulating components are BaO and Li₂O and Al₂O₃The mixture of (A) and (B), in parts by mass, the BaO and Li₂O and Al₂O₃The ratio of (4-5): (0.01-0.1): (0.01 to 0.1) of the above Bi₂O₃And B₂O₃The ratio of (1.9-2.1): 1;

the adjusting components are BaO and SiO₂And Na₂A mixture of O, the BaO and the SiO are calculated according to the mass portion₂And Na₂The ratio of O is (4-5): (0.01-0.1): (0.01 to 0.1) of the above Bi₂O₃And B₂O₃The ratio of (1.9-2.1): 1;

the adjusting component is a mixture of BaO, MgO and CaO, and the ratio of BaO, MgO and CaO is (4-5) in parts by mass: (0.01-0.1): (0.01 to 0.1) of the above Bi₂O₃And B₂O₃The ratio of (1.9-2.1): 1;

the adjusting component is a mixture of BaO, MgO and CaO, and the ratio of BaO, MgO and CaO is (4-5) in parts by mass: (0.01-0.1): (0.01 to 0.1) of the above Bi₂O₃And B₂O₃The ratio of (1) to (0.9): 1;

the adjusting component is a mixture of BaO, MgO and CaO, and the ratio of BaO, MgO and CaO is (4-5) in parts by mass: (0.01-0.1): (0.01 to 0.1) of the above Bi₂O₃And B₂O₃The ratio of (1): (1.9-2.1).

The preparation method of the eutectic point glass powder comprises the following steps:

1) grinding and mixing the raw materials uniformly, and melting at 800-1200 ℃ for 60-180 minutes to obtain glass liquid;

in the step 1), the melting temperature is 900-1100 ℃, and the time is 90-150 minutes.

In the step 1), the raw material is Bi₂O₃、B₂O₃ZnO, ZnO and regulating components, wherein BaO, CaO and Na in the regulating components₂O and Li₂O is prepared from carbonate, SiO in said regulating component₂、Al₂O₃MgO is produced from the oxide itself.

2) And performing water quenching on the glass liquid, naturally cooling to room temperature of 20-25 ℃, performing suction filtration to obtain a precipitate, drying the precipitate to obtain a glass block, and crushing and grinding the glass block to obtain the eutectic point glass powder.

In the step 2), the water quenching method comprises the following steps: and pouring the glass liquid into deionized water.

In the step 2), the drying time is 12-36 hours, and the drying temperature is 50-120 ℃.

In the step 2), the grain size of the eutectic point glass powder is 10-15 microns.

The method for preparing the far-red light boron bismuthate luminescent glass ceramic based on the eutectic point glass powder comprises the steps of uniformly mixing the eutectic point glass powder with the far-red light fluorescent powder, and calcining at 600-700 ℃ for 30-180 minutes to obtain the far-red light boron bismuthate luminescent glass ceramic.

In the above technical scheme, the far-red fluorescent powder is far-red ZnGa₂O₄And (3) fluorescent powder.

In the technical scheme, the ratio of the eutectic point glass powder to the far-red fluorescent powder is (9-11) in parts by mass: (0.1-0.3).

Compared with the prior art, the eutectic-point glass powder has lower glass eutectic temperature, can be eutectic at 600-700 ℃ after being mixed with far-red fluorescent powder, greatly reduces the melting difficulty in practical application, reduces energy consumption, can keep the fluorescence property of the fluorescent powder due to the temperature quenching phenomenon of the fluorescent powder and the eutectic-point glass powder, and is suitable for ZnGa of far-red light₂O₄The far-red light boron bismuthate luminescent glass ceramic is prepared from the fluorescent powder material, and is particularly suitable for LED illumination required by plant growth. The far-red light borobismuthate luminescent glass ceramic takes borobismuthate luminescent glass ceramic as a carrier to be doped with far-red light fluorescent powder, has good chemical and physical stability, and can ensure that far-red light ZnGa is added with a regulating component₂O₄The fluorescent powder material keeps good luminous performance, can meet the requirement on light source intensity in plant growth, effectively avoids the problem of enhancing the power of an LED device and preventing high-temperature thermal quenching under the condition of improving light intensity, and has important application value in the field of LED artificial illumination in plant growth and cultivation.

Drawings

FIG. 1 is an X-ray diffraction spectrum of a far-red light bismuthate boron luminescent glass ceramic obtained in examples 1 to 6;

FIG. 2 is an excitation spectrum of the far-red luminescent bismuthate boron luminescent glass ceramic obtained in examples 1 to 6 at an emission wavelength of 720 nm;

FIG. 3 shows the emission spectra of the far-red bismuthate boron luminescent glass ceramics obtained in examples 1 to 6 under the excitation of a 415nm blue laser.

Detailed Description

The technical scheme of the invention is further explained by combining specific examples.

The grain diameter of the eutectic point glass powder is measured by a laser particle sizer;

uniformly mixing the eutectic point glass powder and far-infrared fluorescent powder, adding absolute ethyl alcohol into a mortar for wet grinding, grinding until the mixture is smooth, and drying for 6 hours;

the X-ray diffraction analyzer is Equinox3000 produced by French Saimer Feishale science and technology company;

the fluorescence spectrum analysis instrument is (Hitachi) F-4600;

the stability test is measured by a powder weight loss method, and the sample loss rate before and after soaking in water for 9 days, alkali and acid for 4 hours is calculated;

BaO，CaO，Na₂o and Li₂O is introduced by the corresponding carbonate, others by the corresponding drug or oxide, BaCO₃The purity of the CaO is 99.0 percent purchased from Tianjin Jiangtian chemical technology Limited company, the purity of the CaO is 99.5 percent purchased from Tianjin Fine chemical research institute, the purity of the ZnO is 99.0 percent purchased from Shanghai Micheln Limited company, other various medicines are purchased from Tianjin Fucheng chemical reagent factory, and the purity is analytical purity.

Far-red light ZnGa₂O₄ZnGa phosphor with spinel structure₂O₄(ZGO) has a large number of defects in the crystal lattice, can emit ultra-long far-infrared light, and its broad emission peak covers the effective wavelength range absorbed by plants. It was prepared by this experimental group. The self-made method is shown in reference documents: li M, Zhang H, Zhang X, et al³⁺doped ZnGa₂O₄ far-red emission phosphor-in-glass:Toward high-power and color-stable plant growth LEDs with responds to all of phytochrome[J].Materials Research Bulletin,2018:226-233.

Examples

The composition of the eutectic point glass powder is shown in the following table 1 in percentage by mass:

TABLE 1

The preparation methods of the low eutectic point glass powder in the above examples are the same, and comprise the following steps:

1) grinding and mixing raw materials corresponding to the compositions of the low-eutectic-point glass powder in the table 1 until the raw materials are uniform, and melting the raw materials in a box-type muffle furnace at the constant temperature of 900 ℃ for 120 minutes to obtain glass liquid; the raw material is Bi₂O₃、B₂O₃ZnO, regulating component of BaO, CaO and Na₂O and Li₂O is prepared from carbonate and SiO in its component is regulated₂、Al₂O₃MgO is produced from the oxide itself.

2) Pouring the glass liquid into deionized water for water quenching, naturally cooling to room temperature of 20-25 ℃, performing suction filtration to obtain precipitates, performing water washing and alcohol washing on the precipitates for 3 times respectively, drying and precipitating in a constant-temperature drying oven at 60 ℃ for 24 hours to obtain glass blocks, and crushing and grinding to obtain eutectic point glass powder, wherein the particle size of the eutectic point glass powder is 10-15 microns.

The water, alkali and acid stability of the eutectic point glass powder is measured by a powder weight loss method: sintering the eutectic point glass powder at 600 ℃ for 120min to obtain blocky glass, respectively soaking the blocky glass in water for 9 days, soaking the blocky glass in 0.1mol/L NaOH aqueous solution for 4h, and soaking the blocky glass in dilute nitric acid with the concentration percentage of 30 wt% for 4h, and testing the mass loss rate of the sample before and after the test, wherein the mass loss rate after soaking in water is shown in table 2, the mass loss rate after soaking in NaOH aqueous solution is shown in table 3, and the mass loss rate after soaking in dilute nitric acid is shown in table 4:

TABLE 2

Sample numbering	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6
							Mass before hydrolysis (g)	0.7416	0.7341	0.7406	0.7588	0.7301	0.7266
Mass after hydrolysis (g)	0.7350	0.7283	0.7368	0.7546	0.7237	0.7205
							Mass loss rate (%)	0.8900	0.7901	0.5131	0.5535	0.8766	0.8395

TABLE 3

Sample numbering	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6
							Mass before alkaline hydrolysis (g)	1.1564	1.5877	2.0795	1.5433	1.2418	1.9070
Mass after alkaline hydrolysis (g)	1.1561	1.5870	2.0791	1.5424	1.2415	1.9052
							Mass loss rate (%)	0.0259	0.0441	0.0192	0.0583	0.0242	0.0944

TABLE 4

Sample numbering	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6
							Mass before acidolysis (g)	2.9521	2.7804	2.2875	2.8041	3.6143	2.1207
Mass after acidolysis (g)	2.5640	2.3678	2.0509	2.4404	3.0870	1.6907
							Mass loss rate (%)	13.146	14.840	10.343	12.970	14.589	20.276

In the water stability experiment shown in table 2, the sample loss rate is lower than 1% before and after soaking in water for 9 days, and the eutectic point glass powder has excellent water erosion resistance, is convenient to use in production and life, has good stability and long service life.

In the alkali stability test of Table 3, it can be seen that although B is contained in the glass₂O₃ZnO and Al₂O₃The glass powder can react with alkali, but a stable glass network structure is formed with other components, so that the alkali corrosion resistance is improved, common silicate glass can easily form sodium silicate with strong alkali to influence the use, and the eutectic point glass powder can be suitable for strong alkali environment.

In the acid stability test of table 4, it can be seen that since the selected nitric acid has strong oxidizing property and higher concentration, the loss is maintained at about 10-20%, and it can be seen through observation that a layer of oxide film is formed on the surface to prevent more loss, and since the acidity in the acid stability test can be rarely reached in life, the daily use can be completely satisfied.

As can be seen in the XRD diffraction pattern of figure 1, an amorphous peak with a larger width exists between 25 and 40 degrees, which is a typical characteristic of a formed glass structure, and the material system is proved to have a more stable capacity of forming a glass network, and example 6 does not contain any adjusting materialThe composition is saved, although the ternary system can form a glass network, the crystallization phenomenon can occur, the negative influence can be generated on the overall performance of the finally formed glass, and the glass network can be stabilized by adding a certain adjusting component, so that the glass formation is facilitated. B is₂O₃And Bi₂O₃As a high content of components, strengthening the formation of the glass network, ZnO and Bi₂O₃Combined control of the high temperature viscosity of the glass, B₂O₃ZnO reduces the required temperature of the whole molten glass, the ternary system enables the glass system to have lower glass eutectic temperature, and the glass system can be eutectic in the range of 600-700 ℃ after being mixed with far-red fluorescent powder, and meanwhile, after the ternary component forms a glass network, the chemical property is relatively stable and cannot be combined with far-red ZnGa₂O₄Elements in the fluorescent powder are subjected to oxidation-reduction reaction, so that the fluorescent performance reduction caused by corrosion of the fluorescent powder is prevented.

The method for preparing far-red light boron bismuthate luminescent glass ceramic by obtaining the eutectic point glass powder based on the embodiments 1-6 comprises the steps of uniformly mixing the eutectic point glass powder with the far-red light fluorescent powder, calcining the mixture for 120 minutes at 600 ℃ in an MM-1000 gold melting furnace, placing the mixture on a copper mold with a groove, and lightly pressing the mixture into a sheet with the thickness of 5MM to obtain the far-red light boron bismuthate luminescent glass ceramic, wherein the far-red light fluorescent powder is far-red light ZnGa₂O₄The fluorescent powder comprises the following components in parts by weight, wherein the ratio of the eutectic point glass powder to the far-red fluorescent powder is 10: 0.2.

as can be seen from the excitation spectrum in fig. 2, under the wavelength of 720nm of the corresponding emission spectrum, the fluorescent powder can be excited by various common lights, such as 250nm ultraviolet light, 415nm blue light and 560nm yellow light, and the range of the using conditions is wide, and due to the temperature quenching phenomenon of the fluorescent powder, the fluorescent powder can maintain the fluorescent property of the fluorescent powder when being co-melted with the fluorescent powder at low temperature, so that the plant growth is facilitated, and the agricultural requirements are met;

as can be seen in the emission spectrum of FIG. 3, under the excitation of 415nm blue light, the light can emit strong far-red light required by plant growth, and has a large peak width, which is beneficial for the plant to regulate and control the plant type of the plant through the change of endogenous hormones of the plant through light quality, thereby improving the yield and the quality.

The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.