阅读说明：本技术 透中波紫外线的含铅玻璃及其制备方法和应用 (Lead-containing glass capable of transmitting medium-wave ultraviolet rays and preparation method and application thereof ) 是由 王晓钟 于 2021-02-05 设计创作，主要内容包括：本发明提供了透中波紫外线含铅硅酸盐玻璃,其组成按重量百分比包括：SiO-260％-75％,B-2O-31％-10％,PbO 1％-8％,CaO 2％-10％,ZnO 0-8％,Na-2O 4％-12％,K-2O 5％-18％。透中波紫外线含铅硅酸盐玻璃的优势在于：用PbO替代了价格较高的TiO-2,降低了原料成本,玻璃成分中引入PbO使玻璃的料性变长,在制作中波紫外线灯的过程中成品率较高,特别是在制作U型和螺旋型的紫外灯时,由于玻璃料性变长、硬化速度慢,玻璃折断的几率小,从而提高了成品率。本发明还涉及透中波紫外线的含铅玻璃的制备方法和应用。(The invention provides a lead silicate glass capable of transmitting medium-wave ultraviolet rays, which comprises the following components in percentage by weight: SiO 2 2 60％‑75％，B 2 O 3 1％‑10％，PbO 1％‑8％，CaO 2％‑10％，ZnO 0‑8％，Na 2 O 4％‑12％，K 2 And 5-18% of O. The advantages of the medium-wave ultraviolet ray transmitting lead-containing silicate glass are that: PbO is used to replace TiO with higher price 2 The cost of raw materials is reduced, the material property of the glass is prolonged by introducing PbO into the glass components, the yield rate is higher in the process of manufacturing medium wave ultraviolet lamps, and particularly, when U-shaped and spiral ultraviolet lamps are manufactured, the probability of glass breakage is small because the material property of the glass is prolonged and the hardening speed is slow, so that the glass is broken, and the cost is reducedAnd the yield is improved. The invention also relates to a preparation method and application of the lead-containing glass capable of transmitting the medium-wave ultraviolet rays.)

1. The lead-containing glass capable of transmitting medium-wave ultraviolet rays is characterized by comprising the following components in percentage by weight:

2. the mid-wave ultraviolet transparent leaded glass of claim 1 wherein the SiO in the leaded glass₂The content of (B) is 64-71 wt%.

3. The mid-wave ultraviolet transparent leaded glass of claim 1 wherein B in the leaded glass₂O₃The weight content of (A) is 2-8%.

4. The mid-wave ultraviolet transparent lead-containing glass according to claim 1, wherein the PbO content in the lead-containing glass is 2% to 6% by weight.

5. The mid-wave ultraviolet transparent leaded glass of claim 1, wherein the leaded glass satisfies at least one of the following conditions:

the weight content of CaO is 3-8%;

the weight content of ZnO is 1-6%;

Na₂the weight content of O is 5-10%;

K₂the weight content of O is 6-17%.

6. The mid-wave ultraviolet transmitting lead-containing glass according to any one of claims 1 to 5, wherein the lead-containing glass having a thickness of 1mm has a transmittance of 40 to 50% for light having a wavelength of 300nm and a transmittance of < 8% for light having a wavelength of 280 nm.

7. The mid-wave ultraviolet light transmitting leaded glass according to any one of claims 1 to 5, characterized in that the leaded glass has an expansion coefficient of (89 ± 1) × 10 at 20 ℃ to 200 ℃^-7The specific gravity of the glass is 2.55 plus or minus 0.015, the softening temperature is 690 plus or minus 10 ℃, the annealing temperature is 520 plus or minus 10 ℃, and the temperature (Tk-100) when the volume resistivity is 100m omega cm is more than or equal to 245 ℃.

8. A medium wave ultraviolet ray transmitting glass tube, a medium wave ultraviolet ray transmitting glass shell or a medium wave ultraviolet ray transmitting glass sheet made of the medium wave ultraviolet ray transmitting lead-containing glass according to any one of claims 1 to 7.

9. A medium wave ultraviolet ray transmitting tube, a medium wave ultraviolet ray transmitting bulb or a medium wave ultraviolet ray transmitting bead made of the medium wave ultraviolet ray transmitting lead-containing glass according to any one of claims 1 to 7.

10. A medium wave ultraviolet ray transmitting lamp (UVB lamp) made of the medium wave ultraviolet ray transmitting lead-containing glass according to any one of claims 1 to 7.

Technical Field

The invention relates to the field of materials, and relates to lead-containing glass capable of transmitting medium-wave ultraviolet rays, which belongs to amber group glass in an electronic glass group, can transmit medium-wave ultraviolet rays of 280-320nm and shield short-wave ultraviolet rays (UVC) and is used for manufacturing a medium-wave ultraviolet lamp (UVB lamp).

Background

The medium-wave ultraviolet ray with the wavelength of 280-320nm can promote the mineral metabolism and the formation of vitamin D in the bodies of human beings and animals, enhance the absorption of calcium and promote the growth of the animals. Most of the medium-wave ultraviolet rays contained in sunlight are absorbed by the ozone layer, and only less than 2 percent of the ultraviolet rays can reach the ground, so that the growth of animals which cannot be irradiated by sunlight for a long time is greatly influenced. Therefore, it is necessary to supplement the irradiation with medium-wave ultraviolet rays, and a method of irradiation with a medium-wave ultraviolet lamp is generally used. And the medium-wave ultraviolet lamp needs to be provided with medium-wave ultraviolet glass capable of transmitting the wavelengths of 280-320 nm.

Disclosure of Invention

The invention relates to a lead-containing medium-wave ultraviolet transmitting glass, lead can shield the passing of short-wave Ultraviolet (UVC) and does not need to add expensive TiO₂The cost of raw materials is reduced, the material property of the glass is prolonged by introducing PbO into the glass components, the yield rate is higher in the process of manufacturing the medium wave ultraviolet lamp, and particularly when manufacturing U-shaped and spiral ultraviolet lamps, the glass has long material property, is soft and has low hardening speed, and the probability of breaking the glass is small, so that the yield is improved. The glass surface prepared according to the invention has no air line, can be well sealed with Dumet wires or other glass of amber group, and the prepared medium wave ultraviolet lamp (UVB lamp) has good sealing performance and long service life.

The invention aims to provide the lead-containing glass for transmitting the medium wave ultraviolet rays, which can be well sealed with Dumet wires or other glass of an amber group in a melting way, has no air rays on the surface of the glass, and can be used for preparing the lead-containing glass for transmitting the medium wave ultraviolet rays, which has good sealing performance of a medium wave ultraviolet lamp (UVB lamp), has no slow air leakage phenomenon and has extremely small attenuation amplitude. The glass comprises the following components in percentage by weight:

further, SiO in the lead-containing glass₂The content of (B) is 64-71 wt%.

Further, B in the lead-containing glass₂O₃The weight content of (A) is 2-8%.

Further, the content of PbO in the lead-containing glass is 2-6% by weight.

Further, the weight content of CaO in the leaded glass is 3-8%.

Furthermore, the content of ZnO in the lead-containing glass is 1-6% by weight.

Further, Na in the lead-containing glass₂The weight content of O is 5-10%.

Further, K in the lead-containing glass₂The weight content of O is 6-17%.

Furthermore, the lead-containing glass with the thickness of 1mm has the transmittance of 40-50% for light with the wavelength of 300nm, and the transmittance of 280nm for light with the wavelength of less than 8%.

Further, the lead-containing glass has an expansion coefficient of (89 +/-1) × 10 at 20-200 DEG C^-7。

Furthermore, the lead-containing glass has a specific gravity of 2.55 +/-0.015, a softening temperature of 690 +/-10 ℃, an annealing temperature of 520 +/-10 ℃ and a temperature (Tk-100) of more than or equal to 245 ℃ when the volume resistivity is 100m omega cm.

The invention also provides a medium wave ultraviolet ray transmitting glass tube, a medium wave ultraviolet ray transmitting glass shell or a medium wave ultraviolet ray transmitting glass sheet which are made of the medium wave ultraviolet ray transmitting lead-containing glass.

The invention also provides a medium wave ultraviolet transmitting lamp tube, a medium wave ultraviolet transmitting bulb or a medium wave ultraviolet transmitting lamp bead which are made of the medium wave ultraviolet transmitting lead-containing glass.

The invention also provides a medium wave ultraviolet ray transmitting lamp (UVB lamp) made of the lead-containing glass transmitting medium wave ultraviolet rays

The invention has the beneficial effects that: lead can shield the passing of short wave Ultraviolet (UVC) and does not add expensive TiO₂The cost of raw materials is reduced, the material property of the glass is prolonged by introducing PbO into the glass components, the yield rate is higher in the process of manufacturing the medium wave ultraviolet lamp, and particularly when manufacturing U-shaped and spiral ultraviolet lamps, the glass has long material property, is soft and has low hardening speed, and the probability of breaking the glass is small, so that the yield is improved. The glass surface of the invention has no air line, and can be well sealed with Dumet wires or other glass of amber group, and the prepared medium wave ultraviolet lamp (UVB lamp) has good sealing performance and long service life. By adjusting the components and content of the glass to obtainThe transmittance of the lead-containing glass with the thickness of 1mm for transmitting the medium-wave ultraviolet glass to the wavelength of 300nm is 40-50%, and the transmittance to the wavelength of 280nm is less than 8%; has an expansion coefficient of (89 +/-1) × 10 at 20-200 deg.C^-7. The glass has a specific gravity of 2.55 +/-0.015, a softening temperature of 690 +/-10 ℃, an annealing temperature of 520 +/-10 ℃ and a temperature (Tk-100) of more than or equal to 245 ℃ when the volume resistivity is 100m omega cm.

Drawings

FIG. 1 is a graph showing the wavelength and transmittance of medium ultraviolet rays of a glass having a thickness of 1mm according to the present invention.

Detailed Description

The lead-containing glass capable of transmitting medium-wave ultraviolet rays consists of the following components in percentage by weight: SiO 2₂ 60％-75％，B₂O₃ 1％-10％，PbO 1％-8％，CaO 2％-10％，ZnO 0-8％，Na₂O 4％-12％，K₂O 5％-18％。

SiO in the Medium-wavelength ultraviolet-transmitting lead-containing glass of the present invention₂In an amount of from 60% to 75%, preferably from 64% to 71%, by weight. SiO 2₂Is the main body of silicate glass, and the framework of the glass is formed by a network of silica tetrahedrons. SiO 2₂When the content of (b) exceeds 75%, the glass is difficult to melt, and the melting temperature needs to be increased and the melting time needs to be prolonged, resulting in excessive energy consumption and reduced production efficiency, and simultaneously, the annealing temperature and softening temperature of the glass are increased, and the expansion coefficient is reduced. Too little results in poor chemical stability of the glass.

The medium-wavelength ultraviolet-transmitting lead-containing glass of the present invention contains B₂O₃1% to 10%, preferably 2% to 8%. B is₂O₃Fluxing reduces the viscosity of the glass and accelerates the clarification process. B is₂O₃Too small a content does not contribute to the deterioration of the chemical stability of the glass.

The lead-containing glass transmitting medium-wave ultraviolet rays contains 1-8%, preferably 2-6% of PbO, and the PbO can reduce the melting temperature and promote melting. The resistivity can be improved, and the annealing temperature and the softening temperature can be reduced. When the content of PbO is less than 2%, the shielding effect on short wave Ultraviolet (UVC) is not enough, and when the content of PbO exceeds 6%, the corrosion on the crucible wall is serious, so that more sand spots and stripes are generated on the glass product.

The medium-wave ultraviolet-transmitting lead-containing glass of the present invention contains CaO in an amount of 2% to 10%, preferably 3% to 8%. CaO together with other alkaline earth oxides can reduce the viscosity of the glass, promote melting, and also improve the chemical stability of the glass. Too little CaO content does not contribute to phase separation of the glass.

The medium-wave ultraviolet-transmitting lead-containing glass of the present invention contains 0 to 8%, preferably 1 to 6% of ZnO. ZnO can obviously improve the chemical stability of the glass, can reduce the viscosity of the glass when being used with other alkaline earth metal oxides, and promotes melting and clarification. Too low a ZnO content does not contribute to devitrification and opacification of the glass due to too much ZnO content.

The medium-ultraviolet ray-transmitting lead-containing glass of the present invention contains (Na)₂O+K₂O) 9% to 30%, preferably 15% to 25%. The medium-wavelength ultraviolet-transmitting lead-containing glass of the present invention contains Na₂O 4％-12％，K₂O5％-18％。Na₂O and K₂O can obviously reduce the viscosity of the glass and promote the melting of the glass, is a good fluxing agent and also determines the expansion coefficient of the glass to a great extent. Too low a content thereof does not contribute to the effect and the coefficient of expansion is too low. Their content too high reduces the chemical stability of the glass, (Na)₂O+K₂O) content of more than 30%, the expansion coefficient of the glass reaches 91 x 10^-7(20 ℃ to 200 ℃) above, and the coefficient of expansion is not matched with that of Dumet wires and other platinum group glass. The ultraviolet lamp cannot be well sealed with the ultraviolet lamp, and the ultraviolet lamp is cracked in situ or has large residual stress in the operation process of manufacturing the medium-wave ultraviolet lamp, and is cracked and leaked in the use process. Na (Na)₂O and K₂And O is introduced simultaneously, so that a double-alkali effect is achieved, and the chemical stability of the glass can be improved. In some embodiments, Na in the glass₂The mass content of O is 5-10%. In some embodiments, K in glass₂The mass content of O is 6-17%.

The lead-containing glass capable of transmitting medium-wave ultraviolet rays is simultaneously introduced with B₂O₃And BaO, and can also reduce the attenuation amplitude of the glass.

The invention being transparent to medium wave ultravioletThe lead-containing glass adopts refined quartz sand as the main raw material. The granularity of the main raw material quartz sand of the lead-containing glass capable of transmitting medium-wave ultraviolet rays is 60-140 meshes. The purity of other raw materials for the medium-wave ultraviolet-transmitting lead-containing glass of the present invention is industrial grade 3 or more. The lead-containing glass capable of transmitting medium-wave ultraviolet rays does not adopt mineral raw materials. The batch of the lead-containing glass capable of transmitting medium-wave ultraviolet rays adopts a small amount of glass to produce a commonly used clarifying agent. The lead-containing glass transmitting medium-wave ultraviolet rays of the present invention is melted in a closed crucible of a crucible furnace. The lead-containing glass capable of transmitting medium-wave ultraviolet rays does not adopt an iron container in the whole production process. The lead-containing glass which transmits medium-wave ultraviolet rays is melted for 4 to 5 hours at the liquid level temperature of 1400 +/-10 ℃, and a glass tube drawn by the melted glass liquid almost has no air lines, sand spots or stripes. Coefficient of expansion: 89 +/-1 x 10^-7(20-200 ℃ C.), transmittance: the glass with the thickness of 1mm has the transmittance of 40-50% for light with the wavelength of 300nm and the transmittance of less than 8% for light with the wavelength of 280 nm.

The following describes the glass making process, which essentially comprises the following steps:

1. selecting materials: the purity of the raw materials is more than industrial grade 3, and mineral raw materials are not adopted.

2. Mixing materials: the components of the lead-containing glass which can transmit medium-wave ultraviolet rays are mixed uniformly.

3. Melting: adding the mixed batch into a closed crucible, melting for 4-5 hours at the liquid level temperature of 1400 +/-10 ℃, and melting into glass liquid.

4. The preparation method comprises the following steps: opening the cylinder to cool the materials to an operable temperature of about 1000-1100 ℃, manually taking the materials, drawing the materials into a specified glass tube or blowing the materials into a glass shell or making the materials into a glass sheet, wherein the surface of the made product is required to be almost free of air lines, sand spots and stripes.

5. Quality inspection: drawing the glass tube or blowing the glass tube into a glass shell or making the glass tube into a glass sheet, checking whether the appearance of the product has air lines, sand points and stripes, and whether the size meets the specified requirements, and removing unqualified products.

It should be understood that the above discussed glass making methods are exemplary only and not intended to limit the present invention and that other suitable making methods may also be employed.

The glass of the present invention belongs to platinum group glass in electronic glass, and is sealed with Dumet wires or other platinum group glass in electronic glass during the manufacture of medium wave ultraviolet lamps, so that the expansion coefficient of the glass of the present invention is matched with that of the Dumet wires or other platinum group glass. If not matched, the sealing cannot be well fused. The Dumet wire has a radial expansion coefficient of (80-100) × 10^-7(20-350 ℃). The expansion coefficient of other platinum group glasses is (87-90) × 10^-7(20- -200 ℃ C.). The glass has the expansion coefficient of (89 +/-1) × 10^-7(20-200 ℃), can be well sealed with Dumet wire or other platinum group glass, so that the prepared medium wave ultraviolet lamp has small residual stress, firm sealing, no slow air leakage phenomenon, stable performance and excellent quality.

The transmittance of the medium-wave ultraviolet ray with the wavelength of 280nm-320nm of the glass for transmitting the medium-wave ultraviolet ray is based on the transmittance of the peak value at the wavelength of 300 nm. The medium-wave ultraviolet lamp with the thickness of 1mm and the wavelength of 300nm and the transmittance of less than 40 percent has poor effect. If > 50%, short-wave Ultraviolet (UVC) rays pass through the composition in a small amount, causing damage to animals. Therefore, the transmittance of the glass for transmitting medium-wave ultraviolet rays is limited to 40-50% at the wavelength of 300nm with the thickness of 1 mm.

In addition, the glass composition of the present invention does not contain Fe₂O₃And SeO₂Therefore, Fe is not present in a large amount₂O₃And SeO₂The ultraviolet rays are completely shielded.

Example 1:

TABLE 1

Oxide compound	Percentage content	Raw materials	Raw material weight (kg)
				SiO2	68.2	Quartz sand	68.2
B2O3	4	Boric acid	7.1
				PbO	3.4	Red lead	3.9
CaO	3.4	Calcium carbonate	6.1
				ZnO	4.2	Zinc oxide	4.2
Na2O	6	Soda ash	10.3
				K2O	2	Potassium nitrate	4.3
K2O	8.8	Potassium carbonate	12.9

The raw materials are weighed according to the weight, fully and uniformly mixed to form glass batch, the batch is added into a closed crucible, the glass batch is melted for 4 to 5 hours at the liquid level temperature of 1400 +/-10 ℃, the crucible is opened to cool the batch to 1000 to 1100 ℃, the batch is manually taken and drawn to form a specified glass tube or blown to form a glass shell or formed into a glass sheet, and each performance reaches the data of implementation 1.

Glasses of examples 2 to 8 were prepared by the preparation method of example 1, except that the weight of the raw materials was changed according to the contents of the respective components, and the preparation steps were the same. The component contents of each example are shown in table 2 below.

TABLE 2

As can be seen from the data of the above examples, the PbO-containing medium wave ultraviolet transmitting glass of the present invention does not contain expensive TiO₂The raw material is saved, and the cost is reduced. In addition, the glass composition of the invention does not contain Fe₂O₃And SeO₂So as to transmit medium wave ultraviolet rays and be suitable for manufacturing medium wave ultraviolet lamps. By reasonably adjusting the components, the performance of the glass can reach: expansion coefficient of (89 +/-1) × 10 at 20-200 deg.C^-7The specific gravity is 2.55 +/-0.015, the softening temperature is 690 +/-10 ℃, the annealing temperature is 520 +/-10 ℃, and the temperature (Tk-100) when the volume resistivity is 100m omega cm is more than or equal to 245 ℃. The transmittance at a thickness of 1mm and a wavelength of 300nm is limited to 40Between% and 50%. Meets the requirements of manufacturing medium wave ultraviolet lamps on various physical and chemical properties of glass and environmental protection.

Those skilled in the art will appreciate that the above embodiments are merely exemplary embodiments and that various changes, substitutions, and alterations can be made without departing from the spirit and scope of the application.