CN109734310B

CN109734310B - High-transmittance optical glass with visible light deep cutoff

Info

Publication number: CN109734310B
Application number: CN201910159724.3A
Authority: CN
Inventors: 沈杰
Original assignee: Nantong Guoguang Optical Glass Co ltd
Current assignee: Nantong Guoguang Optical Glass Co ltd
Priority date: 2019-03-04
Filing date: 2019-03-04
Publication date: 2021-12-03
Anticipated expiration: 2039-03-04
Also published as: CN109734310A

Abstract

The invention provides high-transparency optical glass for visible light deep cut-off, which comprises the following components in parts by weight: 30-40 parts of quartz sand, 13-15 parts of boric acid, 20-30 parts of phosphorus pentoxide, 4-8 parts of aluminum oxide, 8-10 parts of sodium carbonate, 4-6 parts of potassium carbonate, 3-5 parts of calcium carbonate, 1-1.3 parts of a coloring agent A, 2-3.3 parts of a coloring agent B and 1-2 parts of a reducing agent. The transmittance of the high-transmittance optical glass for the visible light deep cut is more than 85% in a 334nm wave band, and the average transmittance of 450nm-650nm is less than 0.001%, so that the visible light deep cut is realized.

Description

High-transmittance optical glass with visible light deep cutoff

Technical Field

The invention relates to glass for medical biological enzyme labeling equipment, in particular to optical glass with deep visible light cut-off and high transmittance in 334nm wave band.

Background

The visible light cut-off glass has wide application in medical detection equipment. The spectral characteristics of optical glass require high transmittance in different ultraviolet bands (254 nm; 313 nm; 334nm, 365nm) while cutting off visible light bands.

At present, similar optical glass at home has two defects:

the transmittance of the 1.334nm wave band is not high, and is generally about 80 percent; at present, the peak transmittance of the optical glass at a 334nm waveband is only about 80%, and the current practical application requirement needs to reach more than 85%.

2. The average transmittance in a visible light wave band, particularly 450nm-650nm, is about 0.1%, the cut-off depth OD is 3, and although the cut-off depth can meet the detection requirement of the current mainstream medical equipment, the cut-off depth is not enough, and the transmission of visible light influences the detection precision, so that the situation with high detection precision requirement cannot be met.

Aiming at the defects in the two aspects, the common practice of the industry is as follows: in order to meet the requirement of high transmittance in the 334nm waveband, the visible light cut-off capability is often required to be sacrificed, so that the requirement of visible light cut-off is met by coating on the basis of the original glass. However, the film plating brings disadvantages that the film plating glass has a long service life, the glass needs to be replaced generally for about 3 years, in addition, the cost is increased more through the secondary processing of the film plating, and the visible light cut-off degree is not ideal.

The CN201610455065.4 invention discloses high-permeability type tri-silver low-e glass, which comprises a glass substrate, wherein fifteen film layers are sequentially and adjacently compounded on a compound surface of the glass substrate from inside to outside, the first film layer is an SSTZrOx layer, the second layer is a ZnAlOx layer, the third layer is a TiOx layer, the fourth layer is an Ag layer, the fifth layer is a ZnAlOx layer, the sixth layer is a SiAlNx layer, the seventh layer is a ZnO layer, the eighth layer is an Ag layer, the ninth layer is a ZnSnO2 layer, the tenth layer is a NiCrOx layer, the eleventh layer is an AZO layer, the twelfth layer is an Ag layer, the thirteenth layer is a CrNxOy layer, the fourteenth layer is a ZnAlOx layer, and the fifteenth layer is a SnO2 layer. Although the light transmittance of the film plated by the method is as high as more than 80%, the cost is increased more, and the film plated by the method is also high in cost.

The invention discloses CN201110375231.7 high-transmittance long-wave ultraviolet glass and a preparation method thereof, wherein the glass comprises the following components: according to mass fraction, the material comprises 262-68% of SiO, 78-4% of Al2O 32, 6-12% of Na2O 6, 2-6% of K2O 2, 5-10% of alkaline earth metal oxide, 7-11% of PbO, 0.1-3% of NiO, 0.1-1% of CoO and 30.1-0.2% of Fe2O30. The ultraviolet light transmission film can transmit long-wave ultraviolet rays with the wavelength of 320nm-400nm, and the maximum ultraviolet transmittance of the ultraviolet light transmission film reaches 79.1 percent; the transmittance can not reach more than 85% of the market demand, and the visible light cut-off degree is not ideal.

Therefore, a new optical glass material is urgently needed to be developed, so that the optical glass has high transmittance at the 334nm waveband, and can meet the function of visible light depth cut-off to meet the market demand.

Disclosure of Invention

The technical problem is as follows: the invention aims to provide optical glass with depth cut-off in a visible light wave band and high transmittance in a 334nm wave band.

The technical scheme is as follows: in order to achieve the purpose, the invention provides the following technical scheme:

the invention relates to high-transparency optical glass for visible light deep cut-off, which comprises the following components in parts by weight:

30-40 parts of quartz sand, 13-15 parts of boric acid, 20-30 parts of phosphorus pentoxide, 4-8 parts of aluminum oxide, 8-10 parts of sodium carbonate, 4-6 parts of potassium carbonate, 3-5 parts of calcium carbonate, 1-1.3 parts of a coloring agent A, 2-3.3 parts of a coloring agent B and 1-2 parts of a reducing agent, uniformly mixing, and then smelting at 1230 +/-5 ℃.

Preferably, the high-transparency optical glass comprises the following components in parts by weight:

30-40 parts of quartz sand, 13-14 parts of boric acid, 20-30 parts of phosphorus pentoxide, 4-8 parts of aluminum oxide, 8-10 parts of sodium carbonate, 4-6 parts of potassium carbonate, 3-5 parts of calcium carbonate, 1-1.3 parts of a coloring agent A, 2-3.3 parts of a coloring agent B and 1-2 parts of a reducing agent.

35 parts of quartz sand, 13 parts of boric acid, 26 parts of phosphorus pentoxide, 7 parts of alumina, 3 parts of a coloring agent B, 9 parts of sodium carbonate, 5 parts of potassium carbonate, 3.5 parts of calcium carbonate, 1.2 parts of a coloring agent A and 1.2 parts of a reducing agent.

Preferably, the reducing agent is lithium aluminum hydride.

Preferably, the colorant a is cobalt oxide.

Preferably, the colorant B is nickel oxide.

Preferably, the ratio of colorant a to colorant B is 1: 1.5.

Preferably, the transmittance of the high-transmittance optical glass at different wavelengths is as follows: 313nm > 75%; 334nm is more than 85 percent; 405nm < 1%; an average transmission between 450nm and 650nm of <0.001% (i.e., OD 5).

Each component constituting the optical glass of the present invention will be described in detail below:

silica in the present invention is a main component formed of glass. Because 334nm high-transmittance glass is needed, a certain proportion of phosphoric acid is added, the transmittance of the glass in a 365nm wave band is better, a glass system which takes silicon dioxide as a main component and phosphoric acid as an auxiliary component is selected, and meanwhile, the visible light part of the glass needs to be cut off, so that the colorant can adopt nickel, and the transmission of the 365nm wave band cannot be influenced when nickel ions are introduced to cut off the visible light. And at P₂O₅-AL₂O₃-B₂O₃In the glass system, the content of alkali metal oxide is less, and nickel ions are mainly hexa-coordinated [ NiO₆]The nickel ion has high transmittance in the ultraviolet part, and the transmittance range also shifts to the ultraviolet short wave direction, and comprehensively, a glass system which takes silicon dioxide as the main component and phosphoric acid as the auxiliary component is adopted.

Boric acid is an important component of the phosphate structured glass system of the present invention. The disadvantage of poor chemical stability of phosphate glass can be improved by adding boric acid. Meanwhile, boric acid is a good fluxing agent, and can lower the melting point of glass. The boric acid is too much to cause "boron abnormality" and is not easily excessively introduced, so that the composition is controlled to 13 to 15 parts by weight, preferably 13 to 14 parts by weight.

The alumina in the present invention forms aluminum phosphate (Al) with phosphoric acid and boric acid as part of the phosphate glass system₂O₃·P₂O₅) With boron orthophosphate (B)₂O₃·P₂O₅) Due to glass formation of AlPO₄And BPO₄The original layered structure of the phosphate is changed into a frame structure by the group, so that the chemical stability of the phosphate glass is improved, and the thermal expansion coefficient is reduced. The component (B) accounts for 4-8 parts by weight, and preferably 7 parts by weight.

Cobalt oxide is used as one of the colorants of the glass of the present invention, and serves to cut off the visible light band in combination with nickel, which is another colorant. Cobalt ion is hexa-coordinated [ NiO ] in phosphate glass₆]There is a strong absorption mainly at 550 nm. The component is 2-3.3 weight portions, preferably 3 weight portions;

in the invention, sodium carbonate mainly serves as a fluxing agent and increases the density and strength of the glass; the component accounts for 8 to 10 weight portions, and the best is 9 weight portions;

the potassium carbonate in the invention mainly plays a role in breaking a net in glass, and can improve the chemical stability, surface tension and crystallization capacity of the glass. The component is 4-6 weight parts, preferably 5 weight parts;

calcium carbonate in the present invention is a divalent metal oxide. The calcium ions have the functions of polarizing bridge oxygen and weakening silicon-oxygen bonds, so that the high-temperature viscosity of the glass can be reduced, meanwhile, non-bridge oxygen is reduced, and the phenomenon that free electrons generated by ionizing radiation are captured by the non-bridge oxygen, so that the ultraviolet band absorption is caused, and the transmittance of the glass in the ultraviolet band is declined. However, since too much increases brittleness of the glass and is liable to devitrify, the composition is controlled to 3 to 5 parts by weight, preferably 3.5 to 4 parts by weight.

The nickel oxide of the invention is used as a colorant for the glass, in combination with another colorant cobalt, for the purpose of cutting off the visible light band. The nickel ions are mainly [ NiO ] in the phosphate glass₆]There is a strong absorption at 430 nm. However, when the amount of the nickel is too large, the transmittance peak shifts from 430nm to a short wavelength, which is very disadvantageous for ultraviolet-transmitting glass, and it has been found through a lot of experiments that it is preferable to incorporate 1 to 1.3 parts by weight of nickel, and the most preferable amount is 1.2 parts by weight, and at the same time, it is necessary to properly mix the amount of the nickel and the cobalt, and the most preferable ratio of the nickel and the cobalt is 1: 1.5.

The inventors have studied the silicate phosphate system of glass using lithium aluminium hydride as the reducing agent. In order to solve the problem of low transmittance in the 334nm waveband, a proper amount of reducing agent is added into a glass formula, and lithium aluminum hydride is used as the reducing agent of the glass in the invention because trace impurity Fe3+ inevitably exists in the glass raw material, thereby influencing the ultraviolet transmittance. Through a large number of experiments, in order to improve the transmittance of an ultraviolet band, a proper reducing agent lithium aluminum hydride is introduced, so that Fe3+ can be reduced to Fe2+, and therefore ultraviolet absorption is reduced, and the ultraviolet transmittance is improved. The specific chemical formula is as follows:

in order to effectively control the iron-containing impurities in the glass raw material, the amount of the lithium aluminum hydride is preferably 1 to 2 parts by weight, more preferably 1.2 parts by weight.

Has the advantages that: compared with the prior art, the invention has the beneficial effects that:

1. the high-transmittance optical glass with the visible light deep cutoff disclosed by the invention introduces a glass reducing agent lithium aluminum hydride for the first time, and eliminates Fe3+ ions as much as possible, so that the high transmittance of an ultraviolet band is improved, and the transmittance of the high-transmittance optical glass at a 334nm band is more than 85%. The technical problem that the current peak value transmittance of the ultraviolet glass in an ultraviolet band is only about 80 percent and the current practical application requirement needs to reach more than 85 percent is solved. Meanwhile, the lithium element can further stabilize the internal structure of the glass and improve the chemical stability of the optical glass.

2. The high-transmittance optical glass for visible light deep cut-off can achieve the optimal dosage by introducing the colorant and adjusting the proportion of the colorant, can reduce the influence on the transmittance of ultraviolet wave bands to the greatest extent, and simultaneously realizes the deep cut-off of visible light under the coordination of the reducing agent lithium aluminum hydride, wherein the transmittance of the glass in 334nm wave bands is more than 85 percent, and the average transmittance of 450nm-650nm is less than 0.001 percent.

3. The high-transparency optical glass with the deep cut-off of visible light does not contain the traditionally used environmental harmful substances such As arsenic (As), lead (Pb) and tellurium (Te) and the fluoride which is harmful to the environment and is easy to volatilize, solves the problem of environmental pollution and is beneficial to environmental protection. The optical glass provided by the invention has the advantages that the formula of the glass composition is reasonably adjusted, the optical glass with deep visible light cut-off and high transmittance in 334nm wave band is prepared, the transmittance of the coated glass can be achieved without coating, the transmittance is greater than 85%, and the deep cut-off of visible light is realized.

Drawings

FIG. 1 is a graph of the spectrum of the glass of example 1.

FIG. 2 is a graph of the spectrum of a currently used glass.

FIG. 3 shows the spectral curves of the novel optical glass of example 1 in comparison with the glasses currently used.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. Elements and features described in one embodiment of the invention may be combined with elements and features shown in one or more embodiments. It should be noted that the illustration omits illustration and description of components and processes not relevant to the present invention that are known to those of ordinary skill in the art for clarity purposes. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.

The invention provides optical glass with visible light deep cut-off and 334nm wave band high transmittance, which comprises the following components in parts by weight:

30-40 parts of quartz sand, 13-15 parts of boric acid, 20-30 parts of phosphorus pentoxide, 4-8 parts of aluminum oxide, 8-10 parts of sodium carbonate, 4-6 parts of potassium carbonate, 3-5 parts of calcium carbonate, 1-1.3 parts of colorant nickel oxide, 2-3.3 parts of colorant cobalt oxide and 1-2 parts of reducing agent.

The reducing agent is lithium aluminum hydride, and the ratio of the colorant nickel oxide to the colorant cobalt oxide is 1: 1.5.

In the embodiment of the invention, all raw materials are AR grade, so that iron-containing impurities in the raw materials are reduced to the maximum extent, and the transmittance of the glass in a 334nm wave band is influenced. After purchasing the AR grade material, the purification is performed again in the factory. The smelting crucible and the blade adopt quartz crucibles, and the quartz crucibles are selected to prevent iron impurities from polluting raw materials.

Example 1

Raw materials: 30 parts of quartz sand, 13 parts of boric acid, 30 parts of phosphorus pentoxide, 4 parts of aluminum oxide, 8 parts of sodium carbonate, 4 parts of potassium carbonate, 3 parts of calcium carbonate, 1 part of cobalt oxide, 3.3 parts of nickel oxide and 1 part of lithium aluminum hydride;

uniformly mixing the raw materials, then feeding at 1150 ℃, completely melting the raw materials, and then feeding for 10 times in total, wherein the feeding interval is about 30 minutes each time; after the charging is finished, the temperature is raised to 1230 ℃, and the temperature raising time is 1.5 hours; the melting temperature was 1250 ℃ for 4 hours. The temperature is reduced from 1250 ℃ to 1120 ℃, the temperature reduction time is 1 hour, and the discharging temperature is about 1100 ℃. And (3) final annealing, cooling at 580 ℃, and closing the power to cool naturally at 5 ℃ per hour to 300 ℃ to obtain the optical glass with visible light deep cut and high transmittance at 334nm waveband.

And testing the spectrum of the ultraviolet glass by a spectrophotometer according to the national standard GB/T15489.1: sample standard test thickness 2.5mm, sample transmittance at different wavelengths: 313nm > 75%; 334nm is more than 85 percent; 405nm < 1%; average transmittance of 450nm-650nm <0.001% (i.e., OD 5)

Example 2

Raw materials: 40 parts of quartz sand, 15 parts of boric acid, 20 parts of phosphorus pentoxide, 8 parts of aluminum oxide, 10 parts of sodium carbonate, 6 parts of potassium carbonate, 5 parts of calcium carbonate, 1.3 parts of cobalt oxide, 2 parts of nickel oxide and 2 parts of lithium aluminum hydride;

Example 3

Raw materials: 35 parts of quartz sand, 13 parts of boric acid, 26 parts of phosphorus pentoxide, 7 parts of aluminum oxide, 9 parts of sodium carbonate, 5 parts of potassium carbonate, 4 parts of calcium carbonate, 1.2 parts of cobalt oxide, 3 parts of nickel oxide and 1.2 parts of lithium aluminum hydride;

Sample testing method

1. Measuring by using a characteristic spectral line D-589.3 nm of sodium element; refractive index Nd 1.526

2. The chromaticity value of glass under D65 standard illuminant illumination was determined according to the Commission on International illumination (CIE):

X＝0.160；y＝0.01；Y＝0.2

3. glass spectra were tested by spectrophotometer: the standard test thickness of the sample is 2.5mm, and the test result of the invention is as follows according to the spectral requirement of national standard GB/T15489.1: 313nm > 75%; 334nm is more than 85 percent; 405nm < 1%; average transmittance of 450nm-650nm <0.001% (i.e., OD 5)

Example 1 sample glass spectral curve testing is shown in figure 1.

Table 1: transmittance of samples at different wavelengths in example 1

	Example 1	At present, optical glass
			Wavelength (nm)	Transmittance (%)	Transmittance (%)
313nm	86.15	81.05
			334nm	85.68	81.7
405nm	0.481	0.4
			Average transmittance of 450nm-650nm	0.0007	0.1

As can be seen from the data in table 1: the glass has good ultraviolet transmission performance, the peak value of the transmittance in the 313nm wave band reaches 86.5%, the average transmittance in the 450nm-650nm wave band of visible light is only 0.0007%, and the effect of visible light deep cut-off is achieved.

As shown in FIG. 1, the spectral curve of the glass of example 1 can be seen from the data in the graph: the optical glass has the advantages of deep visible light cut-off and high transmittance of 334nm, has the transmittance of more than 85 percent at 334nm, and simultaneously reaches OD5 at the visible light cut-off depth.

As shown in fig. 2, for the currently used glass spectrum curve, it can be seen from the data in the graph that: the currently used glass has a transmittance of about 81% at a 334nm wavelength band, and a visible light cut-off transmittance of about 0.1%, that is, a cut-off depth of OD3.

As shown in FIG. 3, the spectrum curve of the new optical glass of the present invention in example 1 compared with the currently used glass can be seen from the data in the graph: the transmittance of the novel optical glass in the 334nm wave band is improved from 80% to more than 85%, which is far higher than that of the glass used at present; according to the optical glass, through the adjustment of the formula, the cut-off transmittance of visible light is improved to be about 0.1 percent, namely the cut-off depth is OD3 to be OD5 in the cut-off performance of visible light wave band, which is far better than that of the glass used at present.

The embodiment and the attached drawings can be used for obtaining that:

1. the transmittance of the optical glass of the invention is more than 85% in a 334nm wave band, and simultaneously the visible light cut-off depth reaches OD 5. The technical problems that the peak transmittance of the optical glass at the 334nm waveband in the prior art is only about 80% and the actual application requirement at present needs to reach more than 85% are solved, the use conditions of the optical glass are expanded, and the application prospect is good.

2. The optical glass of the invention does not contain the traditionally used environmental harmful substances such As arsenic (As), lead (Pb) and tellurium (Te) and the fluoride components which are harmful to the environment and are easy to volatilize, thereby being beneficial to environmental protection.

3. According to the invention, through the improvement of the formula, the deep cut-off of visible light is realized, the transmittance at a 334nm waveband is more than 85%, meanwhile, the visible light cut-off depth reaches OD5, the average transmittance at the visible light waveband, especially 450nm-650nm, is about 0.1%, and the cut-off depth OD is 5; the method avoids adverse factors brought by coating the glass in order to meet the requirement of high transmittance of 334nm wave band in the prior art, because the coated glass has a service life, the glass generally needs to be replaced about 3 years, and in addition, the cost is increased more through secondary coating processing.

Finally, it should be noted that: although the present invention and its advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, means, methods and steps described in the specification. As one of ordinary skill in the art will readily appreciate from the disclosure of the present invention, processes, machines, means, methods, or steps, presently existing or later to be developed that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein may be utilized according to the present invention. Accordingly, the appended claims are intended to include within their scope such processes, devices, means, methods, or steps.

Claims

1. The high-transparency optical glass for the visible light deep cut-off is characterized by comprising the following components in parts by weight:

30-40 parts of quartz sand, 13-15 parts of boric acid, 20-30 parts of phosphorus pentoxide, 4-8 parts of aluminum oxide, 8-10 parts of sodium carbonate, 4-6 parts of potassium carbonate, 3-5 parts of calcium carbonate, 1-1.3 parts of a colorant A, 2-3.3 parts of a colorant B and 1-2 parts of a reducing agent, uniformly mixing, and then smelting at 1230 +/-5 ℃ to prepare the visible light deep cut-off ultraviolet high-transmittance optical glass.

2. The high-transparency optical glass for the deep cut-off of visible light as claimed in claim 1, which is characterized by comprising the following components in parts by weight:

30-40 parts of quartz sand, 13-14 parts of boric acid, 20-30 parts of phosphorus pentoxide, 6-8 parts of aluminum oxide, 8-9 parts of sodium carbonate, 4-5 parts of potassium carbonate, 3.5-4 parts of calcium carbonate, 1.1-1.3 parts of a coloring agent A, 2.5-3.3 parts of a coloring agent B and 1-1.5 parts of a reducing agent.

3. The high-transparency optical glass for the deep cut-off of visible light as claimed in claim 1, which is characterized by comprising the following components in parts by weight:

35 parts of quartz sand, 13 parts of boric acid, 26 parts of phosphorus pentoxide, 7 parts of alumina, 3 parts of a coloring agent B, 9 parts of sodium carbonate, 5 parts of potassium carbonate, 4 parts of calcium carbonate, 1.2 parts of a coloring agent A and 1.2 parts of a reducing agent.

4. The high optical glass with a deep cut-off of visible light according to claim 1, wherein the reducing agent is lithium aluminum hydride.

5. The high transparency optical glass for visible deep cutoff according to claim 1, wherein the colorant a is cobalt oxide.

6. The high optical glass with a deep cut-off of visible light as claimed in claim 1, wherein the colorant B is nickel oxide.

7. The high-transparency optical glass with a deep cut-off of visible light as claimed in claim 1, wherein the mass ratio of the colorant A to the colorant B is 1: 1.5.

8. The high-transmittance optical glass with deep cut-off of visible light as claimed in claim 1, wherein the transmittance of the high-transmittance optical glass at different wavelengths is as follows: 313nm > 75%; 334nm is more than 85 percent; 405nm < 1%; average transmittance of 450nm-650nm is less than 0.001%.