CN115893832B - Infrared filter glass and preparation method thereof - Google Patents
Infrared filter glass and preparation method thereof Download PDFInfo
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Abstract
The invention relates to infrared filter glass which comprises the following raw materials in parts by mass: 12-20 parts of Al (PO) 3 ) 3 5-8 parts of Ba (BO) 2 ) 2 9-14 parts of NaPO 3 7-10 parts of CaSiO 3 2-4 parts of NaBO 2 6-10 parts of Mg (PO) 3 ) 2 5-8 parts of Cu (PO) 3 ) 2 2-4 parts of ZnO,1.1-1.7 parts of SrO and 0.8-1.4 parts of Li 2 CO 3 1.4-2.5 parts of NaF and 0.05-0.1 part of CeO 2 . According to the invention, through refining copper metaphosphate and matching with other raw materials, the infrared filter glass with high visible light transmittance, low near infrared light transmittance and excellent optical performance is obtained, and particularly, the visible light transmittance is still higher near 700-750 nm.
Description
Technical Field
The invention belongs to the technical field of optical filters, and particularly relates to infrared filter glass and a preparation method thereof.
Background
Digital cameras and mobile phone cameras are popular in large numbers, and consumers have higher and higher requirements on imaging effects and quality of the digital cameras. CDD for digital cameras, or CMOS highly sensitive sensors, cover the near infrared region around 1100 nm. These infrared rays affect the color and quality of the final image, and therefore, the camera of the high-end mobile phone and the lens of the digital camera need to filter the infrared rays in order to ensure the imaging quality. The common optical glass has higher transmittance to infrared, especially near infrared, and is difficult to achieve the purpose of infrared filtering. In the case of an infrared filter, or an infrared filter glass, it is common to manufacture an infrared optical glass by adding Cu (II) to a phosphate, for example, in japanese patent JP2006-342045, cuO is added, but the addition of copper oxide tends to precipitate glass crystals, aggravate phase separation, and deteriorate the durability of the optical glass.
CN108675631 discloses a phosphate optical glass, which realizes the near infrared filtering effect by adding Fe element. The patent considers that Fe (II) has an absorption capacity for infrared light and Fe (III) can prevent the transmission of ultraviolet light. However, the presence of Fe element in the glass seriously affects the transmission of visible light, and adversely affects the optical glass for high-end cameras.
CN03154613.7, CN1508087 relates to fluorophosphate optical glass, containing a large amount of F element. However, F has high volatility, and the volatilization of F generated in the glass processing and preparing process is harmful to human bodies. In addition, F has higher electronegativity than oxygen and forms ionic bonds with metal elements, so that the obtained crystal has high crystallization tendency and poor chemical stability.
In addition, the infrared filter glass in the prior art has strong absorption effect in the near infrared band, but also has large absorption in the part with red visible light, namely 700-760nm, which has a very adverse effect on imaging quality.
Optical grade copper metaphosphate is an important additive for infrared filters, and has high requirements on purity and metal impurities of copper metaphosphate, such as Fe, co, mn, cr, and the like, and the impurity content is required to be in ppm level. The main problem of the existing optical grade copper metaphosphate is that the content of metal impurities, especially the content of nonferrous metal Fe is high, and the performance of the optical glass is affected.
CN114275753a, CN110040707a discloses a method for preparing copper metaphosphate, but the content of each metal ion impurity, especially nonferrous metal, in the product is still higher. There is also prior art to add arsenic oxide for infrared filtering purposes, but the use of toxic metallic arsenic is disadvantageous for both preparation and use and has been limited.
The current development trend of cameras is miniaturization, the space of an optical system is required to be as small as possible, in order to meet the current market demand on miniaturization of digital cameras, higher demands are also put forward on an infrared filter, and the filter is expected to have a good infrared filtering effect under the condition of being thinner. However, the infrared filter glass in the prior art cannot effectively achieve the effect. The infrared filter has low enough infrared light transmittance below 0.3mm, and the copper metaphosphate content needs to be increased, but the Cu (II) content is too high, so that the visible light transmittance of the prepared glass of 400-500nm is reduced. The imaging quality is adversely affected and the blue-green color is too strong.
Therefore, the research and development of the infrared filter glass has high visible light transmittance at the thickness of 0.3mm, low near infrared transmittance and great significance and commercial value in improving the performance of novel optical equipment such as digital cameras.
Disclosure of Invention
In order to overcome the defect that the optical performance of the infrared filter glass in the prior art is not excellent enough, an infrared filter with high light transmittance in a visible light region and low light transmittance in a near infrared region needs to be developed.
The invention provides infrared filter glass, which comprises the following raw materials in parts by mass: 12-20 parts of Al (PO) 3 ) 3 5-8 parts of Ba (BO) 2 ) 2 9-14 parts of NaPO 3 7-10 parts of CaSiO 3 2-4 parts of NaBO 2 6-10 parts of Mg (PO) 3 ) 2 5-8 parts of Cu (PO) 3 ) 2 2-4 parts of ZnO,1.1-1.7 parts of SrO and 0.8-1.4 parts of Li 2 CO 3 1.4-2.5 parts of NaF and 0.05-0.1 part of CeO 2 。
Further, the infrared filter glass comprises the following raw materials in parts by mass: 15-18 parts of Al (PO) 3 ) 3 6-7.2 parts of Ba (BO 2 ) 2 10-13 parts of NaPO 3 8.3-9.2 parts of CaSiO 3 2.4-3.1 parts of NaBO 2 7.6 to 9.3 parts of Mg (PO 3 ) 2 5.8-7.2 parts of Cu (PO 3 ) 2 2.8-3.5 parts of ZnO,1.3-1.5 parts of SrO and 1.0-1.3 parts of Li 2 CO 3 1.7-2.1 parts of NaF and 0.15-0.3 part of CeO 2 。
The invention adds a small amount of B and Si elements, in particular Ba (BO) 2 ) 2 ，NaBO 2 ，CaSiO 3 Is added in the form of (c). The addition of appropriate amounts of B and Si elements, in addition to enhancing the chemical stability of the glass, also contributes to the infrared absorption properties. However, the contents of B and Si are not easy to be excessive, and the B element is excessive, so that the infrared absorption is not facilitated; however, excessive Si element makes glass processing and melting difficult.
Further, the raw materials used in the invention are all of optical purity grade, and the main component content of the raw materials is more than or equal to 99%, preferably more than or equal to 99.5%, and more preferably more than or equal to 99.8%. And the total content of nonferrous metal impurities in the raw material is less than or equal to 20ppm, preferably less than or equal to 15ppm.
Further, the infrared filter glass further comprises the following raw materials in parts by mass: 0.02-0.05 part of Y 2 O 3 And/or La 2 O 3 . Adding small amounts of Y 2 O 3 And/or La 2 O 3 The toughness and infrared absorption characteristics of the glass can be improved.
Further, the content of Fe in each raw material is not more than 5ppm, preferably not more than 3ppm.
In a preferred technical scheme of the invention, when the thickness of the infrared filter glass is 0.3mm, the light transmittance of the infrared filter glass is more than 90% in a wave band of 400-600nm, the light transmittance of the infrared filter glass is more than 60% in a wave band of 700-750nm, the light transmittance of the infrared filter glass is less than 15% in a wave band near 800nm, and the light transmittance of the infrared filter glass is less than 2% in a wave band of 900-110 nm.
Further, wherein copper metaphosphate Cu (PO 3 ) 2 The preparation method of the (C) comprises the following steps:
(S1) removing impurities from phosphoric acid through activated carbon adsorption, and extracting and refining by a phosphate extractant to obtain refined phosphoric acid;
(S2) copper powder reacts with an ammonium bicarbonate solution under the action of an oxidant to obtain ammonia-type copper carbonate, and then deamination and calcination are sequentially carried out to obtain high-purity copper oxide;
(S3), refining phosphoric acid obtained in the step (S1) and high-purity copper powder obtained in the step (S2) according to the following steps: the molar ratio of Cu is 2.1-2.2:1, preparing copper dihydrogen phosphate through feeding reaction;
(S4) calcining the copper dihydrogen phosphate to obtain the optical grade copper metaphosphate Cu (PO) 3 ) 2 。
Further, the preparation method of the optical-grade copper metaphosphate comprises the following steps:
(S1) purification of phosphoric acid:
(S101) adding active carbon into phosphoric acid, and performing adsorption and impurity removal to obtain filtrate I;
(S102) adding modified activated carbon into the filtrate I, and performing adsorption and impurity removal to obtain filtrate II; the modified activated carbon is obtained by oxidizing activated carbon in organic solvent dispersion liquid by hydrogen peroxide, washing the activated carbon with water to be neutral, and calcining the activated carbon in ammonia atmosphere;
(S103) adding a phosphate extractant into the filtrate II, standing for layering, and taking a water phase to obtain refined phosphoric acid;
(S2) preparation of high-purity copper oxide:
(S201) introducing carbon dioxide into concentrated ammonia water to obtain an ammonia carbonate solution, simultaneously adding high-purity copper powder and an oxidant, keeping the system at 50-60 ℃ for constant-temperature reaction, and filtering to obtain an ammonia type copper carbonate solution;
(S202) deaminizing the ammoniacal copper carbonate solution to obtain high-purity alkaline copper carbonate;
(S203) calcining the high-purity alkali type copper carbonate to obtain high-purity copper oxide;
(S3) preparation of copper dihydrogen phosphate: feeding the high-purity copper oxide obtained in the step (S2), the refined phosphoric acid obtained in the step (S1) and deionized water, wherein the feeding in the system meets the requirement of P: the molar ratio of Cu is 2.1-2.2:1, reacting to obtain a copper dihydrogen phosphate solution, filtering, and evaporating and crystallizing the filtrate to obtain copper dihydrogen phosphate crystals;
(S4) calcining the copper dihydrogen phosphate to obtain the optical-grade copper metaphosphate.
The quality of copper metaphosphate as an infrared absorbing additive severely affects the quality of the infrared filter glass. The applicant found that in the infrared filter glass, the infrared filter effect can be achieved only by adding a relatively large amount of copper (II) into the glass component. And more Fe is often present in the copper source, which is the main source for introducing Fe hetero atoms into the infrared filter glass. There is no suitable optical grade copper metaphosphate on the market. The applicant found that poor copper metaphosphate quality is mainly due to the high impurity content of the raw material phosphoric acid and copper source, especially the high content of nonferrous metal Fe, which results in poor optical properties. The invention uses three steps of extraction of activated carbon, modified activated carbon and phosphate to purify industrial grade phosphoric acid; the high-purity copper powder is used for preparing ammonia-type copper carbonate through ammonia carbon evaporation, deamination and calcination are carried out to prepare high-purity copper oxide powder, refined and purified phosphoric acid is reacted with the high-purity copper oxide powder to prepare monobasic copper phosphate, finally, the monobasic copper phosphate is calcined to obtain the high-quality copper metaphosphate infrared absorption additive, and the high-quality copper metaphosphate infrared absorption additive is added into infrared filter glass, so that the infrared filter glass can effectively absorb and filter near infrared light, has high visible light transmittance, can improve the quality of the infrared filter glass, and is suitable for infrared filter materials such as modern digital cameras.
The phosphoric acid of the present invention is technical grade phosphoric acid, which is well known in the art, i.e., phosphoric acid at a concentration of about 85%. Of course, phosphoric acid having a concentration of 70 to 90% may be used without particular limitation; the activated carbon is commercial activated carbon, and has specific surface area of 600-800m 2 /g。
Further, in the step (S102), the modified activated carbon is produced by a production method comprising the steps of: adding activated carbon into an organic solvent, adding hydrogen peroxide, oxidizing under the auxiliary condition of microwaves at 20-25 ℃, washing the oxidized activated carbon with deionized water to be neutral, and calcining under the atmosphere of ammonia gas to obtain the catalyst. Preferably, the organic solvent is at least one of ethanol and acetone; the mass ratio of the activated carbon to the hydrogen peroxide is 100:7-10; the concentration of the hydrogen peroxide is 20-30wt%, and the microwave auxiliary condition is that the microwave power is 200-300W and the microwave frequency is 30-40KHz. According to the invention, the aperture of the activated carbon is increased by oxidizing and modifying the activated carbon, and the surface of the activated carbon is modified with a certain content of amino, so that not only can organic impurities in phosphoric acid be adsorbed, but also metal ions of impurities in phosphoric acid can be well adsorbed; the consumption of the subsequent phosphate extractant is reduced; the phosphate metal ion extractant is expensive and difficult to recycle, and the invention firstly uses the impurity removal process of the secondary activated carbon adsorption/modified activated carbon adsorption, so that most metal ion impurities are adsorbed, the load of extraction and purification in the step (S103) is reduced, the consumption of the extractant is reduced, and the cost is reduced.
Further, in the step (S101), the amount of the activated carbon is 3.6 to 5.3wt% based on the mass of phosphoric acid; in the step (S102), the amount of the modified activated carbon is 1.7-2.2wt% of the phosphoric acid; the activated carbon/modified activated carbon has small mass and can not effectively adsorb impurities; the impurity removal efficiency cannot be further improved even if the amount of the activated carbon is too large.
Further, in the step (S103), the phosphate extractant is at least one selected from the group consisting of triethyl phosphate, tripropyl phosphate, tributyl phosphate, and di (2-ethylhexyl) phosphate; the amount of the phosphate extractant is 12-18wt% of the phosphoric acid mass.
In the purification treatment of phosphoric acid, impurities are firstly removed through two-stage activated carbon adsorption, particularly, modified activated carbon is used in the step (S102), so that impurity metal ions in phosphoric acid can be adsorbed to a certain extent, the consumption of an extractant in the step (S103) is reduced, continuous extraction is not needed, the purpose of purifying phosphoric acid can be achieved by only one-time extraction, and the cost of purifying phosphoric acid is reduced.
Further, in the step (S201), the purity of the high-purity copper powder is more than or equal to 99.9 percent, the content of nonferrous metal impurities is less than or equal to 40ppm, and Fe is less than or equal to 8ppm; the oxidant is hydrogen peroxide, oxygen, ozone and air. For cost reasons, air is preferred. The concentration of the concentrated ammonia water is 20-25wt%.
Further, in the step (S201), ammonia water concentration of the ammonia carbon system is maintained at 120-150g/L, ammonium bicarbonate concentration is maintained at 190-230g/L, air intake is 20-25g/min of air intake per liter of ammonia carbon system, copper powder is added at one time in the initial stage of reaction, and copper powder can also be added in batches by continuously supplementing ammonia water and introducing carbon dioxide into the ammonia carbon system; preferably, the copper powder is added in batches, and the content of the copper powder in the ammonia-carbon system is 200-300g/L. Stopping feeding when the concentration of copper ions in the system reaches 1.3-1.7mol/L, continuing stirring and reacting for 1-2h, and filtering to obtain the ammonia copper carbonate solution.
Further, in the step (S202), the ammonia-removing reaction is that ammonia-type copper carbonate solution enters a stripping ammonia-removing tower from the middle upper part, so that materials in the stripping tower are at high temperature to perform decomplexing reaction to generate basic copper carbonate solid, and the generated ammonia gas can be recycled. The temperature of the stripping deamination tower is 120-150 ℃ and the vacuum degree is 0.1-0.2MPa, heating deamination is carried out under the condition, and the volatilized ammonia gas in the deamination process is absorbed and recycled by water.
Further, in the step (S203), the calcination temperature is 400-500 ℃ and the calcination time is 5-10 hours, so that the high-purity copper oxide is obtained.
Further, in the step (S3), the reaction condition of phosphoric acid and copper oxide is 108-112 ℃ for 4-6 hours; filtration is to remove unreacted solid impurities, typically by vacuum filtration. The temperature of the evaporative crystallization is 60-70 ℃, the temperature is not easy to be too high, the crystallization is carried out stably, and the deep blue solid powder is obtained, namely the high-purity copper dihydrogen phosphate. In the step (S4), the calcination temperature is 1500-1650 ℃, the calcination time is 4-8h, and the mixture is naturally cooled to room temperature after calcination. The calcination temperature is not easily too high, otherwise copper pyrophosphate byproducts may be produced.
The second object of the present invention is to provide a method for preparing the above infrared filter glass, comprising the following steps: weighing the materials according to the parts by mass, mixing, putting into a melting device, melting at 1300-1400 ℃, mixing, homogenizing, casting into a die, cooling, forming and annealing to obtain the infrared filter glass.
Further, the temperature in the melting device is raised to 1300-1400 ℃ at a heating rate of 3-5 ℃/min, and the temperature is kept for 7-10h; cooling to 800-900 ℃ at a cooling rate of 5-10 ℃/min in a die, annealing, namely transferring the formed glass to an annealing furnace, performing an annealing procedure at a cooling rate of 1-5 ℃/h, preferably, performing the annealing procedure at a cooling rate of 1-2 ℃/h, cooling to 200-280 ℃, turning off a power supply, and naturally cooling to room temperature to obtain the infrared filter glass. The heating rate during melt mixing is not easy to be too fast, otherwise, the glass materials are not uniformly mixed, and the anisotropic condition occurs; and the cooling rate during annealing is not easy to be too fast, otherwise, crystallization of glass is easy to occur.
Further, the melting device is a quartz crucible, can withstand a high melting temperature, and does not introduce metallic impurities such as Fe.
Further, in order to obtain the thin-layer infrared filter glass, the height of the die is 0.2-2mm, and the thickness of the die is determined according to the application scene of the specific infrared green glass. For example, for an infrared green sheet for a semiconductor image pickup device such as a digital camera CCD, the die height is 0.3 to 0.5mm. For such thin optical glass, it is necessary to consider the mechanical strength of the glass in addition to the optical properties. The length and width of the mold are not particularly limited, and in consideration of molding and practical use of the glass, the length and width are generally independently 50mm to 1000m, such as 100mm,200mm,300mm,500mm.
The invention has the beneficial effects that:
the invention obtains the infrared filter glass with high light transmittance in the visible light region and excellent optical performance with low near infrared light transmittance through screening and proportion optimization of raw material components of the infrared filter glass; particularly, the infrared filter glass has higher visible light transmittance near 700-760nm and low near infrared light transmittance above 800nm, so that the infrared filter glass in the prior art has higher cut-off efficiency in the near infrared band, but has stronger cut-off for the visible light part of 700-760nm, which is unacceptable for the infrared filter glass for digital cameras.
The invention provides a new preparation method for copper metaphosphate which is an important additive of infrared filter glass, and the method is used for purifying and refining raw materials of phosphoric acid and copper oxide, so that metal impurities are reduced from the source. Thus, the optical grade copper metaphosphate product with extremely low metal impurity content and high quality and purity is prepared. The finally prepared infrared filter glass has high quality and good optical performance, and meets the increasingly strict requirements of the photographing optical glass for the optical camera.
Drawings
FIG. 1 is an XRD pattern of copper metaphosphate obtained in preparation example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. The following examples facilitate a better understanding of the present invention, but are not intended to limit the same. The experimental methods in the following examples are conventional methods unless otherwise specified.
In the embodiments of the present invention, reagents and equipment employed may be purchased from conventional commercial sources unless otherwise specified.
Unless otherwise specified, the "parts" are parts by mass, and the "%" are percentages by mass.
The activated carbon is purchased from Shanghai Xinhui and has a specific surface area of about 750m 2 /g。
The high-purity copper powder is purchased from Shanghai Chilean metallurgy, the purity is more than or equal to 99.9%, the content of nonferrous metal impurities is less than or equal to 40ppm, and the Fe is less than or equal to 8ppm.
The infrared filter glass of the invention is prepared from raw materials of Shanghai Taiyang technology Co.
Preparation examplePreparation of copper metaphosphate
Preparation example 1
(S1) purification of phosphoric acid:
(S101) adding 3.6 parts of active carbon into 100 parts of industrial 85% phosphoric acid, uniformly stirring, performing adsorption and impurity removal for 5 hours, and performing vacuum suction filtration after the adsorption is finished to obtain a filtrate I;
(S102) adding 100 parts of active carbon into 500 parts of ethanol, dispersing uniformly to obtain a dispersion liquid of the active carbon, keeping the constant temperature of 25 ℃, slowly adding 30 parts of 30wt% hydrogen peroxide under the auxiliary condition of 300W and 40KHz microwaves, oxidizing, continuously stirring for 4 hours after the hydrogen peroxide is added in 40 minutes, washing to be neutral by deionized water after the oxidation is finished, heating to 500 ℃ under the ammonia atmosphere, preserving heat, calcining for 15 hours, and cooling to room temperature to obtain modified active carbon;
adding 1.7 parts of modified activated carbon into the filtrate I obtained in the step (S101), performing adsorption and impurity removal for 8 hours, and performing vacuum suction filtration to obtain filtrate II;
(S103) adding 12 parts of tributyl phosphate into the filtrate II, vibrating and mixing, standing and layering, and taking a water phase to obtain refined phosphoric acid;
(S2) preparation of high-purity copper oxide:
(S201) introducing carbon dioxide into 25wt% of concentrated ammonia water to obtain a carbon ammonia solution, adding high-purity copper powder in batches, and simultaneously introducing air, wherein the air introducing speed is that 20g/min of air is introduced per liter of the carbon ammonia solution, keeping the system at a constant temperature for reaction at 50 ℃, supplementing ammonia water, regulating the introducing amount of the carbon dioxide, keeping the concentration of the ammonia water in the system at about 120g/L, keeping the concentration of the ammonium bicarbonate at about 190g/L, adding 260g of copper powder per liter of the carbon ammonia solution, keeping the constant temperature for reaction at 50 ℃, monitoring the concentration of copper ions in the system, stopping feeding after the concentration of the copper ions reaches 1.3mol/L, keeping the constant temperature for reaction for 1h, and filtering to obtain an ammonia-type copper carbonate solution;
(S202) ammonia copper carbonate solution enters a stripping deamination tower from the upper part for deamination reaction, the process parameters of the stripping deamination tower are 140 ℃ and 0.1MPa of vacuum degree, and high-purity soda copper carbonate is obtained after deamination reaction; the ammonia gas which is separated out is absorbed and recycled by water;
(S203) calcining the high-purity alkali copper carbonate at 400 ℃ for 10 hours to obtain high-purity copper oxide;
(S3) preparation of copper dihydrogen phosphate: and (3) mixing the high-purity copper oxide obtained in the step (S2) with the refined phosphoric acid obtained in the step (S1) according to the following P: cu=2.1:1, adding deionized water with the mass of 100% of refined phosphoric acid, reacting for 6 hours at 108 ℃, vacuum filtering to remove solid impurities, obtaining a copper dihydrogen phosphate solution, and evaporating and crystallizing at 60 ℃ to obtain deep blue solid powder which is high-purity copper dihydrogen phosphate crystal;
(S4) calcining the high-purity copper dihydrogen phosphate at 1500 ℃ for 6 hours, and naturally cooling to obtain dark green solid powder, thus obtaining the optical grade copper metaphosphate of the product.
FIG. 1 is an XRD pattern of the optical grade copper metaphosphate prepared by 1, which is consistent with the PDF29-0572 standard card, and illustrates that the pure phase of copper metaphosphate is prepared by the method of the present invention.
Preparation example 2
Other conditions are the same as in preparation example 1 except that in step (S101), the amount of activated carbon used is 5.3 parts; in S (102), the using amount of the modified activated carbon is 2.2 parts; in (S103), 12 parts of tributyl phosphate is replaced with 18 parts of di (2-ethylhexyl) phosphate.
Preparation example 3
The other conditions were the same as in preparation example 2 except that in step (S201), air was introduced at a rate of 25g/min per liter of ammonia-carbon solution, the concentration of ammonia water was maintained at around 150g/L, and the concentration of ammonium bicarbonate was maintained at around 230 g/L.
Preparation example 4
The other conditions were the same as in preparation example 2 except that in step (S203), the process parameters of the stripping deamination column were temperature 150℃and vacuum degree 0.15MPa.
Comparative preparation example 1
Other conditions are the same as in preparation example 2 except that in step (S102), the microwave assist is canceled.
Comparative preparation example 2
Other conditions are the same as in preparation example 2 except that in step (S102), calcination is performed under air conditions instead of ammonia gas.
Comparative preparation example 3
The other conditions are the same as in preparation example 2, except that in step (S102), the oxidation of hydrogen peroxide is not performed.
The copper metaphosphate obtained in the preparation example and the comparative preparation example are tested for impurity content by ICP-MS (inductively coupled plasma-mass spectrometry) and the results are shown in the following table 1:
TABLE 1 copper metaphosphate impurity content
| Sample of | Fe/ppm | Co/ppm | Cr/ppm | Pb/ppm | Mn/ppm | Ni/ppm |
| Preparation example 1 | 0.73 | 0.06 | 0.29 | 0.15 | 0.17 | 0.10 |
| Preparation example 2 | 0.65 | 0.04 | 0.26 | 0.12 | 0.11 | 0.07 |
| Preparation example 3 | 0.66 | 0.04 | 0.28 | 0.13 | 0.12 | 0.09 |
| Preparation example 4 | 0.64 | 0.05 | 0.28 | 0.11 | 0.12 | 0.08 |
| Comparative preparation example 1 | 0.88 | 0.12 | 0.37 | 0.26 | 0.26 | 0.17 |
| Comparative preparation example 2 | 1.32 | 0.17 | 0.45 | 0.32 | 0.28 | 0.23 |
| Comparative preparation example 3 | 1.15 | 0.23 | 0.48 | 0.34 | 0.22 | 0.20 |
From the data in Table 1, it can be seen that the copper metaphosphate obtained by the preparation method provided by the invention has high quality, high purity and extremely low metal impurity content, and is suitable for being used as an infrared filter glass additive of a high-end digital camera.
Examples preparation of IR-filter glass
The preparation of the infrared filter glass was carried out according to the formulation of table 2. Wherein Cu (PO) 3 ) 2 Is prepared in preparation example 2 above because of the minimum impurity content.
The specific method comprises the following steps: weighing all materials according to the mass parts of table 2, fully mixing by a high-speed mixer, putting into a melting device provided with a quartz crucible, controlling power, heating to 1300 ℃ at a heating rate of 3-5 ℃/min, fully melting the materials under stirring, preserving heat, smelting for 8 hours, homogenizing, casting into a 100mm multiplied by 0.3m die, cooling to 850 ℃ at a cooling rate of 5-8 ℃/min, cooling to form, transferring into an annealing furnace, cooling to 280 ℃ at an average cooling rate of 2 ℃/h, closing a power supply of the annealing furnace, cooling to room temperature, and finishing annealing to obtain the infrared filter glass.
Table 2 Infrared filter glass formulation
The infrared filter glass prepared in the example was subjected to optical performance test, the thickness of the infrared filter glass was 0.3.+ -. 0.01mm, and the transmittance of the infrared filter glass to light of different wavelengths was measured, and the results are shown in Table 3 below.
Table 3 optical performance test of ir-filter glass
It can be seen that the infrared filter glass prepared by the invention has high light transmittance in the visible light (400-760 nm) band and low light transmittance in the near infrared band (800-1100 nm) at the thickness of 0.3 mm. The infrared filter glass prepared by the formula can achieve a very good infrared filter effect even if the glass is a thin plate glass, does not have adverse effect on the light transmittance of a visible light region, particularly has a visible light region which is close to red light and is 700-760nm, and is very suitable for being used as an infrared filter for a miniaturized digital camera.
Claims (14)
1. The infrared filter glass is characterized by comprising the following raw materials in parts by mass: 12-20 parts of Al (PO) 3 ) 3 5-8 parts of Ba (BO) 2 ) 2 9-14 parts of NaPO 3 7-10 parts of CaSiO 3 2-4 parts of NaBO 2 6-10 parts of Mg (PO) 3 ) 2 5-8 parts of Cu (PO) 3 ) 2 2-4 parts of ZnO,1.1-1.7 parts of SrO and 0.8-1.4 parts of Li 2 CO 3 1.4-2.5 parts of NaF and 0.05-0.1 part of CeO 2 ；
The copper metaphosphate Cu (PO) 3 ) 2 The preparation method of the (C) comprises the following steps:
(S1) purification of phosphoric acid:
(S101) adding active carbon into phosphoric acid, and performing adsorption and impurity removal to obtain filtrate I; the dosage of the activated carbon is 3.6-5.3wt% of the mass of phosphoric acid;
(S102) adding modified activated carbon into the filtrate I, and performing adsorption and impurity removal to obtain filtrate II; the modified activated carbon is prepared by putting activated carbon into an organic solvent, adding hydrogen peroxide, oxidizing under the auxiliary condition of microwaves at 20-25 ℃, washing the oxidized activated carbon with deionized water to be neutral, and calcining under the atmosphere of ammonia gas; the organic solvent is at least one of ethanol and acetone; the mass ratio of the activated carbon to the hydrogen peroxide is 100:7-10; the concentration of the hydrogen peroxide is 20-30wt%, and the microwave auxiliary condition is that the microwave power is 200-300W and the microwave frequency is 30-40KHz; the dosage of the modified activated carbon is 1.7-2.2wt% of the phosphoric acid;
(S103) adding a phosphate extractant into the filtrate II, standing for layering, and taking a water phase to obtain refined phosphoric acid; the phosphate extractant is at least one of triethyl phosphate, tripropyl phosphate, tributyl phosphate and di (2-ethylhexyl) phosphate; the dosage of the phosphate extractant is 12-18wt% of the phosphoric acid mass;
(S2) preparation of high-purity copper oxide:
(S201) introducing carbon dioxide into concentrated ammonia water to obtain an ammonia carbonate solution, simultaneously adding high-purity copper powder and an oxidant, keeping the system at 50-60 ℃ for constant-temperature reaction, and filtering to obtain an ammonia type copper carbonate solution;
(S202) deaminizing the ammoniacal copper carbonate solution to obtain high-purity alkaline copper carbonate;
(S203) calcining the high-purity alkali type copper carbonate to obtain high-purity copper oxide;
(S3) preparation of copper dihydrogen phosphate: feeding the high-purity copper oxide obtained in the step (S2), the refined phosphoric acid obtained in the step (S1) and deionized water, wherein the feeding in the system meets the requirement of P: the molar ratio of Cu is 2.1-2.2:1, reacting to obtain a copper dihydrogen phosphate solution, filtering, and evaporating and crystallizing the filtrate to obtain copper dihydrogen phosphate crystals;
(S4) calcining the copper dihydrogen phosphate to obtain copper metaphosphate Cu (PO) 3 ) 2 。
2. The infrared filter glass according to claim 1, comprising the following raw materials in parts by mass: 15-18 parts of Al (PO) 3 ) 3 6-7.2 parts of Ba (BO 2 ) 2 10-13 parts of NaPO 3 8.3-9.2 parts of CaSiO 3 2.4-3.1 parts of NaBO 2 7.6 to 9.3 parts of Mg (PO 3 ) 2 5.8-7.2 parts of Cu (PO 3 ) 2 2.8-3.5 parts of ZnO,1.3-1.5 parts of SrO and 1.0-1.3 parts of Li 2 CO 3 1.7-2.1 parts of NaF and 0.15-0.3 part of CeO 2 。
3. The infrared filter glass according to claim 1, wherein the raw materials are of optical purity grade, and the content of the main component of the raw materials is not less than 99%; and the total content of nonferrous metal impurities in the raw material is less than or equal to 20 ppm.
4. The infrared filter glass according to claim 3, wherein the main component content of the raw material is not less than 99.5%.
5. The infrared filter glass according to claim 3, wherein the main component content of the raw material is not less than 99.8%.
6. The infrared filter glass according to claim 3, wherein the total content of nonferrous metal impurities in the raw material is 15ppm or less.
7. The infrared filter glass according to claim 3, wherein the content of Fe in each raw material is 5ppm or less.
8. The infrared filter glass according to claim 3, wherein the content of Fe in each raw material is not more than 3ppm.
9. The infrared filter glass according to claim 1, further comprising the following raw materials in parts by mass: 0.02-0.05 part of Y 2 O 3 And/or La 2 O 3 。
10. The infrared filter glass of claim 1, wherein the infrared filter glass has a light transmittance of > 90% in the 400-600nm band, a light transmittance of > 60% in the 700-750nm band, a light transmittance of < 15% in the 800nm vicinity, and a light transmittance of < 2% in the 900-1100nm band at a thickness of 0.3 mm.
11. The infrared filter glass of claim 1, wherein the infrared filter glass has a thickness of 0.1-1mm.
12. The infrared filter glass of claim 11, wherein the infrared filter glass has a thickness of 0.3-0.5mm.
13. The method for preparing the infrared filter glass according to any one of claims 1 to 12, comprising the steps of: weighing the materials according to the parts by mass, mixing, putting into a melting device, melting at 1300-1400 ℃, mixing, homogenizing, casting into a die, cooling, forming and annealing to obtain the infrared filter glass.
14. The preparation method of claim 13, wherein the temperature in the melting device is raised to 1300-1400 ℃ at a heating rate of 3-5 ℃/min, and the melting is performed for 7-10h; cooling to 800-900 deg.c at 5-10 deg.c/min in the mold, annealing in annealing furnace at 1-5 deg.c/h, annealing in annealing program at 1-2 deg.c/h to 200-280 deg.c, turning off the power supply, and cooling naturally to room temperature.
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