CN113003935A - Fluorophosphate optical glass, preparation method thereof and optical element - Google Patents

Fluorophosphate optical glass, preparation method thereof and optical element Download PDF

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CN113003935A
CN113003935A CN202110180057.4A CN202110180057A CN113003935A CN 113003935 A CN113003935 A CN 113003935A CN 202110180057 A CN202110180057 A CN 202110180057A CN 113003935 A CN113003935 A CN 113003935A
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glass
optical glass
fluorophosphate optical
fluorophosphate
optical
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CN113003935B (en
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陈振
霍金龙
聂顺
黄英
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Hubei New Huaguang Information Materials Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/23—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron
    • C03C3/247—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron containing fluorine and phosphorus
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements

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  • Life Sciences & Earth Sciences (AREA)
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  • General Chemical & Material Sciences (AREA)
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  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Glass Compositions (AREA)

Abstract

The invention provides fluorophosphate optical glass, a preparation method thereof and an optical element. The fluorophosphate optical glass comprises the following components in terms of compounds: p2O5：20～37％；AlF3：10～25％；Al2O3：1～8％；BaO：25～30％；BaF2：0～7％；ZnO：0～5％；LiF：11～17％；Sb2O3: 0.01-0.1%; the above percentages are all weight percentages. The fluorophosphate optical glass disclosed by the invention is low in cost, and has good chemical stability and coloring degree; the glass transition temperature is low, which is beneficial to precision compression molding; the specific gravity is low, so that the weight of a glass element and an optical system is reduced; the optical system has excellent achromatism performance and can improve the imaging quality of the optical system; the crystallization temperature is lowerSo that the mass production is easier to realize.

Description

Fluorophosphate optical glass, preparation method thereof and optical element
Technical Field
The invention relates to fluorophosphate optical glass, a preparation method thereof and an optical element, and belongs to the field of optical glass.
Background
Fluorophosphate optical glass is an optical material which combines the advantages of fluoride glass and phosphate glass, and the most prominent characteristic is the adjustability of optical properties brought by the adjustability of large-range components. The optical fiber has ultralow refractive index, ultralow dispersion and higher special relative partial dispersion value, has excellent achromatization performance, is particularly indispensable to a long-focus apochromatic lens, and becomes an indispensable component material in related optical design.
Patent application CN105271726B discloses an optical glass having a refractive index of 1.52 or more and an Abbe number of 71 to 78 or less. However, the disclosed glass contains 1 to 20 mol% of B3+，B3+The introduction of (2) can improve the glass forming performance of the glass. When the amount thereof is excessively introduced, the glass stability is deteriorated.
Patent application CN102260043B discloses an optical glass having a refractive index nd of 1.50 or more and an abbe number ν d of 65 or more. However, the disclosed glass contains 16 mol% to 22.2 mol% of Ba2+8.8 mol% to 11.1 mol% of Ca2+。Ba2+、Ca2+Too much introduction may deteriorate the chemical stability of the glass, and Ca is added2+Too much introduction of (b) also leads to a limitation in the reduction of the abrasion of the glass.
Patent application CN104276759A discloses an optical glass having a refractive index nd of 1.50 or more and an abbe number ν d of 65 or more. However, the disclosed glass contains 14 mol% to 24 mol% Ca2+，Ca2+Too much introduction may deteriorate the chemical stability of the glass, and Ca is added2+Too much introduction of (b) also leads to a limitation in the reduction of the abrasion of the glass.
Disclosure of Invention
Problems to be solved by the invention
The invention aims to provide fluorophosphate optical glass, a preparation method thereof and an optical element. The refractive index n of the fluorophosphate optical glassd1.49 to 1.56 and Abbe number upsilondIs 69 to 75. The fluorophosphate optical glass has good chemical stability and high degreeThe glass has low visible light transmittance and low glass transition temperature, can eliminate the defects of high melting temperature and difficult control of volatile stripes of the conventional optical glass, and can realize stable batch production.
Means for solving the problems
The invention provides fluorophosphate optical glass, which comprises the following components in terms of compounds:
P2O5: 20-37%, preferably 30-37%;
AlF3: 10-25%, preferably 10-20%;
Al2O3: 1-8%, preferably 1-5%;
BaO: 25-30%, preferably 27-30%;
BaF2: 0 to 7%, preferably 0 to 5%;
ZnO: 0 to 5%, preferably 0 to 3%;
LiF: 11-17%, preferably 11-15%;
Sb2O3: 0.01 to 0.1%, preferably 0.01 to 0.05%;
the above percentages are all weight percentages.
The fluorophosphate optical glass according to the present invention, wherein the fluorophosphate optical glass has a refractive index nd1.49 to 1.56 and Abbe number upsilondIs 69 to 75.
The fluorophosphate optical glass according to the present invention, wherein the fluorophosphate optical glass has a coloring degree λ80/λ5λ of (2)80At 350 or less, λ5Below 250 f.
The fluorophosphate optical glass according to the present invention, wherein a crystallization temperature L of the fluorophosphate optical glasstLess than or equal to 680 ℃ and devitrification resistance Tg/LtIs 0.52 or more, and has a glass transition temperature TgIs below 380 ℃.
The fluorophosphate optical glass according to the present invention has an internal transmittance at a wavelength of 700nm of 99.7% or more, an internal transmittance at a wavelength of 400nm of 98.0% or more, and an internal transmittance at a wavelength of 300nm of 70.0% or more when the fluorophosphate optical glass has a thickness of 10 mm.
The fluorophosphate optical glass according to the present invention, wherein the specific gravity of the fluorophosphate optical glass is 3.50g/cm3The following.
The fluorophosphate optical glass according to the present invention, wherein the fluorophosphate optical glass has a water resistance DwClass 1, acid resistance DA3 grade, and the acid corrosion resistance ratio is less than or equal to 0.51 percent.
The fluorophosphate optical glass according to the present invention, wherein a degree of abrasion Fa of the fluorophosphate optical glass is 500 or less.
The invention also provides a preparation method of the fluorophosphate optical glass, which comprises the following steps: the components are weighed according to the proportion, evenly mixed and smelted, and then poured or leaked injected into a forming die or directly pressed and formed.
The present invention further provides an optical element comprising the fluorophosphate optical glass according to the present invention.
ADVANTAGEOUS EFFECTS OF INVENTION
The fluorophosphate optical glass disclosed by the invention is low in cost, and has good chemical stability and coloring degree; the glass transition temperature is low, which is beneficial to precision compression molding; the specific gravity is low, so that the weight of a glass element and an optical system is reduced; the optical system has excellent achromatism performance and can improve the imaging quality of the optical system; meanwhile, the crystallization temperature is lower, so that the mass production is easier to realize.
The preparation method of the fluorophosphate optical glass is simple and easy to implement, the raw materials are easy to obtain, and mass production can be realized.
Detailed Description
Various exemplary embodiments, features and aspects of the invention will be described in detail below. The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
Furthermore, in the following detailed description, numerous specific details are set forth in order to provide a better understanding of the present invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In other instances, methods, means, devices and steps which are well known to those skilled in the art have not been described in detail so as not to obscure the invention.
All units used in the present invention are international standard units unless otherwise stated, and numerical values and numerical ranges appearing in the present invention should be understood to include systematic errors inevitable in industrial production.
The components of the optical glass of the present invention will be described in detail below, and the raw material introduction means takes various forms of compounds capable of introducing the contents of the respective components thereof. As described below, the content of each component is expressed in mass%. In the following description, the predetermined value is included when the predetermined value is equal to or less than the predetermined value or equal to or more than the predetermined value.
When the fluorophosphate optical glass is in a molten state, fluorine in the glass is extremely volatile. The volatilization easily causes the composition difference between the surface layer of the glass and the inner part of the glass, and further causes the glass to show optical non-uniformity, namely glass stripes. The volatilization of fluorine is related to the temperature of the molten glass, and the higher the temperature is, the greater the volatilization degree is. Therefore, in order to reduce the formation of striae, the tapping temperature of the glass should be reduced as much as possible. But lower out-of-furnace forming temperatures are also more likely to cause devitrification of the fluoride glass. The fluorophosphate optical glass designed by the invention can overcome the technical problems, and the obtained glass has good stability and is not easy to opal. Further, the present invention can provide an optical glass having a low refractive index and low dispersion required in optical design. Furthermore, since different optical designs require different degrees of matching of refractive index and dispersion, it is also an object of the present invention to obtain a low-refractive, low-dispersion optical glass that enables flexible matching of refractive index and dispersion.
Hereinafter, various embodiments of the present invention will be described in detail.
The invention provides fluorophosphate optical glass which comprises the following components in terms of compounds:
P2O5: 20-37%, preferably 30-37%;
AlF3: 10-25%, preferably 10-20%;
Al2O3: 1-8%, preferably 1-5%;
BaO: 25-30%, preferably 27-30%;
BaF2: 0 to 7%, preferably 0 to 5%;
ZnO: 0 to 5%, preferably 0 to 3%;
LiF: 11-17%, preferably 11-15%;
Sb2O3: 0.01 to 0.1%, preferably 0.01 to 0.05%;
the total weight of the components can be more than 99 percent;
the above percentages are all weight percentages.
The starting materials are introduced in a variety of forms capable of introducing their respective amounts of the compound. As described below, the contents of the respective components are expressed in weight percent.
P2O5Is a network forming body of glass, and both elements (phosphorus and oxygen) introduced into the glass by the network forming body are components constituting the glass skeleton. Thus P2O5Is an essential component for maintaining the stability of the glass and can effectively improve the mechanical properties of the glass. But P is2O5When the content of (b) is less than 20%, the glass tends to be gradually increased in crystallization and poor in stability; and P is2O5When the content is more than 37%, it is difficult to obtain desired optical properties. Therefore, to obtain the optical glass of the present invention, P2O5The content of (b) is 20 to 37%, preferably 30 to 37%, for example: 22%, 24%, 26%, 28%, 32%, 34%, 36%, etc.
P2O5The raw material has strong moisture absorption, the use and storage process of the raw material is complex, and P is easy to be absorbed after moisture absorption2O5Inaccurate introduction of componentsHas the disadvantages of low cost and high safety. Calculated to be BaO and Al2O3And P2O5Combined as Ba (PO)3)2、Al(PO3)3Starting materials, preferably Ba (PO) is used in the present invention3)2、Al(PO3)3Form (2) introduces P2O5And (4) components.
AlF3The two introduced elements (aluminum and fluorine) are also components forming a glass network framework, and the fluorine element is also used for reducing the dispersion of the product and improving the Abbe number upsilondCritical components of (a). AlF3The glass has the advantages of effective improvement of devitrification resistance and chemical stability of the glass and important significance for improving the mechanical property and the linear expansion coefficient of the glass. In the glass system of the present invention, when AlF3When the content of (2) is less than 10%, it is difficult to increase Abbe number (. nu.) due to decrease of fluorine element in the glassdThe object of (1), i.e. n is difficult to achieved、υdThe matching relationship of (1); when AlF is used3Above 25%, the glass transition temperature TgWill increase greatly, causing the molding temperature to increase, and in addition, AlF3Too large a content also increases the tendency of the glass to opacify, increases brittleness and increases abrasion. Therefore, AlF3The content of (a) is 10 to 25%, preferably 10 to 20%, for example: 12%, 14%, 16%, 18%, 22%, 24%, etc.
Al2O3And part of the glass can enter into the glass network framework, so that the glass has the advantages of improving the devitrification resistance and the chemical stability of the glass and being beneficial to reducing the abrasion degree of a glass product. Al (Al)2O3Is related to AlF3Matched use, in ensuring Al3+Adjusting oxygen-fluorine ratio (O/F) under the premise of constant content, namely adjusting Abbe number upsilondAnd Abbe number upsilondAnd refractive index ndThe matching property of (2). In the glass system of the present invention, when Al is present2O3When the content of (A) is less than 1%, the above effects are not exerted favorably; when Al is present2O3When the content of (b) is more than 8%, the glass transition temperature Tg is greatly increased, the molding temperature is increased, and the tendency of the glass to opal is rapidly increased. Therefore, Al2O3The content is 1-8%, preferably 1-5%, for example: 2%, 3%, 4%, 5%, 6%, 7%, etc.
In the present invention, the meaning of "refractive index and dispersion matching" is: when the refractive index value is determined, the degree of deviation of the dispersion value from the target value is small, and the matching property is good.
BaO is beneficial to improving the devitrification resistance and the refractive index of the glass, and the proper introduction of the BaO can reduce the crystallization temperature L of the glasstImprove the crystallization performance, and BaO is also an essential component for improving the meltability of the glass. In the present invention, when the content of BaO is less than 25%, the chemical stability and devitrification resistance of the glass become poor; however, when the content of BaO is more than 30%, the refractive index of the glass increases, it becomes difficult to achieve desired optical properties, and the specific gravity of the glass also increases, which increases the weight of the designed optical lens. Therefore, the content of BaO in the present invention is 25 to 30%, preferably 27 to 30%, for example: 26%, 27%, 28%, 29%, etc.
BaF2Is effective for improving the devitrification resistance of glass. It can also effectively adjust the refractive index and specific gravity of the glass. However, if the content is more than 7%, the refractive index of the glass increases, and it becomes difficult to obtain desired optical properties and the chemical stability of the glass is lowered. In order to better obtain the optical properties required by the present invention, BaF2The content of (b) is0 to 7%, preferably 0 to 5%, for example: 1%, 2%, 3%, 4%, 5%, 6%, etc.
ZnO is effective for improving alkali resistance of glass. Meanwhile, the refractive index and dispersion of the glass can be effectively adjusted, and in addition, the transition temperature of the glass can be effectively reduced by introducing ZnO. However, if the amount is more than 5%, the glass tends to be devitrified. In order to obtain the optical properties required by the present invention, the amount of ZnO should be controlled in the range of 0-5%, preferably 0-3%, for example: 1%, 2%, 3%, 4%, 5%, etc.
LiF can reduce the transition temperature TgSimultaneously has the functions of reducing dispersion and improving Abbe number upsilondHowever, more LiF will decrease the stability of the glass, increase the tendency of the glass to devitrify and make the glass chemically stableThe qualitative property gradually worsens. Therefore, the content of LiF is 11 to 17%, preferably 11 to 15%, for example: 12%, 13%, 14%, 16%, etc.
Sb2O3Can be optionally added as a defoaming agent, but the content thereof is sufficient to be within 0.1%, and Sb is2O3When the content of (A) exceeds 0.1%, the degree of coloration and internal transmittance of the glass are deteriorated, and the refractive index n is lowereddAnd dispersion increases. Thus, Sb2O3The content of the component is limited to 0.01-0.1%, preferably 0.01-0.05%.
In the present invention, the "contribution to the refractive index" means: the refractive index n of the glass being increased by a certain amount (e.g. 1%) of a certain componentdThe value of (a) is added. The meaning of "contribution to dispersion" is similar, and the term "contribution to dispersion" generally refers to: after a certain amount (e.g., 1%) of a certain component is added, the dispersion of the glass increases.
Fluorine (F) content in glass for lowering refractive index n of glassdAnd dispersion are effective. If the fluorine (F) content is too small, the refractive index and dispersion tend to become large, and the target low refractive index and low dispersion cannot be achieved. On the contrary, if the fluorine (F) content is too high, ionic bonds in the glass are increased, and the feature of small ionic bond energy leads to instability of the glass skeleton, which makes the glass more susceptible to devitrification, and too high fluorine (F) content increases the abrasion degree of the product, and too high abrasion value is not favorable for tolerance control in the finish polishing process of the glass. In the present invention, fluorine (F) in the glass is made of AlF added in a complex manner3、BaF2LiF, and other fluorides are not artificially introduced in the invention.
The present inventors have discovered that the refractive index and dispersion of fluorophosphate optical glass are related to the oxygen-to-fluorine ratio (O/F) in the glass. The higher the oxygen to fluorine ratio (O/F), i.e., the higher the oxygen content, the higher the refractive index of the glass and the greater the dispersion, and a reasonable oxygen to fluorine ratio (O/F) is particularly important for improving the opacifying resistance of the glass. The oxygen-fluorine ratio (O/F) in the glass is controlled by adopting the contents and the proportion of the oxides and the fluorides.
In the present inventionThe clear optical glass has a plurality of excellent technical effects, specifically: the fluorophosphate optical glass has a coloring degree lambda80/λ5λ of (2)80At 350 or less, λ5Below 250 f. Crystallization temperature L of the fluorophosphate optical glasstLess than or equal to 680 ℃ and devitrification resistance Tg/Lt0.52 or more and a glass transition temperature of 380 ℃ or less.
Further, the fluorophosphate optical glass of the present invention has an internal transmittance at a wavelength of 700nm of 99.7% or more, an internal transmittance at a wavelength of 400nm of 98.0% or more, and an internal transmittance at a wavelength of 300nm of 70.0% or more, when the thickness is 10 mm.
The specific gravity of the fluorophosphate optical glass of the present invention is 3.50g/cm3The following. Water resistance D of the fluorophosphate optical glasswClass 1, acid resistance DA3 grade, and the acid corrosion resistance ratio is less than or equal to 0.51 percent. The fluorophosphate optical glass has a degree of abrasion Fa of 500 or less.
The present invention also provides a method for producing a fluorophosphate optical glass according to the present invention, which comprises: the components are weighed according to the proportion, evenly mixed and smelted, and then poured or leaked injected into a forming die for forming or directly pressed for forming.
Specifically, the raw materials are weighed according to a specified proportion, mixed into a batch, smelted in a crucible made of platinum at the temperature of 800-900 ℃, the temperature is raised to 900-1000 ℃ after the raw materials are melted into molten glass, and a stirrer made of platinum is started for stirring and homogenizing, wherein the stirring time is controlled to be 3-8 hours. And after stirring, heating to 1000-1050 ℃, keeping the temperature for 4-9 hours, clarifying to enable bubbles to float sufficiently, then cooling to 700-800 ℃, pouring or leaking into a forming die or carrying out compression molding, and finally annealing and processing to obtain the optical glass.
In order to reduce the optical unevenness (striae) on the glass surface and the pollution to the environment caused by the volatilization of fluorine, it is preferable that in the production of the fluorophosphate optical glass, a cooling cover plate is added on the upper surface of a forming die where the glass liquid flows through, and inert gas is led to the surface of the glass liquid through the cooling cover plate, so that the glass liquid is cooled and formed as soon as possible. In addition, in order to prevent the corrosion of the glass to the melting crucible, the melting is preferably carried out in a non-reducing atmosphere, and oxygen can be introduced into the melting crucible or an oxidation molten pool can be added during the specific operation.
The present invention also provides an optical element comprising a fluorophosphate optical glass according to the present invention. The optical element can be produced by primary or secondary press molding of the fluorophosphate optical glass, and can be used in optical systems of various optical instruments.
Examples
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
In the table, examples 1 to 10 are illustrative of the invention for obtaining the refractive index nd1.49 to 1.56 and Abbe number upsilondTypical experiments for the fluorophosphate optical glass of 69-75.
Examples 1 to 10
The components in the following tables 1 and 2 are calculated, weighed and mixed according to the specified proportion, and put into a crucible made of platinum for smelting at the temperature of 850 ℃, and O is introduced into the crucible in the smelting process2Protecting the surface of the platinum from being corroded, raising the temperature to 950 ℃ after the raw materials are melted into molten glass, starting a stirrer made of the platinum to stir and homogenize, and controlling the stirring time to be 5 hours. After stirring, heating to 1000 ℃, keeping the temperature for 6 hours, clarifying to enable bubbles to float sufficiently, then cooling to 750 ℃, pouring or leaking into a forming die, additionally arranging the cooling cover plate on the forming die, leading inert gas to the surface of molten glass through the cooling cover plate, and solving the problem of fluorine flowThe problem of volatile stripes caused by loss. Finally, annealing and processing are carried out to obtain the optical glass or the optical element of the embodiment 1-10.
Comparative example A, B
The raw materials corresponding to the components in table 2 below were weighed in the prescribed proportions, and prepared by the same preparation method as in examples 1 to 10, to obtain the optical glass of comparative example A, B.
The properties of the obtained fluorophosphate optical glass were measured by the following methods.
The refractive index n of the optical glass is measured according to the test method of GB/T7962.1-2010dAbbe number upsilondThe measurement of (2).
Coloring degree lambda for optical glass short wave transmission spectrum characteristic80/λ5And (4) showing. Lambda [ alpha ]80Refers to the corresponding wavelength, lambda, when the spectral transmittance reaches 80%5The wavelength corresponds to a spectral transmittance of 5%. The light transmittance of a glass having a thickness of 10. + -. 0.1mm which was subjected to parallel face-grinding was measured in accordance with "method for measuring optical glass coloring degree" of JOGIS02-2003, Japan glass industries, Ltd.
Internal transmittance (. tau.) at wavelengths of 700nm, 400nm and 350nm according to the test method of GB/T7962.12-201010mmSample thickness 10 ± 0.1 mm).
The specific gravity of the optical glass obtained was measured according to the test method of GB/T7962.20-2010.
The transition temperature T of the optical glass obtained is measured according to the test method of GB/T7962.16-2010gAnd (6) carrying out testing.
LtThe temperature is liquidus temperature, i.e. upper limit temperature of crystallization, the test is carried out by DTA (differential thermal analysis) method, and the temperature corresponding to the highest heat absorption peak in the DTA curve is Lt。
The water resistance grade D of the obtained optical glass is determined according to the test method of JB/T10576-2006WAnd acid resistance grade DAAnd the acid erosion resistance ratio (percent leaching) were tested.
The abrasion Fa of the optical glass obtained was measured according to the test method of GB/T7962.19-2010.
Table 1: glass compositions and performance parameters for examples 1-6.
Figure BDA0002941201080000111
Table 2: glass compositions and performance parameters for examples 7-10 and comparative example A, B.
Figure BDA0002941201080000121
As can be seen from examples 1 to 10: the invention introduces P2O5The abnormal times of production can be greatly reduced, and the product performance is more stable and controllable. The glasses of the examples had higher chemical stability and lower glass transition temperature than those of the comparative examples, and lower abrasion Fa, which indicated that the products were more suitable for precision press-molding, while the relatively lower abrasion Fa indicated that the products were more convenient for finish polishing, when the same, expected optical constants were achieved.
As can be seen from Table 2, in comparative example A, the content of LiF is lower than the range defined by the present invention, and AlF3Is higher than the range required by the present invention, the refractive index n of the glassdAnd Abbe number upsilondThe glass transition temperature is increased, which is not beneficial to precision mould pressing processing, the specific gravity is obviously increased, the acid corrosion resistance ratio is also increased, the chemical stability of the glass is deteriorated, and the abrasion degree Fa is also increased, which is not beneficial to tolerance control in the process of fine grinding and polishing of the glass.
In comparative example B, the content of BaO was less than the range defined in the present invention, and Al2O3Is higher than the range required by the present invention, the refractive index n of the glassdAnd Abbe number upsilondAre out of the scope of the present invention, and have acid resistance DAThe grade 4, the acid corrosion resistance ratio is greatly increased, which indicates that the chemical stability of the glass is seriously deteriorated, the glass transition temperature is increased, the precision mould pressing processing is not facilitated, and the abrasion degree Fa is also increasedMoreover, the tolerance control in the process of glass fine grinding and polishing is not facilitated.
Therefore, the raw materials are weighed and mixed according to the proportion provided by the invention, the batch materials are put into a smelting device for manufacturing platinum, the raw materials are smelted by adopting proper oxidation, stirring, clarification and cooling processes, then the mixture is smelted by adopting proper forming processes such as leakage injection, inert gas cooling protection, cooling solidification and the like, and finally the low-refractive-index and low-dispersion optical glass which is free of devitrification, has the refractive index of 1.49-1.56 and the Abbe number upsilond of 69-75 can be stably produced by post-treatment such as annealing, processing and the like. The optical glass has ultralow refractive index, ultralow dispersion and higher special relative partial dispersion value, and has excellent achromatization performance. The optical glass also has a low softening point, can be made into an aspheric lens through secondary compression, and is an excellent optical material for producing digital products.
Industrial applicability
The fluorophosphate optical glass of the present invention and the production method thereof can be industrially produced, and the optical element of the present invention can be used in optical systems of various optical instruments.
The above examples of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.

Claims (10)

1. A fluorophosphate optical glass, characterized by comprising the following components in terms of compounds:
P2O5: 20-37%, preferably 30-37%;
AlF3: 10-25%, preferably 10-20%;
Al2O3：1～8％preferably 1-5%;
BaO: 25-30%, preferably 27-30%;
BaF2: 0 to 7%, preferably 0 to 5%;
ZnO: 0 to 5%, preferably 0 to 3%;
LiF: 11-17%, preferably 11-15%;
Sb2O3: 0.01 to 0.1%, preferably 0.01 to 0.05%;
the above percentages are all weight percentages.
2. Fluorophosphate optical glass according to claim 1, characterized in that the fluorophosphate optical glass has a refractive index nd1.49 to 1.56 and Abbe number upsilondIs 69 to 75.
3. Fluorophosphate optical glass according to claim 1 or 2, characterized in that the fluorophosphate optical glass has a coloring degree λ80/λ5λ of (2)80At 350 or less, λ5Below 250 f.
4. The fluorophosphate optical glass according to any one of claims 1 to 3, wherein the fluorophosphate optical glass has a crystallization temperature LtLess than or equal to 680 ℃ and devitrification resistance Tg/LtIs 0.52 or more, and has a glass transition temperature TgIs below 380 ℃.
5. A fluorophosphate optical glass according to any one of claims 1 to 4, characterized in that when the fluorophosphate optical glass has a thickness of 10mm, the internal transmittance at a wavelength of 700nm is 99.7% or more, the internal transmittance at a wavelength of 400nm is 98.0% or more, and the internal transmittance at a wavelength of 300nm is 70.0% or more.
6. The fluorophosphate optical glass according to any one of claims 1 to 5, wherein the specific gravity of the fluorophosphate optical glass is 3.50g/cm3The following.
7. A fluorophosphate optical glass according to any one of claims 1 to 6, characterized in that the fluorophosphate optical glass has a water resistance DwClass 1, acid resistance DA3 grade, and the acid corrosion resistance ratio is less than or equal to 0.51 percent.
8. The fluorophosphate optical glass according to any one of claims 1 to 7, wherein the fluorophosphate optical glass has a degree of abrasion Fa of 500 or less.
9. A method for producing a fluorophosphate optical glass according to any one of claims 1 to 8, characterized by comprising: the components are weighed according to the proportion, evenly mixed and smelted, and then poured or leaked injected into a forming die or directly pressed and formed.
10. An optical element comprising a fluorophosphate optical glass according to any one of claims 1 to 8.
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CN107628749A (en) * 2017-09-27 2018-01-26 湖北新华光信息材料有限公司 Fluorophosphate optical glass and preparation method thereof and optical element
CN110114321A (en) * 2016-12-07 2019-08-09 株式会社小原 Optical glass, preform and optical element
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JP2007131497A (en) * 2005-11-11 2007-05-31 Fujinon Corp Optical glass and its manufacture method
CN102674689A (en) * 2011-03-17 2012-09-19 株式会社小原 Optical glass, optical component and preformed base
CN105036550A (en) * 2014-04-25 2015-11-11 株式会社小原 Optical glass, optical element and fabric preform
CN110114321A (en) * 2016-12-07 2019-08-09 株式会社小原 Optical glass, preform and optical element
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