CN116514394A - 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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Publication number
CN116514394A
CN116514394A CN202310585795.6A CN202310585795A CN116514394A CN 116514394 A CN116514394 A CN 116514394A CN 202310585795 A CN202310585795 A CN 202310585795A CN 116514394 A CN116514394 A CN 116514394A
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optical glass
glass
fluorophosphate optical
fluorophosphate
content
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陈振
霍金龙
沈义梅
戎俊华
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Hubei New Huaguang Information Materials Co Ltd
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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
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B11/00—Pressing molten glass or performed glass reheated to equivalent low viscosity without blowing
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
    • Y02P40/57—Improving the yield, e-g- reduction of reject rates

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (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: al (PO) 3 ) 3 ：5％～12％；AlF 3 ：22％～33％；BaF 2 ：7.5％～15％；SrF 2 ：20％～30％；CaF 2 ：20％～30％；MgF 2 ：2％～7％；YF 3 :0.5 to 8 percent; liF:0.05 to 0.45 percent; the percentages are mass percentages; refractive index n of the fluorophosphate optical glass d Is 1.43 to 1.46, abbe number v d 90 to 100. The fluorophosphate optical glass of the present invention has sufficiently high internal transmittance in the visible light range. In addition, the fluorophosphate glass of the invention has low cost, good chemical stability and adhesionChromaticity; the glass transition temperature is lower, which is beneficial to precision compression molding.

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
The low refractive index, low dispersion fluorophosphate optical glass has low dispersion property and superior property of eliminating secondary spectrum special dispersion, and is widely used in lens modules of optical instruments for high-precision chromatic aberration correction, and has become an indispensable component material in related optical designs. In recent years, with rapid development of digitization and high precision of optical devices, imaging pixels are increasingly improved, and thus resolution requirements are also increasingly high.
The optical glass disclosed in the patent application CN102745899A, CN1931761A contains more than 5% of P 5+ While too much P is introduced 5+ Will inevitably introduce more O 2- Resulting in an increase in dispersion and a lower dispersion value cannot be obtained.
Fluorophosphate optical glass disclosed in patent application CN102674689a, wherein Zn 2+ The content of Zn is 0.5-15%, zn 2+ Has larger ionic radius and too much Zn is introduced 2+ The network structure of the glass is destroyed, and the crystallization performance, chemical stability and coloring degree of the glass are reduced. In addition, if Zn (PO) 3 ) 2 Introduction of Zn 2+ Will inevitably introduce more O 2- Resulting in an increase in dispersion and a lower dispersion value cannot be obtained.
Fluorophosphate optical glass disclosed in patent application CN101544468B, wherein O 2- /P 5+ More O is introduced at a molar ratio of more than 3.5 2- Resulting in an increase in dispersion and a lower dispersion value cannot be obtained. O in the invention 2- /P 5+ The molar ratio of (2) was 3.
The fluorophosphate optical glass disclosed in patent application CN106904831A contains 0.5-8% of LiF, and is characterized by Li + Is smaller in radius, too much Li + The alkali resistance of the glass can be drastically reduced, the abrasion degree is reduced, the subsequent processing and coating processes of the optical glass lens are seriously affected, the crystallization performance is also deteriorated, the stripes caused by crystallization in the melting process are serious, and the yield of the glass is greatly reduced.
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. Refractive index n of the fluorophosphate optical glass d Is 1.43 to 1.46, abbe number v d 90 to 100. The fluorophosphate optical glass has good chemical stability, high visible light transmittance and lower glass transition temperature, and can eliminate the defects of high melting temperature and difficult control of volatile stripes of the existing optical glass.
Furthermore, the invention also provides a preparation method of the fluorophosphate optical glass, which is simple and easy to implement, raw materials are easy to obtain, and stable mass production can be realized.
Solution for solving the problem
The invention provides a fluorophosphate optical glass, which comprises the following components in terms of compounds:
Al(PO 3 ) 3 :5% -12%, preferably 6% -10%;
AlF 3 :22% -33%, preferably 23% -30%;
BaF 2 :7.5% -15%, preferably 9% -13%;
SrF 2 :20% -30%, preferably 22% -29%;
CaF 2 :20% -30%, preferably 22% -28%;
MgF 2 :2% -7%, preferably 2% -5%;
YF 3 :0.5 to 8 percent, preferably 0.5 to 6 percent;
LiF:0.05 to 0.45%, preferably 0.1 to 0.35%;
the percentages are mass percentages;
refractive index n of the fluorophosphate optical glass d Is 1.43 to 1.46, abbe number v d 90 to 100.
The fluorophosphate optical glass according to the present invention, wherein, in weight percent, baF 2 Content of (2) and CaF 2 Contains (1)Ratio of quantity BaF 2 /CaF 2 0.35 to 0.72, preferably 0.36 to 0.64; and/or BaF 2 Content of (2) and MgF 2 And CaF 2 Ratio of the sum of the contents of BaF 2 /(MgF 2 +CaF 2 ) 0.3 to 0.64, preferably 0.32 to 0.56; and/or the number of the groups of groups,
Al(PO 3 ) 3 ratio of content of (2) to content of LiF Al (PO 3 ) 3 The ratio of LiF is 13 to 180, preferably 13 to 150.
The fluorophosphate optical glass according to the present invention, wherein the composition of the fluorophosphate optical glass does not contain P 2 O 5 、NaF、KF、SnF 4 、La 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Ta 2 O 5 、GeO 2 At least one of, caO, baO, srO and MgO.
The fluorophosphate optical glass according to the present invention, wherein the fluorophosphate optical glass has an upper crystallization limit temperature L t At a glass transition temperature T of 680 ℃ or lower g Is below 440 ℃; and/or the number of the groups of groups,
devitrification resistance T of the fluorophosphate optical glass g /L t Greater than 0.64.
The fluorophosphate optical glass according to the present invention, wherein the fluorophosphate optical glass has a coloring degree lambda 80 /λ 5 Lambda of (a) 80 310nm or less, lambda 5 Is 190nm or less.
The fluorophosphate optical glass according to the present invention, wherein the specific gravity of the fluorophosphate optical glass is 3.80g/cm 3 The following is given.
The fluorophosphate optical glass of the present invention, wherein the fluorophosphate optical glass has alkali resistance R OH (S) is 4 or more stages; and/or
Abrasion degree F of the fluorophosphate optical glass A 455 or less.
The invention also provides a preparation method of the fluorophosphate optical glass, which comprises the following steps: weighing and uniformly mixing the components according to the proportion, smelting, and fully escaping volatile gas in the smelting process; preferably, the smelting temperature is 800-900 ℃; then casting or leaking into a forming die, or directly pressing and forming.
The preparation method of the invention further comprises, after smelting, heating to 900-1000 ℃ in a closed environment and starting a stirrer to stir, wherein the stirring time is controlled to be 3-8 h; heating to 1000-1050 ℃ after stirring, preserving heat for 4-9 h, clarifying to enable bubbles to fully float, and then reducing the temperature to 600-700 ℃.
The invention also provides an optical element comprising a fluorophosphate optical glass according to the invention.
ADVANTAGEOUS EFFECTS OF INVENTION
The fluorophosphate optical glass of the present invention has sufficiently high internal transmittance in the visible light range. In addition, the fluorophosphate glass has low cost, good chemical stability and good staining degree; the glass transition temperature is low, which is beneficial to precision compression molding; the specific gravity is low, and the weight of the glass element and the optical system is reduced; the achromatic performance is excellent, and the imaging quality of an optical system can be improved; meanwhile, the crystallization temperature is lower, so that mass production is easier to realize.
Furthermore, the preparation method of the fluorophosphate optical glass is simple and feasible, raw materials are easy to obtain, and the fluorophosphate optical glass is suitable for mass production.
Detailed Description
Various exemplary embodiments, features and aspects of the invention are described in detail below. The word "exemplary" is used 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 illustration of the 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, well known methods, procedures, means, equipment and steps have not been described in detail so as not to obscure the present invention.
Unless otherwise indicated, all units used in this specification are units of international standard, and numerical values, ranges of values, etc. appearing in the present invention are understood to include systematic errors unavoidable in industrial production.
In the present specification, the meaning of "can" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
Reference throughout this specification to "some specific/preferred embodiments," "other specific/preferred embodiments," "an embodiment," and so forth, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the elements may be combined in any suitable manner in the various embodiments.
In the present specification, the numerical range indicated by the term "numerical value a to numerical value B" means a range including the end point numerical value A, B.
In the present specification, when "normal temperature" or "room temperature" is used, the temperature may be 10 to 40 ℃.
The invention firstly provides an optical glass which comprises the following components in terms of compounds:
Al(PO 3 ) 3 :5% -12%, preferably 6% -10%;
AlF 3 :22% -33%, preferably 23% -30%;
BaF 2 :7.5% -15%, preferably 9% -13%;
SrF 2 :20% -30%, preferably 22% -29%;
CaF 2 :20% -30%, preferably 22% -28%;
MgF 2 :2% -7%, preferably 2% -5%;
YF 3 ：0.5％about 8%, preferably 0.5% to 6%;
LiF:0.05 to 0.45%, preferably 0.1 to 0.35%;
the percentages are mass percentages;
refractive index n of the fluorophosphate optical glass d Is 1.43 to 1.46, abbe number v d 90 to 100.
The raw materials are introduced in various forms capable of introducing the corresponding contents thereof. The content of each component is expressed in mass percent as described below.
Al(PO 3 ) 3 Is an essential component for introducing Al, P and O into glass. Al, P and O are main elements constituting a glass skeleton, and can promote the formation of stable glass and improve the mechanical properties and chemical durability of the glass. Al (PO) 3 ) 3 When the content of (C) is less than 5%, the crystallization tendency of the glass is increased, and the mechanical properties and stability are deteriorated, while Al (PO) 3 ) 3 When the content of (2) is more than 12%, the refractive index and dispersion increase, and low-refractive-index and low-dispersion optical glass cannot be obtained. Thus, al (PO) 3 ) 3 The content of (2) may be controlled to 5% to 12%, preferably 6% to 10%.
AlF 3 Both elements (aluminum and fluorine) are components forming the skeleton of the glass network, and the fluorine element is also used for reducing the dispersion of the product and increasing the Abbe number v d Is a key component of (a) a (b). AlF (AlF) 3 Is effective in improving devitrification resistance and chemical stability of glass, and has important significance in improving mechanical property and linear expansion coefficient of glass. In the glass system of the present invention, when AlF 3 When the content of (2) is less than 22%, it is difficult to achieve an increase in Abbe number v due to a decrease in fluorine element in the glass d Is difficult to achieve n d 、υ d Is a matching relationship of (a); while when AlF 3 When the content of (C) is more than 33%, the glass transition temperature Tg increases greatly, resulting in an increase in molding temperature, and AlF 3 Too high a content also increases the opacifying tendency of the glass, increases brittleness and increases abrasion. Therefore AlF 3 The content of (2) is 22% to 33%, preferably 23% to 30%.
BaF 2 Can effectively adjust the refractive index of the glass and improve the crystallization performance of the glass. BaF (Baf) 2 When the content of (C) is less than 7.5%, these effects cannot be sufficiently obtained. BaF (Baf) 2 If the content of (b) is more than 15%, the refractive index of the glass becomes excessively large, and it is difficult to achieve desired optical properties, and the chemical stability of the glass is also lowered. In the present invention, baF 2 The content of (2) may be controlled to 7.5% to 15%, preferably 9% to 13%.
CaF 2 Can reduce the dispersion of the glass and improve the stability of the glass. CaF (CaF) 2 When the content of (C) is less than 20%, these effects cannot be sufficiently obtained. CaF (CaF) 2 If the content of (b) is more than 30%, the glass may not sufficiently achieve the desired optical properties, and the chemical stability of the glass may be reduced to increase the crystallization tendency of the glass. In the present invention, caF 2 The content of (2) may be controlled to 20% to 30%, preferably 22% to 28%.
Further, the inventors have found that when the ratio BaF 2 /CaF 2 When the content is too low, the crystallization resistance and chemical stability of the glass are reduced; when ratio BaF 2 /CaF 2 If the specific gravity of the glass is too high, the weight of the glass is increased, and it is difficult to achieve the purpose of weight reduction. Thus, baF will be used in the present invention 2 /CaF 2 The values are defined as 0.35 to 0.72, preferably 0.36 to 0.64.
SrF 2 Can effectively adjust the refractive index of the glass and improve the crystallization performance of the glass. SrF (SrF) 2 When the content of (C) is less than 20%, these effects cannot be sufficiently obtained. SrF (SrF) 2 If the content of (b) is more than 30%, the desired optical properties of the glass may not be sufficiently achieved, and the chemical stability of the glass may be lowered. In the present invention, srF 2 The content of (2) may be controlled to 20% to 30%, preferably 22% to 29%.
MgF 2 Are added as optional components in the present invention. MgF (MgF) 2 The dispersion and refractive index of the glass can be reduced, and the chemical stability of the glass can be improved. MgF (MgF) 2 When the content of (b) is less than 2%, low dispersion and refractive index cannot be formed. But MgF 2 If the content of (2) is more than 7%, the composition will causeThe devitrification property of the glass is deteriorated. Thus, in the present invention, mgF 2 The amount of (2) to (7), preferably 2% to (5).
Further, the inventor has found that BaF 2 /(CaF 2 +MgF 2 ) The value of (2) is closely related to crystallization property, chemical stability and the like of glass. When BaF 2 /(CaF 2 +MgF 2 ) When the value of (2) is too low, the devitrification resistance of the glass becomes poor, and the chemical stability becomes poor; when BaF 2 /(CaF 2 +MgF 2 ) If the value of (2) is too high, the specific gravity of the glass increases, and the dispersion of the glass increases, so that low dispersion cannot be formed. Thus, baF will be used in the present invention 2 /(CaF 2 +MgF 2 ) The value of (2) is limited to 0.3 to 0.64, preferably 0.32 to 0.56.
YF 3 Is beneficial to adjusting the optical properties of the glass such as refractive index, dispersion and the like, can obviously improve the chemical stability of the glass, increases the forming viscosity of the glass and is beneficial to forming the glass. However, if the glass is excessively introduced, the crystallization resistance of the glass is lowered, the refractive index and dispersion are greatly improved, and the desired optical properties cannot be achieved. Thus, in the present invention, YF 3 The amount of (2) may be controlled to be 0.5% to 8%, preferably 0.5% to 6%.
As a result of the study by the inventors, it was found that LiF in the present invention can reduce the surface tension during glass melting and effectively eliminate the bubble problem in fluorophosphorus glass, and LiF is present as an essential component in the present invention, but when the content exceeds 0.45%, since Li + The chemical stability of the glass is lowered, the crystallization property of the glass is deteriorated, and the abrasion degree is increased. Thus, in the present invention, the amount of LiF can be controlled between 0.05% and 0.45%, preferably between 0.1% and 0.35%.
Further, as a result of the studies of the present inventors, it was found that Al (PO 3 ) 3 The ratio of LiF is closely related to the devitrification properties of the glass when Al (PO 3 ) 3 When LiF is too low, the devitrification property of the glass becomes poor; when Al (PO) 3 ) 3 When the ratio of LiF is too high, the refractive index and dispersion will be greatly improved, and the effects of low refraction and low dispersion cannot be realizedAnd bubble foreign matters in the melting process are difficult to eliminate. Thus, in the present invention, al (PO 3 ) 3 The ratio of/LiF is controlled to be 13 to 180, preferably 13 to 150.
The fluorine (F) content in the glass is responsible for reducing the refractive index n of the glass d And dispersion is effective. If the fluorine (F) content is too small, the refractive index and dispersion tend to become large, and the objective of low refractive index and low dispersion cannot be achieved. Conversely, if the fluorine (F) content is too high, the ionic bonds in the glass will increase, and the characteristic of smaller ionic bond energy will lead to instability of the glass skeleton, which will make the glass easier to devitrify, and too high fluorine (F) content will also increase the abrasion of the product, while too high abrasion value will be detrimental to tolerance control in the glass finish polishing process. In the present invention, fluorine (F) in glass is added by recombination to AlF 3 、BaF 2 、CaF 2 、SrF 2 、MgF 2 LiF, and other fluorides are not artificially introduced in the present invention.
The present invention finds that the refractive index and dispersion of fluorophosphate glass are related to the oxygen to fluorine ratio (O/F) in the glass. The larger the oxygen-fluorine ratio (O/F), i.e., the higher the oxygen content, the higher the refractive index of the glass, the greater the dispersion, and a reasonable oxygen-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 content and the proportion of the oxide and the fluoride.
The hydroxyl (OH) content of the glass is closely related to the alkali resistance of the glass. The hydroxyl can damage the network structure of the glass in the glass, so that the stability of the glass skeleton is reduced, and when the glass skeleton is corroded by alkaline solution, the structure is more easily damaged, so that the alkali resistance of the glass is greatly reduced. Thus, in the present invention, hydroxyl groups in the glass are reduced as much as possible.
Further, the composition of the fluorophosphate optical glass of the present invention does not contain P 2 O 5 、NaF、KF、SnF 4 、La 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Ta 2 O 5 、GeO 2 Of, caO, baO, srO and MgOAt least one, and preferably none, of the components is present.
In the present invention, the fluorophosphate optical glass has an upper crystallization limit temperature L t At a glass transition temperature T of 680 ℃ or lower g Is below 440 ℃; and/or, the fluorophosphate optical glass has devitrification resistance T g /L t Greater than 0.64. The coloration lambda of the fluorophosphate optical glass 80 /λ 5 Lambda of (a) 80 310nm or less, lambda 5 Is 190nm or less. The specific gravity of the fluorophosphate optical glass is 3.80g/cm 3 The following is given. Alkali resistance R of the fluorophosphate optical glass OH (S) is 4 or more stages; abrasion degree F of the fluorophosphate optical glass A 455 or less.
Further, the invention also provides a preparation method of the fluorophosphate optical glass, which is characterized by comprising the following steps: weighing and uniformly mixing the components according to the proportion, smelting, and fully escaping volatile gas in the smelting process; preferably, the smelting temperature is 800-900 ℃; then casting or leaking into a forming die, or directly pressing and forming.
In the invention, when the glass powder is just put into the crucible, a large amount of volatile matters are generated due to the strong volatilization characteristic of the fluoride, and the hydroxyl groups in the glass are H due to the large amount of volatile matters 2 The O is carried out in a form, so that the hydroxyl content in the glass can be greatly reduced, and therefore, the optical glass manufacturing process needs to be processed in an open mode during the smelting process, so that volatile gas can fully escape.
Further, after smelting, the method further comprises the steps of raising the temperature to 900-1000 ℃ and starting a stirrer to stir, wherein the stirring time is controlled to be 3-8 hours; heating to 1000-1050 ℃ after stirring, preserving heat for 4-9 h, clarifying to enable bubbles to fully float, and then reducing the temperature to 600-700 ℃.
Specifically, sealing treatment is needed in the stirring, homogenizing, clarifying, cooling and discharging stages after smelting is completed, at this time, the glass is largely volatilized in the smelting process, the volatilization amount is greatly reduced, and if the glass is opened, H in the air can be caused 2 O is carried out again in the glass liquid, so that the content of hydroxyl is increased, and therefore, the optical glass manufacturing process needs to carry out sealing treatment in the stages of stirring, homogenizing, clarifying, cooling and discharging.
In order to reduce optical unevenness (streaks) and environmental pollution caused by volatilization of fluorine on the surface of the glass, it is preferable that a cooling cover plate is added to the upper surface of the forming mold through which molten glass flows in the production of the fluorophosphate glass, and an inert gas is introduced to the surface of the molten glass through the cooling cover plate, so that the molten glass is cooled and formed as soon as possible. In addition, in order to prevent the glass from corroding the smelting crucible, preferably, smelting is carried out in a non-reducing atmosphere, and oxygen can be introduced into the smelting crucible or an oxidation molten pool can be added during specific operation.
In addition, the invention also provides an optical element comprising the fluorophosphate optical glass according to the invention. The optical element can be produced by carrying out primary or secondary pressing on 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 it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Examples 1 to 20 in the table are examples of the present invention for explaining the obtaining of the refractive index n d Is 1.43 to 1.46, abbe number v d Typical experiments for fluorophosphate optical glasses of 90 to 100.
Examples 1 to 20
The components in the following tables 1, 2, 3 and 4 are calculated, weighed and mixed according to a specified proportion, and are put into a crucible made of platinum to be smelted at the temperature of 850 ℃, and the crucible is opened in the smelting process, so that gas can fully escape; after the raw materials are melted into glass liquid, in a closed environment, the temperature is increased to 950 ℃ and a stirrer made of platinum is started for stirring and homogenizing, the stirring time is controlled to be 5 hours, after stirring is completed, the temperature is increased to 1000 ℃ and the temperature is kept for 6 hours, clarification is carried out, bubbles are fully floated, then the temperature is reduced to 750 ℃ for casting or leaking into a forming die, the cooling cover plate is additionally arranged on the forming die, inert gas is led to the surface of the glass liquid through the cooling cover plate, and the problem of volatilization stripes caused by fluorine loss is solved. Finally, the optical glasses or optical elements of examples 1 to 20 were obtained by annealing and processing.
Comparative examples A to C
The optical glass of comparative example A, B, C was obtained by weighing the raw materials corresponding to the components in table 4 below in a predetermined ratio and preparing the same by the same method as in examples 1 to 20.
Comparative example D
The raw materials corresponding to the components of example 1 are weighed according to a specified proportion, the comparative example D is different from example 1 in that the smelting process is subjected to sealing treatment, and after smelting, a crucible is opened in the stirring, homogenizing, clarifying and cooling tapping stage, and the rest is identical.
Comparative example E
The raw materials corresponding to the components of example 1 are weighed according to a specified proportion, the comparative example E is different from example 1 in that the smelting process is subjected to sealing treatment, and the sealing treatment is also performed in the stirring, homogenizing, clarifying, cooling and discharging stages after smelting is completed, and the rest are completely the same.
Performance testing
The properties of the obtained fluorophosphate optical glass were measured by the following methods.
The refractive index nd and the Abbe number vd of the fluorophosphate optical glass are measured according to the test method of GB/T7962.1-2010.
Coloring degree lambda for optical glass shortwave transmission spectrum characteristic 80 /λ 5 And (3) representing. Lambda (lambda) 80 Refers to the corresponding wavelength lambda when the spectral transmittance reaches 80 percent 5 Refers to the corresponding wavelength when the spectral transmittance reaches 5%. Optical glass coloration degree measuring method according to JOGIS02-2003 of Japanese glass industry AssociationMethod ", the light transmittance of glass having a thickness of 10.+ -. 0.1mm subjected to parallel face-to-face polishing was measured. In the detection, λ is the factor of 5 The lower measurement limit of (2) is 190nm, and thus lambda 5 The measurement results of (2) were 190nm or less.
According to the test method of GB/T7962.12-2010, the internal transmittance (. Tau.) at the positions of 700nm, 400nm and 300nm is measured 10 Sample thickness of 10±0.1 mm).
The specific gravity of the obtained optical glass was measured according to the test method of GB/T7962.20-2010.
The transition temperature T of the optical glass obtained was measured according to the test method of GB/T7962.16-2010 g Testing was performed.
L t The temperature corresponding to the highest temperature heat absorption peak in the DTA curve is L t 。
Abrasion degree F of the obtained optical glass according to the test method of GB/T7962.19-2010 A Testing was performed.
R for stabilizing alkali-resistant action of optical glass OH (S) the test was performed by immersing six-face polished samples having dimensions of 40 mm. Times.40 mm. Times.5 mm in a sodium hydroxide solution with a temperature of 50.+ -. 3 ℃ and a concentration of 0.01mol/L under sufficient stirring for 15 hours.
The hydroxyl group content in the glass cannot be quantitatively tested, but the hydroxyl group has obvious absorption peak in the 3000nm wave band, so the hydroxyl group content in the glass is characterized by testing the 3000nm transmittance of the glass in the invention. According to the test method of GB/T7962.12-2010, the internal transmittance (τ) at a wavelength of 3000nm 10 Sample thickness of 10±0.1 mm).
TABLE 1 glass Components and Performance parameters for examples 1-6
TABLE 2 glass Components and Performance parameters for examples 7-12
TABLE 3 glass Components and Performance parameters for examples 13-18
TABLE 4 glass compositions and performance parameters for examples 19-20 and comparative example A, B, C
TABLE 5 Performance parameters for example 1 and comparative example D, E
As can be seen from examples 1 to 20: the present invention preferably uses Al (PO) 3 ) 3 Form of (c) introduction of P 2 O 5 Its advantages are greatly reduced abnormal times and stable and controllable performance. The glass of the examples had higher chemical stability and lower glass transition temperature than the comparative examples when the same, expected optical constants were achieved, and the lower glass transition temperature values indicated that the product was more suitable for precision press molding.
In comparative example A, when the content of LiF is more than 0.45%, R OH The (S) value increases sharply, the leaching quality increases, the alkali resistance stability becomes poor, the chemical stability of the glass becomes poor, T g /L t The value becomes smaller and the crystallization property of the glass becomes worse. Degree of abrasion F at the same time A And also increases, which is detrimental to tolerance control during the glass finish polishing process.
In comparative example B, baF 2 Is less than 7.5% so that BaF 2 /(CaF 2 +MgF 2 ) The ratio is lower than 0.3, and the alkali resistance D A Is in the order of 5, the number of the stages is 5,D A the leaching quality is greatly increased, which indicates that the chemical stability of the glass is seriously deteriorated, T g The decrease in the value of/Lt indicates that the crystallization property of the glass is poor, the glass is not easily molded, and the abrasion degree is also poor.
In comparative example C, al (PO 3 ) 3 The ratio of LiF is too low, other compositions are within the limits of the invention, nd, vd, alkali resistance, abrasion resistance, specific gravity are in accordance with the limits of the invention, but due to Al (PO) 3 ) 3 The ratio of/LiF is lower than 13, and the crystallization property is deteriorated.
As can be seen from Table 5, the preparation method of comparative example D, E is different from example 1 in that the glass has a higher hydroxyl group content and a lower transmittance in the 3000nm band, resulting in deterioration of alkali resistance, and the glass prepared by the preparation method of example 1 has a lower hydroxyl group content, a high transmittance in the 3000nm band and an improved alkali resistance.
It should be noted that, although the technical solution of the present invention is described in specific examples, those skilled in the art can understand that the present invention should not be limited thereto.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described. The terminology used herein was chosen in order to best explain the principles of the embodiments, the practical application, or the technical improvements in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.

Claims (10)

1. A fluorophosphate optical glass, characterized in that it comprises the following components in terms of compounds:
Al(PO 3 ) 3 :5% -12%, preferably 6% -10%;
AlF 3 :22% -33%, preferably 23% -30%;
BaF 2 :7.5% -15%, preferably 9% -13%;
SrF 2 :20% -30%, preferably 22% -29%;
CaF 2 :20% -30%, preferably 22% -28%;
MgF 2 :2% -7%, preferably 2% -5%;
YF 3 :0.5 to 8 percent, preferably 0.5 to 6 percent;
LiF:0.05 to 0.45%, preferably 0.1 to 0.35%;
the percentages are mass percentages;
refractive index n of the fluorophosphate optical glass d Is 1.43 to 1.46, abbe number v d 90 to 100.
2. The fluorophosphate optical glass according to claim 1, wherein the BaF is in weight percent 2 Content of (2) and CaF 2 Ratio of the content of BaF 2 /CaF 2 0.35 to 0.72, preferably 0.36 to 0.64; and/or the number of the groups of groups,
BaF 2 content of (2) and MgF 2 And CaF 2 Ratio of the sum of the contents of BaF 2 /(MgF 2 +CaF 2 ) 0.3 to 0.64, preferably 0.32 to 0.56; and/or the number of the groups of groups,
Al(PO 3 ) 3 ratio of content of (2) to content of LiF Al (PO 3 ) 3 The ratio of LiF is 13 to 180, preferably 13 to 150.
3. The optical glass according to claim 1 or 2, wherein the fluorophosphate optical glass does not contain P in its composition 2 O 5 、NaF、KF、SnF 4 、La 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Ta 2 O 5 、GeO 2 At least one of, caO, baO, srO and MgO.
4. A fluorophosphate optical glass according to any one of claims 1 to 3, wherein the fluorophosphate optical glass has a crystallization upper limit temperature L t At a glass transition temperature T of 680 ℃ or lower g Is below 440 ℃; and/or the number of the groups of groups,
devitrification resistance T of the fluorophosphate optical glass g /L t Greater than 0.64.
5. The fluorophosphate optical glass according to any one of claims 1 to 4, wherein the fluorophosphate optical glass has a coloring degree λ of 80 /λ 5 Lambda of (a) 80 310nm or less, lambda 5 Is 190nm or less.
6. The fluorophosphate optical glass according to any one of claims 1 to 5, wherein the fluorophosphate optical glass has a specific gravity of 3.80g/cm 3 The following is given.
7. The fluorophosphate optical glass according to any one of claims 1 to 6, wherein the fluorophosphate optical glass has alkali resistance R OH (S) is 4 or more stages; and/or
Abrasion degree F of the fluorophosphate optical glass A 455 or less.
8. A method for producing the fluorophosphate optical glass according to any one of claims 1 to 7, comprising: weighing and uniformly mixing the components according to the proportion, smelting, and fully escaping volatile gas in the smelting process; preferably, the smelting temperature is 800-900 ℃; then casting or leaking into a forming die, or directly pressing and forming.
9. The preparation method according to claim 8, further comprising, after the smelting, raising the temperature to 900-1000 ℃ and starting a stirrer to stir in a closed environment, wherein the stirring time is controlled to be 3-8 h; heating to 1000-1050 ℃ after stirring, preserving heat for 4-9 h, clarifying to enable bubbles to fully float, and then reducing the temperature to 600-700 ℃.
10. An optical element comprising the fluorophosphate optical glass according to any one of claims 1 to 7.
CN202310585795.6A 2023-05-23 2023-05-23 Fluorophosphate optical glass, preparation method thereof and optical element Pending CN116514394A (en)

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