CN116514394A - Fluorophosphate optical glass, its preparation method and optical element - Google Patents

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

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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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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/12Silica-free oxide glass compositions
    • C03C3/23Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron
    • C03C3/247Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron containing fluorine and phosphorus
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03BMANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B11/00Pressing molten glass or performed glass reheated to equivalent low viscosity without blowing
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03BMANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00Other methods of shaping glass
    • C03B19/02Other methods of shaping glass by casting molten glass, e.g. injection moulding
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00Technologies relating to the processing of minerals
    • Y02P40/50Glass production, e.g. reusing waste heat during processing or shaping
    • Y02P40/57Improving 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)
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  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Glass Compositions (AREA)

Abstract

本发明提供一种氟磷酸盐光学玻璃及其制备方法和光学元件。氟磷酸盐光学玻璃包含以化合物计的以下组分:Al(PO3)3:5%~12%;AlF3:22%~33%;BaF2:7.5%~15%;SrF2:20%~30%;CaF2:20%~30%;MgF2:2%~7%;YF3:0.5%~8%;LiF:0.05%~0.45%;上述百分比均为质量百分比;所述氟磷酸盐光学玻璃的折射率nd为1.43~1.46,阿贝数υd为90~100。本发明的氟磷酸盐光学玻璃在可见光范围内的内部透过率足够高。并且,本发明的氟磷酸盐玻璃不仅成本低,还具有良好的化学稳定性、着色度;玻璃转变温度较低,有利于精密模压成型。The invention provides a fluorophosphate optical glass, a preparation method thereof and an optical element. Fluorophosphate optical glass contains the following components in terms of compounds: Al(PO 3 ) 3 : 5% to 12%; AlF 3 : 22% to 33%; BaF 2 : 7.5% to 15%; SrF 2 : 20% ~30%; CaF 2 : 20%~30%; MgF 2 : 2%~7%; YF 3 : 0.5%~8%; LiF: 0.05%~0.45%; The refractive index n d of salt optical glass is 1.43-1.46, and the Abbe number υ d is 90-100. The fluorophosphate optical glass of the present invention has a sufficiently high internal transmittance in the visible light range. Moreover, the fluorophosphate glass of the present invention not only has low cost, but also has good chemical stability and coloring degree; the glass transition temperature is low, which is beneficial to precision molding.

Description

氟磷酸盐光学玻璃及其制备方法和光学元件Fluorophosphate optical glass, its preparation method and optical element

技术领域technical field

本发明涉及一种氟磷酸盐光学玻璃及其制备方法和光学元件,属于光学玻璃领域。The invention relates to a fluorophosphate optical glass, a preparation method thereof and an optical element, belonging to the field of optical glass.

背景技术Background technique

低折射率、低色散的氟磷酸盐光学玻璃因为具有低色散特性和消除二级光谱特殊色散的优越特性,被广泛应用于高精度色差校正用的光学仪器的镜头模组中,已成为相关光学设计中不可或缺的元器件材料。近年来,随着光学设备的数字化和高精密化的迅速发展,成像像素日趋提高,因而对分辨率的要求也越来越高。Fluorophosphate optical glass with low refractive index and low dispersion is widely used in the lens module of optical instruments for high-precision chromatic aberration correction because of its low dispersion characteristics and the superior characteristics of eliminating the special dispersion of the secondary spectrum. Indispensable component material in the design. In recent years, with the rapid development of digitalization and high precision of optical equipment, the imaging pixels are increasing day by day, so the requirements for resolution are also getting higher and higher.

专利申请CN102745899A、CN1931761A公开的光学玻璃,其中均含有5%以上的P5+,而过多的引入P5+将不可避免的引入较多的O2-,导致色散增加,而无法获得更低的色散值。The optical glasses disclosed in patent applications CN102745899A and CN1931761A all contain more than 5% P 5+ , and too much introduction of P 5+ will inevitably introduce more O 2- , resulting in increased dispersion, and cannot obtain lower dispersion value.

专利申请CN102674689A公开的氟磷酸盐光学玻璃,其中Zn2+的含量为0.5-15%,Zn2+具有较大的离子半径,过多的引入Zn2+将破坏玻璃的网络结构,降低玻璃的析晶性能、化学稳定性和着色度。另外,如果以Zn(PO3)2引入Zn2+将不可避免的引入较多的O2-,导致色散增加,而无法获得更低的色散值。Patent application CN102674689A discloses fluorophosphate optical glass, wherein the content of Zn 2+ is 0.5-15%, and Zn 2+ has a larger ion radius, too much introduction of Zn 2+ will destroy the network structure of the glass and reduce the Crystallization properties, chemical stability and degree of coloration. In addition, if Zn 2+ is introduced by Zn(PO 3 ) 2 , more O 2- will inevitably be introduced, resulting in increased dispersion, but a lower dispersion value cannot be obtained.

专利申请CN101544468B公开的氟磷酸盐光学玻璃,其中O2-/P5+的摩尔比大于3.5,引入较多的O2-,导致色散增加,而无法获得更低的色散值。本发明中O2-/P5+的摩尔比为3。In the fluorophosphate optical glass disclosed in patent application CN101544468B, the molar ratio of O 2- /P 5+ is greater than 3.5, and more O 2- is introduced, resulting in increased dispersion, but cannot obtain a lower dispersion value. The molar ratio of O 2− /P 5+ in the present invention is 3.

专利申请CN106904831A公开的氟磷酸盐光学玻璃,其含有0.5%~8%的LiF,因Li+的半径较小,过多的Li+会导致玻璃的耐碱性能急剧下降,磨耗度变差,严重影响后续对光学玻璃镜片的加工及镀膜工艺,同时析晶性能变差,熔制过程中析晶导致的条纹严重,大大降低玻璃的良品率。The fluorophosphate optical glass disclosed in the patent application CN106904831A contains 0.5% to 8% of LiF. Because the radius of Li + is small, too much Li + will lead to a sharp decline in the alkali resistance of the glass, and the degree of wear will deteriorate, seriously It affects the subsequent processing and coating process of optical glass lenses, and at the same time, the devitrification performance becomes worse, and the stripes caused by devitrification during the melting process are serious, which greatly reduces the yield of glass.

发明内容Contents of the invention

发明要解决的问题The problem to be solved by the invention

本发明的目的在于提供一种氟磷酸盐光学玻璃及其制备方法和光学元件。所述氟磷酸盐光学玻璃的折射率nd为1.43~1.46,阿贝数υd为90~100。所述氟磷酸盐光学玻璃具有良好的化学稳定性和高的可见光透过率以及较低的玻璃转变温度,且能够消除现有的光学玻璃的熔制温度高、挥发条纹难控制的缺陷。The object of the present invention is to provide a kind of fluorophosphate optical glass and its preparation method and optical element. The refractive index n d of the fluorophosphate optical glass is 1.43-1.46, and the Abbe number υ d is 90-100. The fluorophosphate optical glass has good chemical stability, high visible light transmittance and low glass transition temperature, and can eliminate the defects of high melting temperature and difficult control of volatilization streaks in the existing optical glass.

进一步地,本发明还提供一种氟磷酸盐光学玻璃的制备方法,该制备方法简单易行,原料易于获取,同时还能够实现稳定批量生产。Further, the present invention also provides a preparation method of fluorophosphate optical glass, which is simple and easy to obtain raw materials, and can realize stable mass production at the same time.

用于解决问题的方案solutions to problems

本发明提供一种氟磷酸盐光学玻璃,其包含以化合物计的以下组分:The invention provides a kind of fluorophosphate optical glass, which comprises the following components in terms of compounds:

Al(PO3)3:5%~12%,优选6%~10%;Al(PO 3 ) 3 : 5% to 12%, preferably 6% to 10%;

AlF3:22%~33%,优选23%~30%;AlF 3 : 22% to 33%, preferably 23% to 30%;

BaF2:7.5%~15%,优选9%~13%;BaF 2 : 7.5% to 15%, preferably 9% to 13%;

SrF2:20%~30%,优选22%~29%;SrF 2 : 20% to 30%, preferably 22% to 29%;

CaF2:20%~30%,优选22%~28%;CaF 2 : 20% to 30%, preferably 22% to 28%;

MgF2:2%~7%,优选2%~5%;MgF 2 : 2% to 7%, preferably 2% to 5%;

YF3:0.5%~8%,优选0.5%~6%;YF 3 : 0.5% to 8%, preferably 0.5% to 6%;

LiF:0.05%~0.45%,优选0.1%~0.35%;LiF: 0.05% to 0.45%, preferably 0.1% to 0.35%;

上述百分比均为质量百分比;The above percentages are all percentages by mass;

所述氟磷酸盐光学玻璃的折射率nd为1.43~1.46,阿贝数υd为90~100。The refractive index n d of the fluorophosphate optical glass is 1.43-1.46, and the Abbe number υ d is 90-100.

根据本发明所述的氟磷酸盐光学玻璃,其中,以重量百分比计,BaF2的含量与CaF2的含量之比BaF2/CaF2为0.35~0.72,优选0.36~0.64;和/或,BaF2的含量与MgF2和CaF2的含量之和的比值BaF2/(MgF2+CaF2)为0.3~0.64,优选0.32~0.56;和/或,According to the fluorophosphate optical glass of the present invention, wherein, in terms of weight percentage, the ratio BaF 2 /CaF 2 of the content of BaF 2 to the content of CaF 2 is 0.35-0.72, preferably 0.36-0.64; and/or, BaF The ratio BaF 2 /(MgF 2 +CaF 2 ) of the content of 2 to the sum of the contents of MgF 2 and CaF 2 is 0.3-0.64, preferably 0.32-0.56; and/or,

Al(PO3)3的含量与LiF的含量之比Al(PO3)3/LiF为13~180,优选13~150。The ratio Al(PO 3 ) 3 /LiF of the content of Al(PO 3 ) 3 to the content of LiF is 13-180, preferably 13-150.

根据本发明所述的氟磷酸盐光学玻璃,其中,所述氟磷酸盐光学玻璃的组成中不含有P2O5、NaF、KF、SnF4、La2O3、Gd2O3、Y2O3、Yb2O3、Ta2O5、GeO2、CaO、BaO、SrO和MgO中的至少一种。According to the fluorophosphate optical glass of 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 At least one of O 3 , Yb 2 O 3 , Ta 2 O 5 , GeO 2 , CaO, BaO, SrO, and MgO.

根据本发明所述的氟磷酸盐光学玻璃,其中,所述氟磷酸盐光学玻璃的析晶上限温度Lt为680℃以下,玻璃转变温度Tg为440℃以下;和/或,According to the fluorophosphate optical glass of the present invention, wherein, the crystallization upper limit temperature L t of the fluorophosphate optical glass is lower than 680° C., and the glass transition temperature T g is lower than 440° C.; and/or,

所述氟磷酸盐光学玻璃的耐失透性Tg/Lt大于0.64。The devitrification resistance T g /L t of the fluorophosphate optical glass is greater than 0.64.

根据本发明所述的氟磷酸盐光学玻璃,其中,所述氟磷酸盐光学玻璃的着色度λ805中的λ80为310nm以下,λ5为190nm以下。According to the fluorophosphate optical glass of the present invention, λ 80 of the coloring degree λ 805 of the fluorophosphate optical glass is 310nm or less, and λ 5 is 190nm or less.

根据本发明所述的氟磷酸盐光学玻璃,其中,所述氟磷酸盐光学玻璃的比重为3.80g/cm3以下。According to the fluorophosphate optical glass of the present invention, wherein the specific gravity of the fluorophosphate optical glass is 3.80 g/cm 3 or less.

根据本发明所述的氟磷酸盐光学玻璃,其中,所述氟磷酸盐光学玻璃的耐碱性ROH(S)为4级及以上;和/或According to the fluorophosphate optical glass of the present invention, wherein, the alkali resistance R OH (S) of the fluorophosphate optical glass is grade 4 or above; and/or

所述氟磷酸盐光学玻璃的磨耗度FA为455以下。The abrasion degree F A of the fluorophosphate optical glass is 455 or less.

本发明还提供一种根据本发明所述的氟磷酸盐光学玻璃的制备方法,其包括:将各组分按照比例称量、混合均匀后进行熔炼,并且在所述熔炼过程中,使挥发气体充分逸出;优选地,所述熔炼的温度为800~900℃;然后浇注或漏注在成型模具中,或者直接压制成型。The present invention also provides a method for preparing the fluorophosphate optical glass according to the present invention, which includes: weighing each component according to the proportion, mixing them uniformly and then melting them, and during the melting process, making the volatile gas fully escape; preferably, the temperature of the smelting is 800-900°C; and then poured or leaked into the forming mold, or directly pressed into shape.

根据本发明所述的制备方法,其中,在所述熔炼之后还包括,在密闭环境下,将温度升高至900~1000℃并开启搅拌器进行搅拌,搅拌时间控制在3~8h;搅拌完成后升温至1000~1050℃并保温4~9h,进行澄清,使气泡充分上浮,然后将温度降至600~700℃。According to the preparation method of the present invention, after the smelting, it also includes, in a closed environment, raising the temperature to 900-1000°C and turning on the stirrer for stirring, and the stirring time is controlled at 3-8h; the stirring is completed Afterwards, raise the temperature to 1000-1050°C and keep it warm for 4-9 hours for clarification to make the bubbles fully float up, and then lower the temperature to 600-700°C.

本发明还提供一种光学元件,其包括根据本发明所述的氟磷酸盐光学玻璃。The present invention also provides an optical element comprising the fluorophosphate optical glass according to the present invention.

发明的效果The effect of the invention

本发明的氟磷酸盐光学玻璃在可见光范围内的内部透过率足够高。并且,本发明的氟磷酸盐玻璃不仅成本低,还具有良好的化学稳定性、着色度;玻璃转变温度较低,有利于精密模压成型;其比重较低,减轻了玻璃元件和光学系统的重量;具有优良的消色差性能,能够改善光学系统的成像质量;同时析晶温度较低,使其更容易实现批量生产。The fluorophosphate optical glass of the present invention has a sufficiently high internal transmittance in the visible light range. Moreover, the fluorophosphate glass of the present invention not only has low cost, but also has good chemical stability and coloring degree; the glass transition temperature is low, which is conducive to precision molding; its specific gravity is low, which reduces the weight of glass components and optical systems ; It has excellent achromatic performance, which can improve the imaging quality of the optical system; at the same time, the crystallization temperature is low, making it easier to achieve mass production.

进一步地,本发明的氟磷酸盐光学玻璃的制备方法简单易行,原料易于获取,适合大批量生产。Furthermore, the preparation method of the fluorophosphate optical glass of the present invention is simple and feasible, the raw materials are easy to obtain, and are suitable for mass production.

具体实施方式Detailed ways

以下将详细说明本发明的各种示例性实施例、特征和方面。在这里专用的词“示例性”意为“用作例子、实施例或说明性”。这里作为“示例性”所说明的任何实施例不必解释为优于或好于其它实施例。Various exemplary embodiments, features, and aspects of the invention are 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 superior or better than other embodiments.

另外,为了更好地说明本发明,在下文的具体实施方式中给出了众多的具体细节。本领域技术人员应当理解,没有某些具体细节,本发明同样可以实施。在另外一些实例中,对于本领域技术人员熟知的方法、手段、器材和步骤未作详细描述,以便于凸显本发明的主旨。In addition, in order to better illustrate the present invention, numerous specific details are given in the specific embodiments below. It will be understood by those skilled in the art that the present invention may be practiced without certain of the specific details. In other instances, methods, means, devices and steps well known to those skilled in the art are not described in detail in order to highlight the gist of the present invention.

如无特殊声明,本说明书中所使用的单位均为国际标准单位,并且本发明中出现的数值,数值范围,均应当理解为包含了工业生产中所不可避免的系统性误差。Unless otherwise stated, the units used in this specification are all international standard units, and the numerical values and numerical ranges appearing in the present invention should be understood as including inevitable systematic errors in industrial production.

本说明书中,使用“可以”表示的含义包括了进行某种处理以及不进行某种处理两方面的含义。In this specification, the meaning expressed by "may" includes the meaning of performing certain processing and not performing certain processing.

本说明书中,所提及的“一些具体/优选的实施方案”、“另一些具体/优选的实施方案”、“实施方案”等是指所描述的与该实施方案有关的特定要素(例如,特征、结构、性质和/或特性)包括在此处所述的至少一种实施方案中,并且可存在于其它实施方案中或者可不存在于其它实施方案中。另外,应理解,所述要素可以任何合适的方式组合在各种实施方案中。In this specification, references to "some specific/preferred embodiments", "other specific/preferred embodiments", "embodiments" and the like refer to specific elements described in relation to the embodiments (for example, A feature, structure, property, and/or characteristic) 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 described elements may be combined in any suitable manner in the various embodiments.

本说明书中,使用“数值A~数值B”表示的数值范围是指包含端点数值A、B的范围。In this specification, the numerical range represented by "numerical value A - numerical value B" means the range which includes numerical value A and B of an end point.

本说明书中,使用“常温”、“室温”时,其温度可以是10~40℃。In the present specification, when "normal temperature" and "room temperature" are used, the temperature may be 10 to 40°C.

本发明首先提供一种光学玻璃,其包含以化合物计的以下组分:The present invention firstly provides an optical glass, which comprises the following components in terms of compounds:

Al(PO3)3:5%~12%,优选6%~10%;Al(PO 3 ) 3 : 5% to 12%, preferably 6% to 10%;

AlF3:22%~33%,优选23%~30%;AlF 3 : 22% to 33%, preferably 23% to 30%;

BaF2:7.5%~15%,优选9%~13%;BaF 2 : 7.5% to 15%, preferably 9% to 13%;

SrF2:20%~30%,优选22%~29%;SrF 2 : 20% to 30%, preferably 22% to 29%;

CaF2:20%~30%,优选22%~28%;CaF 2 : 20% to 30%, preferably 22% to 28%;

MgF2:2%~7%,优选2%~5%;MgF 2 : 2% to 7%, preferably 2% to 5%;

YF3:0.5%~8%,优选0.5%~6%;YF 3 : 0.5% to 8%, preferably 0.5% to 6%;

LiF:0.05%~0.45%,优选0.1%~0.35%;LiF: 0.05% to 0.45%, preferably 0.1% to 0.35%;

上述百分比均为质量百分比;The above percentages are all percentages by mass;

所述氟磷酸盐光学玻璃的折射率nd为1.43~1.46,阿贝数υd为90~100。The refractive index n d of the fluorophosphate optical glass is 1.43-1.46, and the Abbe number υ d is 90-100.

原料引入方式采用能够引入其相应含量的化合物的多种形式。如下所述中,各组分的含量是以质量百分比来表示的。The raw material introduction mode adopts various forms capable of introducing the compound in its corresponding content. In the following description, the content of each component is expressed in mass percentage.

Al(PO3)3是用于在玻璃中引入Al、P、O的必须组分。Al、P、O是构成玻璃骨架的主要元素,能够促进稳定玻璃的形成以及提高玻璃的机械性能和化学耐久性。Al(PO3)3的含量低于5%时,增加玻璃的析晶倾向,使机械性能和稳定性变差,而Al(PO3)3的含量高于12%时,折射率和色散增大,无法获得低折射、低色散光学玻璃。因此,Al(PO3)3的含量可以控制为5%~12%,优选为6%~10%。Al(PO 3 ) 3 is an essential component for introducing Al, P, O into glass. Al, P, and O are the main elements constituting the glass skeleton, which can promote the formation of stable glass and improve the mechanical properties and chemical durability of glass. When the content of Al(PO 3 ) 3 is lower than 5%, the crystallization tendency of the glass will be increased, and the mechanical properties and stability will be deteriorated, while when the content of Al(PO 3 ) 3 is higher than 12%, the refractive index and dispersion will increase. Large, can not obtain low refraction, low dispersion optical glass. Therefore, the content of Al(PO 3 ) 3 can be controlled to be 5%-12%, preferably 6%-10%.

AlF3引入的两种元素(铝和氟)也都是构成玻璃网络骨架的组分,而氟元素也是降低产品色散、提高阿贝数υd的关键性成分。AlF3对提高玻璃的耐失透性和化学稳定性有效,对提高玻璃的机械性能和线膨胀系数也具有重要意义。在本发明的玻璃系统中,当AlF3的含量低于22%时,因玻璃中氟元素的减少而难以实现提高阿贝数υd的目标,即难以实现nd、υd的匹配关系;而当AlF3的含量高于33%时,玻璃的转变温度Tg会大幅度上升,造成成型温度升高,另外,AlF3含量过大也会使玻璃的乳浊趋势增大、脆性增加、磨耗度增大。所以,AlF3的含量为22%~33%,优选为23%~30%。The two elements (aluminum and fluorine) introduced by AlF 3 are also components that constitute the glass network skeleton, and fluorine is also a key component to reduce product dispersion and increase the Abbe number υd . AlF 3 is effective for improving the devitrification resistance and chemical stability of glass, and is also of great significance for improving the mechanical properties and linear expansion coefficient of glass. In the glass system of the present invention, when the content of AlF3 is lower than 22%, it is difficult to achieve the goal of increasing the Abbe number υd due to the reduction of fluorine in the glass, that is, it is difficult to realize the matching relationship of nd and υd ; When the AlF 3 content is higher than 33%, the transition temperature Tg of the glass will increase significantly, resulting in an increase in the forming temperature. In addition, the excessive AlF 3 content will also increase the opacity tendency of the glass, increase the brittleness, and wear. degree increases. Therefore, the content of AlF 3 is 22% to 33%, preferably 23% to 30%.

BaF2可以有效地调整玻璃的折射率和提高玻璃的析晶性能。BaF2的含量低于7.5%时,不能充分地达到这些效果。BaF2的含量高于15%时,则会使玻璃折射率过度变大,很难达到预想的光学性质,同时也会降低玻璃的化学稳定性。本发明中,BaF2的含量可以控制为7.5%~15%,优选9%~13%。BaF 2 can effectively adjust the refractive index of glass and improve the crystallization performance of glass. When the content of BaF 2 is less than 7.5%, these effects cannot be sufficiently obtained. When the content of BaF 2 is higher than 15%, the refractive index of the glass will be excessively increased, making it difficult to achieve the desired optical properties, and at the same time, the chemical stability of the glass will be reduced. In the present invention, the content of BaF 2 can be controlled to be 7.5%-15%, preferably 9%-13%.

CaF2可以降低玻璃的色散和提高玻璃的稳定性。CaF2的含量低于20%时,不能充分达到这些效果。CaF2的含量高于30%时,则会使玻璃不能充分达到预想的光学性质,同时也会降低玻璃的化学稳定性,增加玻璃的析晶倾向。本发明中,CaF2的含量可以控制为20%~30%,优选为22%~28%。CaF 2 can reduce the dispersion of the glass and improve the stability of the glass. When the content of CaF 2 is less than 20%, these effects cannot be sufficiently obtained. When the content of CaF 2 is higher than 30%, the glass cannot fully achieve the expected optical properties, and at the same time, the chemical stability of the glass will be reduced, and the crystallization tendency of the glass will be increased. In the present invention, the content of CaF 2 can be controlled to be 20%-30%, preferably 22%-28%.

进一步地,经发明人研究发现,当比值BaF2/CaF2过低时,玻璃的抗析晶能力、化学稳定性下降;当比值BaF2/CaF2过高时,玻璃的比重增加,难以达到轻量化的目的。因此,本发明中将BaF2/CaF2值限定为0.35~0.72,优选0.36~0.64。Further, the inventors found that when the ratio BaF 2 /CaF 2 is too low, the anti-devitrification ability and chemical stability of the glass decrease; when the ratio BaF 2 /CaF 2 is too high, the specific gravity of the glass increases, making it difficult to achieve Lightweight purpose. Therefore, in the present invention, the BaF 2 /CaF 2 value is limited to 0.35-0.72, preferably 0.36-0.64.

SrF2可以有效地调整玻璃的折射率和提高玻璃的析晶性能。SrF2的含量低于20%时,不能充分地达到这些效果。SrF2的含量高于30%时,则会使玻璃不能充分达到预想的光学性质,同时也会降低玻璃的化学稳定性。本发明中,SrF2的含量可以控制为20%~30%,优选22%~29%。SrF 2 can effectively adjust the refractive index of glass and improve the crystallization performance of glass. When the content of SrF 2 is less than 20%, these effects cannot be sufficiently obtained. When the content of SrF 2 is higher than 30%, the glass cannot fully achieve the expected optical properties, and the chemical stability of the glass will also be reduced. In the present invention, the content of SrF 2 can be controlled at 20%-30%, preferably 22%-29%.

MgF2在本发明中是作为任选的组分加入的。MgF2可以降低玻璃的色散和折射率,同时可以提高玻璃的化学稳定性。MgF2的含量低于2%时,无法形成低的色散和折射率。但MgF2的含量高于7%时,会使玻璃的析晶性能恶化。因此,本发明中,MgF2的量可以控制为2%~7%,优选2%~5%。MgF 2 is added as an optional component in the present invention. MgF 2 can reduce the dispersion and refractive index of the glass, and at the same time can improve the chemical stability of the glass. When the content of MgF 2 is less than 2%, low dispersion and refractive index cannot be formed. However, when the content of MgF2 is higher than 7%, the crystallization performance of the glass will be deteriorated. Therefore, in the present invention, the amount of MgF 2 can be controlled at 2%-7%, preferably 2%-5%.

进一步地,经发明人研究发现,BaF2/(CaF2+MgF2)的值与玻璃的析晶性能、化学稳定性等密切相关。当BaF2/(CaF2+MgF2)的值过低时,玻璃的抗析晶性能变差,并且化学稳定性也会变差;当BaF2/(CaF2+MgF2)的值过高时,玻璃的比重增大,并且玻璃的色散会增大,无法形成低的色散。因此,本发明中将BaF2/(CaF2+MgF2)的值限定在0.3~0.64,优选0.32~0.56。Furthermore, the inventors found that the value of BaF 2 /(CaF 2 +MgF 2 ) is closely related to the crystallization performance and chemical stability of the glass. When the value of BaF 2 /(CaF 2 +MgF 2 ) is too low, the anti-devitrification performance of the glass will be deteriorated, and the chemical stability will also be deteriorated; when the value of BaF 2 /(CaF 2 +MgF 2 ) is too high , the specific gravity of the glass increases, and the dispersion of the glass increases, making it impossible to form a low dispersion. Therefore, in the present invention, the value of BaF 2 /(CaF 2 +MgF 2 ) is limited to 0.3-0.64, preferably 0.32-0.56.

YF3对调节玻璃的折射率和色散等光学性能有益,并可以明显改善玻璃的化学稳定性,增大玻璃的成型粘度,有利于玻璃的成型。但是,如果过量引入则会使玻璃的抗析晶性能下降,折射率和色散大幅度提高,无法达到预想的光学性质。因此,本发明中,YF3的量可以控制为0.5%~8%,优选0.5%~6%。YF 3 is beneficial to adjust the optical properties of glass such as refractive index and dispersion, and can obviously improve the chemical stability of glass, increase the molding viscosity of glass, and is beneficial to the molding of glass. However, if it is introduced in excess, the devitrification resistance of the glass will be reduced, the refractive index and dispersion will be greatly increased, and the expected optical properties cannot be achieved. Therefore, in the present invention, the amount of YF 3 can be controlled at 0.5% to 8%, preferably 0.5% to 6%.

经发明人研究发现,在本发明中LiF能够降低玻璃熔炼过程时的表面张力,有效消除氟磷玻璃中的气泡问题,因此在发明中LiF是作为必要成分存在,但是当其含量超过0.45%时,由于Li+的特性,玻璃的化学稳定性会下降,同时玻璃的析晶性能变差,磨耗度也会增大。因此,本发明中,LiF的量可以控制在0.05%~0.45%之间,优选0.1%~0.35%。The inventors have found that LiF can reduce the surface tension during the glass melting process in the present invention and effectively eliminate the bubble problem in fluorophosphorus glass. Therefore, LiF exists as an essential component in the invention, but when its content exceeds 0.45%. , due to the characteristics of Li + , the chemical stability of the glass will decrease, and at the same time, the crystallization performance of the glass will deteriorate, and the degree of wear will increase. Therefore, in the present invention, the amount of LiF can be controlled between 0.05%-0.45%, preferably 0.1%-0.35%.

进一步地,经本发明人研究发现,Al(PO3)3/LiF比值与玻璃的析晶性能密切相关,当Al(PO3)3/LiF过低时,玻璃的析晶性能变差;当Al(PO3)3/LiF过高时,折射率和色散将会大幅度提高,无法实现低折射、低色散的效果,同时熔制过程中的气泡异物难以消除。因此,本发明中,Al(PO3)3/LiF比值控制为13~180,优选13~150。Further, the inventors found that the Al(PO 3 ) 3 /LiF ratio is closely related to the crystallization performance of the glass, and when the Al(PO 3 ) 3 /LiF is too low, the crystallization performance of the glass becomes worse; when When the Al(PO 3 ) 3 /LiF is too high, the refractive index and dispersion will be greatly increased, and the effects of low refraction and low dispersion cannot be achieved, and it is difficult to eliminate bubbles and foreign matter during the melting process. Therefore, in the present invention, the ratio of Al(PO 3 ) 3 /LiF is controlled to be 13-180, preferably 13-150.

玻璃中的氟(F)含量对降低玻璃的折射率nd和色散是有效的。如果氟(F)含量过少,则折射率和色散趋于变大,无法实现低折射率、低色散的目标。反之,如果氟(F)含量过多,则玻璃中的离子键就会增加,而离子键键能较小的特点会导致玻璃骨架的不稳定,这会使玻璃更容易失透,并且氟(F)含量过多也会使产品的磨耗度增大,而过大的磨耗度值不利于玻璃精磨抛光过程中的公差控制。在本发明中,玻璃中的氟(F)由复合添加的AlF3、BaF2、CaF2、SrF2、MgF2、LiF来引入,另外,本发明中不人为引入其它氟化物。The fluorine (F) content in the glass is effective in reducing the refractive index nd and dispersion of the glass. If the fluorine (F) content is too small, the refractive index and dispersion tend to increase, and the goals of low refractive index and low dispersion cannot be achieved. Conversely, if the fluorine (F) content is too much, the ionic bond in the glass will increase, and the characteristics of the small ionic bond energy will lead to the instability of the glass skeleton, which will make the glass more likely to devitrify, and the fluorine ( F) Too much content will also increase the abrasiveness of the product, and an excessively large abrasiveness value is not conducive to tolerance control in the process of fine grinding and polishing of glass. In the present invention, the fluorine (F) in the glass is introduced by composite addition of AlF 3 , BaF 2 , CaF 2 , SrF 2 , MgF 2 , LiF, and other fluorides are not artificially introduced in the present invention.

本发明发现氟磷酸盐玻璃的折射率和色散与玻璃中的氧氟比(O/F)有关。氧氟比(O/F)越大,即氧含量越高,玻璃的折射率越高,色散越大,并且合理的氧氟比(O/F)对于提高玻璃的耐乳浊性能尤为重要。在本发明中采用了上述氧化物和氟化物的含量与配比对玻璃中的氧氟比(O/F)进行控制。The inventors have discovered that the refractive index and dispersion of fluorophosphate glasses are related to the oxygen to fluorine ratio (O/F) in the glass. The larger the oxygen-fluorine ratio (O/F), that is, the higher the oxygen content, the higher the refractive index of the glass and the greater the dispersion, and a reasonable oxygen-fluorine ratio (O/F) is particularly important for improving the opacification resistance of the glass. In the present invention, the content and ratio of the above-mentioned oxides and fluorides are used to control the oxygen-fluorine ratio (O/F) in the glass.

玻璃中的羟基(OH)含量对玻璃的耐碱性能密切相关。羟基在玻璃中会破坏玻璃的网络结构,降低玻璃骨架的稳定性,在受到碱性溶液的侵蚀时,结构更加容易受到破坏,会大大降低玻璃的耐碱性能。因此在本发明中,会尽可能降低玻璃中的羟基。The hydroxyl (OH) content in glass is closely related to the alkali resistance of glass. The hydroxyl group in the glass will destroy the network structure of the glass and reduce the stability of the glass skeleton. When it is eroded by alkaline solution, the structure is more easily damaged, which will greatly reduce the alkali resistance of the glass. Therefore, in the present invention, the hydroxyl groups in the glass are reduced as much as possible.

进一步地,本发明的所述氟磷酸盐光学玻璃的组成中不含有P2O5、NaF、KF、SnF4、La2O3、Gd2O3、Y2O3、Yb2O3、Ta2O5、GeO2、CaO、BaO、SrO和MgO中的至少一种,优选都不含有。Furthermore, 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 , At least one of Ta 2 O 5 , GeO 2 , CaO, BaO, SrO, and MgO is preferably not contained.

在本发明中,所述氟磷酸盐光学玻璃的析晶上限温度Lt为680℃以下,玻璃转变温度Tg为440℃以下;和/或,所述氟磷酸盐光学玻璃的耐失透性Tg/Lt大于0.64。所述氟磷酸盐光学玻璃的着色度λ805中的λ80为310nm以下,λ5为190nm以下。所述氟磷酸盐光学玻璃的比重为3.80g/cm3以下。所述氟磷酸盐光学玻璃的耐碱性ROH(S)为4级及以上;所述氟磷酸盐光学玻璃的磨耗度FA为455以下。In the present invention, the crystallization upper limit temperature L t of the fluorophosphate optical glass is below 680°C, and the glass transition temperature Tg is below 440°C; and/or, the devitrification resistance of the fluorophosphate optical glass is T g /L t is greater than 0.64. In the coloring degree λ 805 of the fluorophosphate optical glass, λ 80 is less than 310nm, and λ 5 is less than 190nm. The specific gravity of the fluorophosphate optical glass is below 3.80 g/cm 3 . The alkali resistance R OH (S) of the fluorophosphate optical glass is grade 4 or above; the abrasion degree F A of the fluorophosphate optical glass is below 455.

进一步地,本发明还提供一种根据本发明所述的氟磷酸盐光学玻璃的制备方法,其特征在于,包括:将各组分按照比例称量、混合均匀后进行熔炼,并且在所述熔炼过程中,使挥发气体充分逸出;优选地,所述熔炼的温度为800~900℃;然后浇注或漏注在成型模具中,或者直接压制成型。Further, the present invention also provides a method for preparing the fluorophosphate optical glass according to the present invention, which is characterized in that it includes: weighing and mixing each component according to the proportion and then melting them, and during the melting During the process, the volatile gas is fully released; preferably, the melting temperature is 800-900° C.; and then poured or leaked into a molding mold, or directly pressed into shape.

在本发明中,玻璃粉料刚投入坩埚中,因氟化物强烈的挥发特性会产生大量的挥发物,由于氟化物大量挥发会使玻璃中的羟基以H2O的形式带出,可以大大降低玻璃中的羟基含量,因此本发明的光学玻璃制造过程在熔炼过程时需开方式处理,从而使挥发气体充分逸出。In the present invention, as soon as the glass powder is put into the crucible, a large amount of volatiles will be produced due to the strong volatility of fluorides. Due to the large amount of volatilization of fluorides, the hydroxyl groups in the glass will be taken out in the form of H2O , which can greatly reduce The hydroxyl content in the glass, therefore, the manufacturing process of the optical glass of the present invention needs to be handled in an open way during the melting process, so that the volatile gas can fully escape.

进一步,在所述熔炼之后还包括,将温度升高至900~1000℃并开启搅拌器进行搅拌,搅拌时间控制在3~8h;搅拌完成后升温至1000~1050℃并保温4~9h,进行澄清,使气泡充分上浮,然后将温度降至600~700℃。Further, after the smelting, it also includes raising the temperature to 900-1000°C and turning on the stirrer for stirring, and the stirring time is controlled at 3-8h; after the stirring is completed, the temperature is raised to 1000-1050°C and kept for 4-9h, and Clarify, make the bubbles fully float, and then lower the temperature to 600-700 °C.

具体地,熔炼完成后在搅拌、均化、澄清、降温出炉阶段需进行密封处理,此时玻璃经过熔炼过程的大量挥发,挥发量大大降低,如果开放将会导致空气中的H2O再次进行玻璃液中,增大羟基的含量,因此本发明的光学玻璃制造过程在搅拌、均化、澄清、降温出炉阶段需进行密封处理。Specifically, after the smelting is completed, it needs to be sealed during the stages of stirring, homogenizing, clarification, and cooling down. At this time, the glass undergoes a large amount of volatilization during the smelting process, and the volatilization amount is greatly reduced. If it is opened, the H 2 O in the air will be released again In the molten glass, the content of hydroxyl groups increases, so the optical glass manufacturing process of the present invention needs to be sealed during the stages of stirring, homogenizing, clarifying, and cooling out of the furnace.

氟磷酸盐玻璃因含有大量的氟而具有强烈的挥发性,为了减弱玻璃表面因氟挥发而产生的光学不均匀性(条纹)及对环境的污染,优选的,在氟磷酸盐玻璃的生产中,在成型模具上玻璃液流经的上表面加设冷却盖板,将惰性气体通过冷却盖板通向玻璃液表面,使玻璃液尽快冷却成型。另外,为防止玻璃对熔炼坩埚的侵蚀,优选的,在非还原气氛中熔炼,具体操作时可以在熔炼埚内通入氧气或加设氧化熔池。Fluorophosphate glass has strong volatility because it contains a large amount of fluorine. In order to reduce the optical inhomogeneity (stripe) and environmental pollution caused by the volatilization of fluorine on the glass surface, it is preferred to use it in the production of fluorophosphate glass A cooling cover plate is added on the upper surface of the forming mold where the molten glass flows, and the inert gas is passed through the cooling cover plate to the surface of the molten glass, so that the molten glass is cooled and formed as soon as possible. In addition, in order to prevent the glass from corroding the melting crucible, it is preferred to melt in a non-reducing atmosphere. During specific operations, oxygen can be introduced into the melting crucible or an oxidation melting pool can be added.

另外,本发明还提供一种光学元件,其包括根据本发明的氟磷酸盐光学玻璃。可以通过对氟磷酸盐光学玻璃进行一次或二次压型生产制得光学元件,光学元件可以用在各类光学仪器的光学系统中。In addition, the present invention also provides an optical element comprising the fluorophosphate optical glass according to the present invention. Optical elements can be produced by one-time or two-time pressing of fluorophosphate optical glass, and the optical elements can be used in the optical systems of various optical instruments.

实施例下面将结合实施例对本发明的实施方案进行详细描述,但是本领域技术人员将会理解,下列实施例仅用于说明本发明,而不应视为限定本发明的范围。实施例中未注明具体条件者,按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者,均为可以通过市购获得的常规产品。EXAMPLES The embodiments of the present invention will be described in detail below in conjunction with examples, but those skilled in the art will understand that the following examples are only for illustrating the present invention and should not be considered as limiting the scope of the present invention. Those who do not indicate the specific conditions in the examples are carried out according to the conventional conditions or the conditions suggested by the manufacturer. The reagents or instruments used were not indicated by the manufacturer, and they were all commercially available conventional products.

表中实施例1~20是本发明用于说明获得折射率nd为1.43~1.46,阿贝数υd为90~100的氟磷酸盐光学玻璃的典型实验。Examples 1-20 in the table are typical experiments for obtaining fluorophosphate optical glass whose refractive index n d is 1.43-1.46 and Abbe number υ d is 90-100 according to the present invention.

实施例1~20Examples 1-20

将下表1、表2、表3、表4中的各组分按规定的比例计算、称取、混合,投入到铂金制作的坩埚中于850℃的温度下进行熔炼,熔炼过程中坩埚敞口,使气体充分逸出;待原料熔解成玻璃液后,在密闭环境下,将温度升高至950℃并开启铂金制作的搅拌器进行搅拌、均化,搅拌时间控制在5h,搅拌完成后,升温至1000℃并保温6h,进行澄清,使气泡充分上浮,然后将温度降至750℃浇注或漏注在成型模具中,并在成型模具上加设如上所述的冷却盖板,将惰性气体通过冷却盖板通向玻璃液表面,解决氟流失引起的挥发条纹问题。最后经退火、加工得到实施例1~20的光学玻璃或光学元件。Calculate, weigh and mix the components in the following Table 1, Table 2, Table 3 and Table 4 according to the specified ratio, and put them into a crucible made of platinum for melting at a temperature of 850°C. During the melting process, the crucible is open. to allow the gas to fully escape; after the raw materials are melted into molten glass, in a closed environment, raise the temperature to 950°C and turn on the platinum stirrer to stir and homogenize, the stirring time is controlled at 5h, after the stirring is completed , raise the temperature to 1000°C and keep it warm for 6 hours, clarify and make the bubbles fully float up, then lower the temperature to 750°C and pour or leak into the forming mold, and add the above-mentioned cooling cover on the forming mold to make the inert The gas passes through the cooling cover plate to the surface of the molten glass to solve the problem of volatilization streaks caused by fluorine loss. Finally, the optical glasses or optical elements of Examples 1-20 are obtained through annealing and processing.

比较例A-CComparative Examples A-C

将下表4中的组分对应的原料分别按规定的比例称取,采用与实施例1~20相同的制备方法进行制备,获得比较例A、B、C的光学玻璃。The raw materials corresponding to the components in the following Table 4 were weighed according to the specified proportions, and prepared by the same preparation method as in Examples 1-20 to obtain the optical glasses of Comparative Examples A, B, and C.

比较例Dcomparative example D

按照实施例1的组分对应的原料按规定的比例称取,比较例D与实施例1的区别在于熔炼过程进行密封处理,熔炼完成后在搅拌、均化、澄清、降温出炉阶段坩埚敞口,其余完全相同。The raw materials corresponding to the components of Example 1 are weighed according to the specified ratio. The difference between Comparative Example D and Example 1 is that the smelting process is sealed. , and the rest are identical.

比较例EComparative Example E

按照实施例1的组分对应的原料按规定的比例称取,比较例E与实施例1的区别在于熔炼过程进行密封处理,熔炼完成后在搅拌、均化、澄清、降温出炉阶段也进行密封处理,其余完全相同。The raw materials corresponding to the components of Example 1 are weighed according to the specified ratio. The difference between Comparative Example E and Example 1 is that the smelting process is sealed, and after the smelting is completed, it is also sealed in the stages of stirring, homogenization, clarification, and cooling. Processing, the rest is exactly the same.

性能测试Performance Testing

获得的氟磷酸盐光学玻璃的各项性能通过下列方法测量。Various properties of the obtained fluorophosphate optical glass were measured by the following methods.

按照GB/T7962.1-2010的测试方法对所述氟磷酸盐光学玻璃进行折射率nd、阿贝数υd的测量。According to the test method of GB/T7962.1-2010, the refractive index nd and the Abbe number υd of the fluorophosphate optical glass are measured.

光学玻璃短波透射光谱特性用着色度λ805表示。λ80是指光谱透过率达到80%时对应的波长,λ5是指光谱透过率达到5%时对应的波长。按照日本玻璃工业协会JOGIS02-2003的“光学玻璃着色度测定方法”,测定经平行的对面研磨的厚度为10±0.1mm的玻璃的光线透过率。需要说明的是,在进行检测时,由于λ5的测量下限是190nm,因此,λ5的测量结果均为190nm以下。The short-wave transmission spectral characteristics of optical glass are expressed by coloring degree λ 805 . λ 80 refers to the corresponding wavelength when the spectral transmittance reaches 80%, and λ 5 refers to the corresponding wavelength when the spectral transmittance reaches 5%. According to JOGIS02-2003 "Measurement Method of Coloring Degree of Optical Glass" of Japan Glass Industry Association, the light transmittance of glass with a thickness of 10 ± 0.1 mm after parallel face-to-face grinding was measured. It should be noted that when detecting, since the lower limit of measurement of λ5 is 190nm, the measurement results of λ5 are all below 190nm.

按照GB/T7962.12-2010的测试方法,对波长在700nm、400nm、300nm位置的内部透过率(τ10,样品厚度为10±0.1mm)进行测定。According to the test method of GB/T7962.12-2010, the internal transmittance (τ 10 , sample thickness 10±0.1mm) at wavelengths of 700nm, 400nm and 300nm was measured.

按照GB/T7962.20-2010的测试方法对所得光学玻璃的比重进行测试。According to the test method of GB/T7962.20-2010, the specific gravity of the obtained optical glass is tested.

按照GB/T7962.16-2010的测试方法对所得光学玻璃的转变温度Tg进行测试。The transition temperature T g of the obtained optical glass was tested according to the test method of GB/T7962.16-2010.

Lt为液相线温度,即析晶上限温度,其测试是采用DTA(差热分析)方法进行的,DTA曲线中温度最高的热吸收峰对应的温度即为LtL t is the liquidus temperature, that is, the 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 L t .

按照GB/T7962.19-2010的测试方法对所得光学玻璃的磨耗度FA进行测试。According to the test method of GB/T7962.19-2010, the degree of abrasion F A of the obtained optical glass is tested.

光学玻璃耐碱作用稳定性用ROH(S)表示,其测试是将六面抛光尺寸为40mm×40mm×5mm的试样,浸渍于充分搅拌、温度恒定为50℃±3℃、浓度为0.01mol/L的氢氧化钠溶液中15小时。The alkali-resistant stability of optical glass is expressed by R OH (S). The test is to immerse a six-sided polished sample with a size of 40mm×40mm×5mm in a well-stirred, constant temperature of 50°C±3°C and a concentration of 0.01 mol/L sodium hydroxide solution for 15 hours.

玻璃中羟基含量无法定量测试,但是羟基在3000nm波段会有明显的吸收峰,因此在本发明中通过测试玻璃3000nm透过率来表征玻璃中羟基的含量。按照GB/T7962.12-2010的测试方法,对波长在3000nm位置的内部透过率(τ10,样品厚度为10±0.1mm)进行测定。The hydroxyl content in the glass cannot be quantitatively tested, but the hydroxyl group has an obvious absorption peak in the 3000nm band, so in the present invention, the content of the hydroxyl group in the glass is characterized by testing the 3000nm transmittance of the glass. According to the test method of GB/T7962.12-2010, the internal transmittance (τ 10 , sample thickness 10±0.1mm) at the wavelength of 3000nm was measured.

表1实施例1-6的玻璃组分及性能参数Glass composition and performance parameter of table 1 embodiment 1-6

表2实施例7-12的玻璃组分及性能参数Glass components and performance parameters of table 2 embodiment 7-12

表3实施例13-18的玻璃组分及性能参数Glass composition and performance parameter of table 3 embodiment 13-18

表4实施例19-20及比较例A、B、C的玻璃组分及性能参数Glass components and performance parameters of Table 4 Examples 19-20 and Comparative Examples A, B, and C

表5实施例1及比较例D、E的性能参数The performance parameter of table 5 embodiment 1 and comparative example D, E

从实施例1~20中可以看出:本发明优选使用了以Al(PO3)3的形式引入P2O5,其好处是使生产异常次数大幅降低、使产品性能更稳定可控。在达到相同的、预期的光学常数时,实施例的玻璃具有比比较例更高的化学稳定性和较低的玻璃转变温度,更低的玻璃转变温度值说明产品更适合进行精密模压加工。It can be seen from Examples 1-20 that the present invention preferably uses the introduction of P 2 O 5 in the form of Al(PO 3 ) 3 , which has the advantage of greatly reducing the number of production abnormalities and making the product performance more stable and controllable. When the same and expected optical constants are achieved, the glass of the embodiment has higher chemical stability and lower glass transition temperature than the comparative example, and the lower glass transition temperature indicates that the product is more suitable for precision molding.

比较例A中,LiF的含量高于0.45%时,ROH(S)值急剧增大,浸出质量增大,耐碱作用稳定性变差,玻璃的化学稳定性变差,Tg/Lt值变小,玻璃的析晶性能也变差。同时磨耗度FA也增加,不利于玻璃精磨抛光过程中的公差控制。In Comparative Example A, when the LiF content is higher than 0.45%, the R OH (S) value increases sharply, the leaching quality increases, the stability of alkali resistance becomes worse, and the chemical stability of the glass becomes worse, T g /L t The smaller the value, the worse the crystallization performance of the glass. At the same time, the degree of abrasion F A also increases, which is not conducive to the tolerance control in the process of fine grinding and polishing of glass.

比较例B中,BaF2的含量低于7.5%,使得BaF2/(CaF2+MgF2)比值低于0.3,耐碱性DA为5级,DA浸出质量大大增加,说明玻璃的化学稳定性严重变差,Tg/Lt值减小,说明玻璃的析晶性能变差,不利于玻璃的成型,同时磨耗度也变差。In comparative example B, the content of BaF 2 is lower than 7.5%, so that the ratio of BaF 2 /(CaF 2 +MgF 2 ) is lower than 0.3, the alkali resistance D A is grade 5, and the leaching quality of D A is greatly increased, which shows that the chemical properties of glass The stability deteriorates seriously, and the T g /Lt value decreases, indicating that the crystallization performance of the glass deteriorates, which is not conducive to the forming of the glass, and at the same time, the abrasion degree also deteriorates.

比较例C中,Al(PO3)3/LiF比值过低,其他组成均在本发明限定范围内,nd、vd、耐碱性、磨耗度、比重均符合本发明的限定范围,但是由于Al(PO3)3/LiF比值低于13,析晶性能变差。In comparative example C, the ratio of Al(PO 3 ) 3 /LiF is too low, other compositions are all within the limits of the present invention, nd, vd, alkali resistance, abrasion, and specific gravity are all in line with the limits of the present invention, but due to Al When the ratio of (PO 3 ) 3 /LiF is lower than 13, the crystallization performance becomes worse.

从表5可以看出,比较例D、E的制备方法与实施例1不同,其中玻璃中羟基含量较高,3000nm波段透过率较低,导致耐碱性能变差,实施例1的制备方法制备得到的玻璃的羟基含量较少,3000nm波段透过率高,耐碱性性能提高。It can be seen from Table 5 that the preparation methods of Comparative Examples D and E are different from those of Example 1, wherein the hydroxyl content in the glass is relatively high, and the transmittance in the 3000nm band is low, resulting in poor alkali resistance. The preparation method of Example 1 The prepared glass has less hydroxyl group content, high transmittance in the 3000nm band, and improved alkali resistance.

需要说明的是,尽管以具体实例介绍了本发明的技术方案,但本领域技术人员能够理解,本发明应不限于此。It should be noted that although the technical solutions of the present invention are described with specific examples, those skilled in the art can understand that the present invention should not be limited thereto.

以上已经描述了本发明的各实施例,上述说明是示例性的,并非穷尽性的,并且也不限于所披露的各实施例。在不偏离所说明的各实施例的范围和精神的情况下,对于本技术领域的普通技术人员来说许多修改和变更都是显而易见的。本文中所用术语的选择,旨在最好地解释各实施例的原理、实际应用或对市场中的技术改进,或者使本技术领域的其它普通技术人员能理解本文披露的各实施例。Having described various embodiments of the present invention, the foregoing description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and alterations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is chosen to best explain the principle of each embodiment, practical application or technical improvement in the market, or to enable other ordinary skilled in the art to understand each embodiment disclosed herein.

Claims (10)

1.一种氟磷酸盐光学玻璃,其特征在于,其包含以化合物计的以下组分:1. A fluorophosphate optical glass, characterized in that it comprises the following components in terms of compounds: Al(PO3)3:5%~12%,优选6%~10%;Al(PO 3 ) 3 : 5% to 12%, preferably 6% to 10%; AlF3:22%~33%,优选23%~30%;AlF 3 : 22% to 33%, preferably 23% to 30%; BaF2:7.5%~15%,优选9%~13%;BaF 2 : 7.5% to 15%, preferably 9% to 13%; SrF2:20%~30%,优选22%~29%;SrF 2 : 20% to 30%, preferably 22% to 29%; CaF2:20%~30%,优选22%~28%;CaF 2 : 20% to 30%, preferably 22% to 28%; MgF2:2%~7%,优选2%~5%;MgF 2 : 2% to 7%, preferably 2% to 5%; YF3:0.5%~8%,优选0.5%~6%;YF 3 : 0.5% to 8%, preferably 0.5% to 6%; LiF:0.05%~0.45%,优选0.1%~0.35%;LiF: 0.05% to 0.45%, preferably 0.1% to 0.35%; 上述百分比均为质量百分比;The above percentages are all percentages by mass; 所述氟磷酸盐光学玻璃的折射率nd为1.43~1.46,阿贝数υd为90~100。The refractive index n d of the fluorophosphate optical glass is 1.43-1.46, and the Abbe number υ d is 90-100. 2.根据权利要求1所述的氟磷酸盐光学玻璃,其特征在于,以重量百分比计,BaF2的含量与CaF2的含量之比BaF2/CaF2为0.35~0.72,优选0.36~0.64;和/或,2. The fluorophosphate optical glass according to claim 1, characterized in that, in terms of weight percent, the ratio BaF 2 /CaF 2 between the content of BaF 2 and the content of CaF 2 is 0.35-0.72, preferably 0.36-0.64; and / or, BaF2的含量与MgF2和CaF2的含量之和的比值BaF2/(MgF2+CaF2)为0.3~0.64,优选0.32~0.56;和/或,The ratio BaF 2 /(MgF 2 +CaF 2 ) of the content of BaF 2 to the sum of the contents of MgF 2 and CaF 2 is 0.3-0.64, preferably 0.32-0.56; and/or, Al(PO3)3的含量与LiF的含量之比Al(PO3)3/LiF为13~180,优选13~150。The ratio Al(PO 3 ) 3 /LiF of the content of Al(PO 3 ) 3 to the content of LiF is 13-180, preferably 13-150. 3.根据权利要求1或2所述的光学玻璃,其特征在于,所述氟磷酸盐光学玻璃的组成中不含有P2O5、NaF、KF、SnF4、La2O3、Gd2O3、Y2O3、Yb2O3、Ta2O5、GeO2、CaO、BaO、SrO和MgO中的至少一种。3. The optical glass according to claim 1 or 2, characterized in that 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. At least one of Y 2 O 3 , Yb 2 O 3 , Ta 2 O 5 , GeO 2 , CaO, BaO, SrO and MgO. 4.根据权利要求1-3任一项所述的氟磷酸盐光学玻璃,其特征在于,所述氟磷酸盐光学玻璃的析晶上限温度Lt为680℃以下,玻璃转变温度Tg为440℃以下;和/或,4. The fluorophosphate optical glass according to any one of claims 1-3, characterized in that the crystallization upper limit temperature L t of the fluorophosphate optical glass is below 680° C., and the glass transition temperature T g is 440° C. below °C; and/or, 所述氟磷酸盐光学玻璃的耐失透性Tg/Lt大于0.64。The devitrification resistance T g /L t of the fluorophosphate optical glass is greater than 0.64. 5.根据权利要求1-4任一项所述的氟磷酸盐光学玻璃,其特征在于,所述氟磷酸盐光学玻璃的着色度λ805中的λ80为310nm以下,λ5为190nm以下。5. according to the described fluorophosphate optical glass of any one of claim 1-4, it is characterized in that, λ 80 in the coloring degree λ 805 of described fluorophosphate optical glass is below 310nm, and λ 5 is Below 190nm. 6.根据权利要求1-5任一项所述的氟磷酸盐光学玻璃,其特征在于,所述氟磷酸盐光学玻璃的比重为3.80g/cm3以下。6. The fluorophosphate optical glass according to any one of claims 1-5, characterized in that, the specific gravity of the fluorophosphate optical glass is 3.80 g/cm 3 or less. 7.根据权利要求1-6任一项所述的氟磷酸盐光学玻璃,其特征在于,所述氟磷酸盐光学玻璃的耐碱性ROH(S)为4级及以上;和/或7. The fluorophosphate optical glass according to any one of claims 1-6, characterized in that, the alkali resistance R OH (S) of the fluorophosphate optical glass is 4 grades and above; and/or 所述氟磷酸盐光学玻璃的磨耗度FA为455以下。The abrasion degree F A of the fluorophosphate optical glass is 455 or less. 8.一种根据权利要求1-7任一项所述的氟磷酸盐光学玻璃的制备方法,其特征在于,包括:将各组分按照比例称量、混合均匀后进行熔炼,并且在所述熔炼过程中,使挥发气体充分逸出;优选地,所述熔炼的温度为800~900℃;然后浇注或漏注在成型模具中,或者直接压制成型。8. A method for preparing the fluorophosphate optical glass according to any one of claims 1-7, characterized in that it comprises: weighing each component according to the proportion, mixing them uniformly and then melting them, and During the smelting process, the volatile gas is fully released; preferably, the temperature of the smelting is 800-900° C.; and then poured or leaked into a molding mold, or directly pressed into shape. 9.根据权利要求8所述的制备方法,其特征在于,在所述熔炼之后还包括,在密闭环境下,将温度升高至900~1000℃并开启搅拌器进行搅拌,搅拌时间控制在3~8h;搅拌完成后升温至1000~1050℃并保温4~9h,进行澄清,使气泡充分上浮,然后将温度降至600~700℃。9. The preparation method according to claim 8, characterized in that, after the smelting, it also includes, in a closed environment, raising the temperature to 900-1000°C and turning on the stirrer for stirring, and the stirring time is controlled at 3 ~8h; After the stirring is completed, raise the temperature to 1000~1050°C and keep it warm for 4~9h to clarify and make the bubbles fully float up, and then lower the temperature to 600~700°C. 10.一种光学元件,其特征在于,包括根据权利要求1-7任一项所述的氟磷酸盐光学玻璃。10. An optical element, comprising the fluorophosphate optical glass according to any one of claims 1-7.
CN202310585795.6A 2023-05-23 2023-05-23 Fluorophosphate optical glass, its preparation method and optical element Pending CN116514394A (en)

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JP2008088047A (en) * 2006-09-07 2008-04-17 Ohara Inc Glass
CN101164938A (en) * 2006-10-10 2008-04-23 株式会社小原 Optical glass
JP2015067459A (en) * 2013-09-26 2015-04-13 旭硝子株式会社 Fluorophosphate glass, preform for press molding and optical element
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5654249A (en) * 1979-10-04 1981-05-14 Ohara Inc Fluoride glass
US5017520A (en) * 1988-12-01 1991-05-21 Sumita Optical Glass, Inc. Fluorosphosphate optical glass
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CN101164938A (en) * 2006-10-10 2008-04-23 株式会社小原 Optical glass
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