WO2020114255A1 - 重镧火石玻璃及其预制件、光学元件和光学仪器 - Google Patents
重镧火石玻璃及其预制件、光学元件和光学仪器 Download PDFInfo
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- WO2020114255A1 WO2020114255A1 PCT/CN2019/119809 CN2019119809W WO2020114255A1 WO 2020114255 A1 WO2020114255 A1 WO 2020114255A1 CN 2019119809 W CN2019119809 W CN 2019119809W WO 2020114255 A1 WO2020114255 A1 WO 2020114255A1
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- lanthanum flint
- heavy lanthanum
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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
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
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- 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
Definitions
- the invention belongs to the field of optical glass, and particularly relates to a heavy lanthanum flint glass and its prefabricated parts, optical elements and optical instruments.
- Heavy lanthanum flint glass with refractive index (nd) of 1.86-1.92 and Abbe number (vd) of 25-30 is widely used in the lens of precision optical instruments. These heavy lanthanum flint glass can meet the requirements of modern precision molding process, However, the existing heavy lanthanum flint glass has a higher refractive index temperature coefficient.
- the refractive index of optical glass is a function of temperature.
- the change in refractive index caused by unit temperature is the temperature coefficient of glass refractive index. It is a key performance parameter that measures the influence of temperature on the refractive index of optical glass. When the temperature rises, the glass expands by heat The density is reduced and the refractive index is decreased.
- the existing heavy lanthanum flint glass has a high crystallization upper limit temperature, the glass has poor stability during high-temperature processing, and the thermal processing process is difficult, which limits its range of use.
- the current high-density and high-color heavy lanthanum flint glass can not meet people's requirements for light and miniaturized instruments and equipment and high transmittance.
- the object of the present invention is to provide a heavy lanthanum flint glass with a refractive index (nd) of 1.86 to 1.92 and an Abbe number (vd) of 25-30, which can meet the requirements of precision instruments.
- nd refractive index
- vd Abbe number
- the invention further provides preforms, optical elements and optical instruments made from the heavy lanthanum flint glass.
- Heavy lanthanum flint glass contains, by weight %: SiO 2 : 12-30%, Ln 2 O 3 : 10-25%, the Ln 2 O 3 is La 2 O 3 , Gd 2 O 3 , Y 2 O The total content of 3 and Yb 2 O 3 , TiO 2 +Nb 2 O 5 +WO 3 +Bi 2 O 3 : 10.5%-40%, B 2 O 3 :0-10%, RO: 20-35%, said RO is one or more of BaO, CaO, MgO and SrO, ZrO 2 : 0.5-10%, where (SiO 2 +TiO 2 )/(B 2 O 3 +Nb 2 O 5 ) is 1-30.
- the above-mentioned heavy lanthanum flint glass further contains, by weight %: Rn 2 O: 0-8%, and the Rn 2 O is one or more of Li 2 O, Na 2 O and K 2 O Species, Sb 2 O 3 : 0-1%, ZnO: 0-7%, Ta 2 O 5 : 0-10%, Al 2 O 3 : 0-10%.
- Heavy lanthanum flint glass consists of 12-30% SiO 2 and 10-25% Ln 2 O 3 in terms of % by weight.
- the Ln 2 O 3 is La 2 O 3 , Gd 2 O 3 , Y 2 O 3
- the Rn 2 O is Li 2 O, Na 2 O and K 2 O
- each component satisfies one or more of the following four situations:
- B 2 O 3 /TiO 2 is greater than 0 and less than or equal to 1;
- BaO/B 2 O 3 is greater than 0 and less than or equal to 70;
- the aforementioned heavy lanthanum flint glass wherein: SiO 2 : 15-25%, and/or Ln 2 O 3 : 12-22%, and/or TiO 2 +Nb 2 O 5 +WO 3 +Bi 2 O 3 : 17-33%, and/or RO: 22-32%, and/or ZrO 2 : 2-8%, and/or B 2 O 3 : 0.5-6%, and/or Rn 2 O: 0.5- 6%, and/or Sb 2 O 3 : 0-0.5%, and/or ZnO: 0-5%, and/or Ta 2 O 5 : 0-5%, and/or Al 2 O 3 : 0-5 %.
- each component satisfies one or more of the following five situations:
- B 2 O 3 /TiO 2 is 0.02-0.4;
- BaO/B 2 O 3 is 3.6-64;
- SiO 2 +TiO 2 is 30-50%
- B 2 O 3 /SiO 2 is 0.02-0.4.
- the aforementioned heavy lanthanum flint glass wherein: SiO 2 : 18-23%, and/or Ln 2 O 3 : 13-18%, and/or TiO 2 +Nb 2 O 5 +WO 3 +Bi 2 O 3 : 22-31%, and/or RO: 23-30%, and/or ZrO 2 : 2-6%, and/or B 2 O 3 : 1-4%, and/or Rn 2 O: 1- 5%, and/or Sb 2 O 3 : 0-0.2%, and/or ZnO: 0-3%, and/or Ta 2 O 5 free , and/or Al 2 O 3 free .
- each component satisfies one or more of the following five situations:
- B 2 O 3 /TiO 2 is 0.02-0.23;
- BaO/B 2 O 3 is 5-30;
- SiO 2 +TiO 2 is 37-50%
- B 2 O 3 /SiO 2 is 0.02-0.34.
- the aforementioned heavy lanthanum flint glass wherein: TiO 2 : 10-30%, and/or Nb 2 O 5 : 0.5-10%; preferably, TiO 2 : 15-25%, and/or Nb 2 O 5 : 2-8%; more preferably, TiO 2 : 19-24%, and/or Nb 2 O 5 : 3-7%.
- the aforementioned heavy lanthanum flint glass wherein: La 2 O 3 : 10-25%, and/or BaO: 20-35%, and/or Na 2 O: 0-8%; preferably, La 2 O 3 : 12-22%, and/or BaO: 22-32%, and/or Na 2 O: 0.5-6%; more preferably, La 2 O 3 : 13-18%, and/or BaO: 23- 30%, and/or Na 2 O: 1-5%.
- the aforementioned heavy lanthanum flint glass has a ⁇ 70 of 450 nm or less, preferably 440 nm or less, and more preferably 430 nm or less; its ⁇ 5 is 390 nm or less, preferably 385 nm or less, more preferably 380 nm or less; density ( ⁇ ) 4.5g/cm 3 or less, preferably 4.3g/cm 3 or less, more preferably 4.25g/cm 3 or less; upper limit temperature of crystallization is 1200°C or less, preferably 1180°C or less; temperature coefficient of refractive index is 2.4 ⁇ 10 -6 /°C or lower, preferably 2.3 ⁇ 10 -6 /°C or lower.
- the aforementioned heavy lanthanum flint glass has a refractive index (nd) of 1.86-1.92, preferably 1.86-1.91, more preferably 1.87-1.90; and an Abbe number (vd) of 25-30, preferably 25-29 , More preferably 26-29.
- the aforementioned heavy lanthanum flint glass has a transition temperature (T g ) of 720° C. or less, preferably 710° C. or less, and more preferably 705° C. or less; water resistance stability (D W ) is 2 or more, preferably Class 1; acid resistance stability (D A ) is class 2 or more, preferably class 1.
- T g transition temperature
- D W water resistance stability
- D A acid resistance stability
- the glass preform is made of the aforementioned heavy lanthanum flint glass.
- the optical element is made of the aforementioned heavy lanthanum flint glass or glass preform.
- Optical instruments are made using the aforementioned optical elements.
- the beneficial effect of the present invention is that, through a reasonable composition ratio, the heavy lanthanum flint glass has excellent refractive index temperature coefficient, crystallization upper limit temperature, ⁇ 70 , ⁇ while ensuring the required refractive index and Abbe number 5 and chemical stability and other properties, suitable for popularization and application in precision instruments that require high transmittance, high imaging quality, and small thermal aberration.
- each glass component refers to the weight content, expressed in weight %, which is the weight of a certain component or several groups
- weight % is the weight of a certain component or several groups
- the sum of the weights of the points accounts for the percentage of the total weight of the optical glass; the ratio of each glass component, or the sum of several components, is the ratio of the corresponding weight content or the weight content after the sum.
- the heavy lanthanum flint glass of the present invention contains, by weight %: SiO 2 : 12-30%, Ln 2 O 3 : 10-25%, the Ln 2 O 3 is La 2 O 3 , Gd 2 O 3 , The total content of Y 2 O 3 and Yb 2 O 3 , TiO 2 +Nb 2 O 5 +WO 3 +Bi 2 O 3 : 10.5-40%, B 2 O 3 :0-10%, RO: 20-35% , The RO is one or more of BaO, CaO, MgO and SrO, ZrO 2 : 0.5-10%, where (SiO 2 +TiO 2 )/(B 2 O 3 +Nb 2 O 5 ) is 1 -30.
- SiO 2 is a network-forming body of glass and is a main component constituting a glass skeleton.
- the content of SiO 2 is closely related to the crystallization resistance, transmittance, refractive index and dispersion of glass. If its content is less than 12%, the refractive index and dispersion of the glass do not meet the design expectations, and at the same time the devitrification resistance and transmittance of the glass will be greatly reduced; if its content is higher than 30%, the solubility and resistance of the glass Crystallization performance will decrease, and the refractive index and dispersion will not meet the design expectations. Therefore, in the present invention, the content of SiO 2 is set to 12-30%, preferably 15-25%, further preferably 18-23%.
- B 2 O 3 is also a glass network forming component and is an optional component in the present invention.
- the introduction of B 2 O 3 can improve the glass meltability and resistance to devitrification, but when its introduction exceeds 10%, the glass-forming stability decreases and the refractive index decreases, so
- the content of B 2 O 3 is set to 0-10%, preferably 0.5-6%, further preferably 1-4%.
- SiO 2 and B 2 O 3 not only have their own unique functions, but also affect each other's glass formation stability and glass transition temperature (T g ).
- T g glass transition temperature
- the B 2 O 3 /SiO 2 ratio is set to 0.02-0.4, more preferably 0.02-0.34.
- the rare earth oxides Ln 2 O 3 (La 2 O 3 , Gd 2 O 3 , Y 2 O 3 and Yb 2 O 3 ) help to increase the refractive index of the glass.
- the total content Ln 2 O 3 of La 2 O 3 , Gd 2 O 3 , Y 2 O 3 and Yb 2 O 3 is set to 10-25%, preferably 12-22%, and more preferably 13-18%.
- the rare earth oxide of the present invention may contain 10-25% La 2 O 3 , preferably 12-22% La 2 O 3 , more preferably 13-18% La 2 O 3 , to further Increase the refractive index of the glass, increase the transmittance of the visible light band, reduce the temperature coefficient of the refractive index of the glass, and improve the resistance to devitrification.
- TiO 2 , Nb 2 O 5 , WO 3 and Bi 2 O 3 all have the effect of increasing the refractive index but also increasing the dispersion
- the upper limit of TiO 2 +Nb 2 O 5 +WO 3 +Bi 2 O 3 is set to 40%, and the preferred upper limit is 33%.
- the preferred upper limit is 31%.
- the lower limit is set to 10.5%, and the preferred lower limit is 17 %, the lower limit is 22%.
- the heavy lanthanum flint glass of the present invention it is preferable to use a combination of TiO 2 and Nb 2 O 5 to obtain a better refractive index and Abbe number.
- Adding more than 10% of TiO 2 to the glass of the present invention can participate in the formation of the glass network, increase the stability of the glass against crystallization, and can partially replace the expensive Nb 2 O 5 , WO 3 , Bi 2 O 3 , but the content is high At 30%, the glass transmittance will decrease and the glass coloring tendency will increase; the proper introduction of Nb 2 O 5 can make the glass more stable and improve the devitrification resistance.
- the TiO The content of 2 is set to 10-30%, preferably 15-25%, more preferably 19-24%; the content of Nb 2 O 5 is set to 0.5-10%, preferably 2-8%, more preferably 3- 7%.
- the present invention preferably has B 2 O 3 /TiO 2 greater than 0 and less than or equal to 1, more preferably B 2 O 3 /TiO 2 is 0.02-0.4, further Preferably, B 2 O 3 /TiO 2 is 0.02-0.23.
- SiO 2 +TiO 2 is preferably 30-50%, more preferably 37-50%.
- the inventors found that when the ratio (SiO 2 +TiO 2 )/(B 2 O 3 +Nb 2 O 5 ) is less than 1, the glass stability deteriorates, the upper limit temperature of crystallization increases, and the refractive index temperature coefficient increases , The thermal aberration is large, and the specific gravity of the glass increases, making it difficult to achieve the goal of weight reduction; however, when the ratio is greater than 30, it will cause the glass transmittance to decrease and the coloring tendency to increase significantly.
- the ratio (SiO 2 +TiO 2 )/(B 2 O 3 +Nb 2 O 5 ) is limited to 1-30, and the more preferred ratio (SiO 2 +TiO 2 )/(B 2 O 3 +Nb 2 O 5 ) is 2.15-20, and a further preferred ratio (SiO 2 +TiO 2 )/(B 2 O 3 +Nb 2 O 5 ) is 3.36-12.
- RO belongs to alkaline earth metal oxides and is one or more of CaO, MgO, SrO and BaO.
- the alkaline earth metal oxide can increase the Young's modulus of the glass, reduce the high temperature viscosity of the glass, balance the glass components, and improve the melting performance of the glass.
- the present invention sets the value of RO to 20-35%, preferably 22-32%, and more preferably 23-30%.
- the alkaline earth metal oxide of the present invention may contain 20-35% BaO, preferably 22-32% BaO, more preferably 23-30% BaO, to further reduce the refractive index temperature coefficient of the glass, Improve the devitrification resistance and chemical stability of glass.
- the addition ratio of BaO and B 2 O 3 has an important effect on the temperature coefficient of refractive index of glass, stability against water action (D W ), and stability against acid action (D A ).
- D W stability against water action
- D A stability against acid action
- BaO/B 2 O 3 is greater than 0
- the glass meltability is improved, and the temperature coefficient of the refractive index of the glass can be reduced, and the thermal aberration can be reduced.
- BaO/B 2 O 3 is set to be greater than 0 and less than or equal to 70, preferably BaO/B 2 O 3 is 3.6-64, and more preferably BaO/B 2 O 3 is 5-30.
- ZrO 2 is an essential component in the present invention, and is a kind of high-refraction low-dispersion oxide.
- the content of ZrO 2 is more than 0.5% in the glass, the refractive index of the glass can be increased and the dispersion can be adjusted. At the same time, it can improve the crystallization resistance and chemical stability of the glass.
- the content thereof is set to 0.5-10%, preferably 2-8%, further preferably 3-7%.
- ZrO 2 adjusts nd, vd, ⁇ 70 and ⁇ 5 of the glass together with the components La 2 O 3 , SiO 2 and TiO 2 in the glass of the present invention, as well as the crystallization upper limit temperature and refractive index temperature coefficient.
- the preferred ratio range is 0.7-6, when the value is less than 0.7 , The glass meltability becomes worse, the stability becomes worse, and the refractive index decreases; when (La 2 O 3 +TiO 2 +ZrO 2 )/SiO 2 is higher than 6, the transmittance of the visible light region of the glass decreases and the degree of coloring becomes difference. More preferably, the ratio range of (La 2 O 3 +TiO 2 +ZrO 2 )/SiO 2 is 1.2-5, and the most preferred ratio range is 1.5-4.
- the preferred ratio range is 0.75-6.5, which is Below 6.5, more excellent optical transmission performance and better resistance to crystallization can be obtained; however, when the value is less than 0.75 or greater than 6.5, it will be difficult to maintain the refractive index temperature coefficient at 2.4 ⁇ 10 -6 /°C In the following, both the optical properties and the devitrification resistance are significantly deteriorated.
- the ratio (SiO 2 +La 2 O 3 +ZrO 2 )/TiO 2 is in the range of 1.1-3.7, and the most preferred range is 1.2-2.
- Rn 2 O is an alkali metal oxide, which is one or more of Li 2 O, Na 2 O, and K 2 O, and is an optional component in the present invention.
- an appropriate amount of alkali metal oxide can obtain the expected high-temperature viscosity.
- the value of Rn 2 O is set to 0-8%, preferably 0.5-6%, and more preferably 1-5%.
- the alkali metal oxide of the present invention may contain 0-8% Na 2 O, preferably 0.5-6% Na 2 O, more preferably 1-5% Na 2 O, further reducing the glass Transition temperature improves the melting performance of glass.
- ZnO can adjust the refractive index and dispersion of glass, improve the crystallization resistance of glass, reduce the transition temperature of glass, and improve the chemical stability of glass. ZnO can also reduce the high-temperature viscosity of the glass, so that the glass can be smelted at a lower temperature, which can increase the transmittance of the glass. However, if the amount of ZnO added is too large, the anti-crystallization property of the glass will decline, and at the same time, the high temperature viscosity is small, which makes it difficult to form.
- ZnO is an optional component, and its content is 0-7%, preferably 0-5%, and more preferably 0-3%.
- Ta 2 O 5 can play the role of increasing the refractive index and reducing the dispersion. It is an optional component in the heavy lanthanum flint glass of the present invention, and its content is 0-10%, preferably 0-5%. Since it is expensive, it is more preferable not to contain Ta 2 O 5 .
- Al 2 O 3 can reduce the thermal expansion coefficient of glass and improve the thermal stability of glass.
- a high Al 2 O 3 concentration generally lowers the liquidus viscosity of the glass.
- the content is set to 0-10%, preferably 0-5%, and more preferably does not contain Al 2 O 3 .
- the heavy lanthanum flint glass of the present invention may incorporate 0-1%, preferably 0-0.5% of clarifier Sb 2 O 3 .
- the glass properties of the present invention are not impaired, a small amount of other components not mentioned above, such as P 2 O 5 , TeO 2 , GeO 2 , Lu 2 O 3, etc., can be added as needed.
- transition metal components such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag, and Mo
- the glass is colored, and absorption occurs at a specific wavelength in the visible light region.
- the properties of the present invention for improving the visible light transmittance effect are weakened. Therefore, it is preferred that the optical glass having a transmittance for the wavelength in the visible light region is not actually included.
- does not contain or “does not contain” “0%” described in the present invention means that the compound, molecule or element is not intentionally added as a raw material to the heavy lanthanum flint glass of the present invention; but as a raw material for producing glass and/or There will be some impurities or components that are not intentionally added in the equipment, and will be contained in the final heavy lanthanum flint glass in a small amount or trace amount, which is also within the protection scope of the present invention patent.
- one component can affect many properties of glass.
- the optimization of a certain performance by the same component may bring about the deterioration of another performance. Therefore, the mutual coordination and mutual restriction of multiple components are particularly important in the entire glass system.
- the heavy lanthanum flint glass obtained by the inventors of the present invention through experimental research at nd, vd, ⁇ 70 , ⁇ 5 , ⁇ , crystallization upper limit temperature, refractive index temperature coefficient, D W , D A , glass-forming stability or transition temperature (T g ) and other aspects have excellent performance.
- the refractive index (nd) is tested according to the method of GB/T7962.1-2010.
- the dispersion coefficient (ie Abbe number, vd) is tested according to the method of GB/T7962.1-2010.
- ⁇ 70 refers to the wavelength corresponding to the glass transmittance reaching 70%
- ⁇ 5 refers to the wavelength corresponding to the glass transmittance reaching 5%.
- the measurement of ⁇ 70 is the use of glass with two opposite planes parallel to each other and optically polished with a thickness of 10 ⁇ 0.1 mm, measuring the spectral transmittance in the wavelength range from 280 nm to 700 nm and exhibiting a wavelength of 70% transmittance .
- the temperature coefficient of the refractive index is tested according to the method specified in GB/T 7962.4-2010, and the temperature coefficient of the refractive index of 20-40°C is determined.
- the glass transition temperature (T g ) is measured according to the method specified in GB/T7962.16-2010, unit: °C.
- the test method for the upper limit temperature of crystallization is: the crystallization performance of the glass is measured by the ladder furnace method, the glass is made into a sample of 180*10*10mm, the side is polished, and placed in a furnace with a temperature gradient (5°C/cm) After warming up to 1400°C for 4 hours, take it out and let it cool down to room temperature. Observe the devitrification of the glass under a microscope. The highest temperature corresponding to the crystals in the glass is the upper limit of the devitrification temperature of the glass. The lower the upper crystallization temperature of the glass, the stronger the stability of the glass at high temperature, and the better the process performance.
- D W Water resistance stability
- the acid resistance stability (D A ) is tested according to GB/T17129.
- the density ( ⁇ ) is tested in accordance with "GB/T 7962.20-1987 Colorless Optical Glass Test Method Density Test Method".
- the heavy lanthanum flint glass of the present invention has the following properties: the refractive index (nd) is 1.86-1.92, preferably 1.86-1.91, more preferably 1.87-1.90; the Abbe number (vd) is 25-30, preferably 25-29, more preferably 26-29; the transition temperature ( Tg ) is 720°C or lower, preferably 710°C or lower, more preferably 705°C or lower; ⁇ 70 is 450nm or lower, preferably 440nm or lower, more preferably 430nm ⁇ 5 is 390 nm or less, preferably 385 nm or less, and more preferably 380 nm or less; density ( ⁇ ) is 4.5 g/cm 3 or less, preferably 4.3 g/cm 3 or less, more preferably 4.25 g/cm 3 or less; Water resistance stability (D W ) is 2 or more, preferably 1; acid resistance stability (D A ) is 2 or more, preferably 1; crystal
- Both the glass preform of the present invention and the optical element are formed of the aforementioned heavy lanthanum flint glass of the present invention.
- the glass preform of the present invention has high refractive index and lower refractive index temperature coefficient characteristics;
- the optical element of the present invention has high refractive index and lower refractive index temperature coefficient characteristics, and can provide various optical lenses and prisms with high optical value element.
- lenses include various lenses such as concave meniscus lenses, convex meniscus lenses, biconvex lenses, biconcave lenses, plano-convex lenses, and plano-concave lenses whose spherical surfaces are spherical or aspherical.
- the prism since the prism has a relatively high refractive index, it is possible to realize a compact, wide-angle optical system by combining it in the imaging optical system and bending the optical path toward the desired direction.
- optical elements formed by the optical glass of the present invention can be used to make optical instruments such as camera equipment, camera equipment, display equipment and monitoring equipment.
- the heavy lanthanum flint glass obtained in Examples 1-36 was cut to a predetermined size, and then a release agent was evenly coated on the surface, and then heated and softened, and subjected to pressure molding to produce concave meniscus lenses and convex Preforms for various lenses and prisms such as meniscus lenses, biconvex lenses, biconcave lenses, plano-convex lenses, plano-concave lenses, etc.
- the heavy lanthanum flint glass obtained in Examples 1-36 is used to form a preform for precision press molding, which is then processed by precision press molding into the shape of a lens and a prism to produce a preform.
- each preform is ground and ground to produce various lenses and prisms such as concave meniscus lenses, convex meniscus lenses, biconvex lenses, biconcave lenses, plano-convex lenses, and plano-concave lenses.
- An anti-reflection film may also be coated on the surface of the obtained optical element.
- optical elements produced by the above optical element embodiments can be used in, for example, imaging equipment, sensors, microscopes, medical technology, digital projection, communication, optical communication through optical design and the use of one or more optical elements to form optical components or optical components Technology/information transmission, optics/illumination in the automotive field, lithography technology, excimer lasers, wafers, computer chips, and integrated circuits and electronic devices including such circuits and chips, are particularly useful for imaging equipment and devices in the automotive field.
Abstract
Description
Claims (16)
- 重镧火石玻璃,其特征在于,以重量%计,含有:SiO 2:12-30%,Ln 2O 3:10-25%,所述Ln 2O 3为La 2O 3、Gd 2O 3、Y 2O 3和Yb 2O 3的合计含量,TiO 2+Nb 2O 5+WO 3+Bi 2O 3:10.5-40%,B 2O 3:0-10%,RO:20-35%,所述RO为BaO、CaO、MgO和SrO中的一种或多种,ZrO 2:0.5-10%,其中(SiO 2+TiO 2)/(B 2O 3+Nb 2O 5)为1-30。
- 根据权利要求1所述的重镧火石玻璃,其特征在于,以重量%计,还含有:Rn 2O:0-8%,所述Rn 2O为Li 2O、Na 2O和K 2O中的一种或多种,Sb 2O 3:0-1%,ZnO:0-7%,Ta 2O 5:0-10%,Al 2O 3:0-10%。
- 重镧火石玻璃,其特征在于,以重量%计,由12-30%的SiO 2,10-25%的Ln 2O 3,所述Ln 2O 3为La 2O 3、Gd 2O 3、Y 2O 3和Yb 2O 3的合计含量,10.5-40%的TiO 2+Nb 2O 5+WO 3+Bi 2O 3,20-35%的RO,所述RO为BaO、CaO、MgO和SrO中的一种或多种,0.5-10%的ZrO 2,0-10%的B 2O 3,0-8%的Rn 2O,所述Rn 2O为Li 2O、Na 2O和K 2O中的一种或多种,0-1%的Sb 2O 3,0-7%的ZnO,0-10%的Ta 2O 5,和0-10%的Al 2O 3组成,其中(SiO 2+TiO 2)/(B 2O 3+Nb 2O 5)为1-30。
- 根据权利要求1-3任意一项所述的重镧火石玻璃,其特征在于,各组分含量满足以下4种情形中的一种或一种以上:1)B 2O 3/TiO 2大于0且小于等于1;2)BaO/B 2O 3大于0且小于等于70;3)(La 2O 3+TiO 2+ZrO 2)/SiO 2为0.7-6;4)(SiO 2+La 2O 3+ZrO 2)/TiO 2为0.75-6.5。
- 根据权利要求1-3任意一项所述的重镧火石玻璃,其特征在于:SiO 2:15-25%,和/或Ln 2O 3:12-22%,和/或TiO 2+Nb 2O 5+WO 3+Bi 2O 3:17-33%,和/或RO:22-32%,和/或ZrO 2:2-8%,和/或B 2O 3:0.5-6%,和/或Rn 2O:0.5-6%,和/或Sb 2O 3:0-0.5%,和/或ZnO:0-5%,和/或Ta 2O 5:0-5%,和/或Al 2O 3:0-5%。
- 根据权利要求1-3任意一项所述的重镧火石玻璃,其特征在于,各组分含量满足以下5种情形中的一种或一种以上:1)B 2O 3/TiO 2为0.02-0.4;2)BaO/B 2O 3为3.6-64;3)(La 2O 3+TiO 2+ZrO 2)/SiO 2为1.2-5;4)(SiO 2+La 2O 3+ZrO 2)/TiO 2为1.1-3.7;5)(SiO 2+TiO 2)/(B 2O 3+Nb 2O 5)为2.15-20。
- 根据权利要求1-3任意一项所述的重镧火石玻璃,其特征在于:SiO 2:18-23%,和/或Ln 2O 3:13-18%,和/或TiO 2+Nb 2O 5+WO 3+Bi 2O 3:22-31%,和/或RO:23-30%,和/或ZrO 2:2-6%,和/或B 2O 3:1-4%,和/或Rn 2O:1-5%,和/或Sb 2O 3:0-0.2%,和/或ZnO:0-3%,和/或不含Ta 2O 5,和/或不含Al 2O 3。
- 根据权利要求1-3任意一项所述的重镧火石玻璃,其特征在于,各组分含量满足以下5种情形中的一种或一种以上:1)B 2O 3/TiO 2为0.02-0.23;2)BaO/B 2O 3为5-30;3)(La 2O 3+TiO 2+ZrO 2)/SiO 2为1.5-4;4)(SiO 2+La 2O 3+ZrO 2)/TiO 2为1.2-2.0;5)(SiO 2+TiO 2)/(B 2O 3+Nb 2O 5)为3.36-12.00。
- 根据权利要求1-3任意一项所述的重镧火石玻璃,其特征在于:TiO 2:10-30%,和/或Nb 2O 5:0.5-10%;优选地,TiO 2:15-25%,和/或Nb 2O 5:2-8%;更优地,TiO 2:19-24%,和/或Nb 2O 5:3-7%。
- 根据权利要求1-3任意一项所述的重镧火石玻璃,其特征在于:La 2O 3:10-25%,和/或BaO:20-35%,和/或Na 2O:0-8%;优选地,La 2O 3:12-22%,和/或BaO:22-32%,和/或Na 2O:0.5-6%;更优地,La 2O 3:13-18%,和/或BaO:23-30%,和/或Na 2O:1-5%。
- 根据权利要求1-3任意一项所述的重镧火石玻璃,其特征在于,所述玻璃的λ 70为450nm以下,优选为440nm以下,更优选为430nm以下;λ 5为390nm以下,优选为385nm以下,更优选为380nm以下;所述玻璃的密度(ρ)为4.5g/cm 3以下,优选为4.3g/cm 3以下,更优选为4.25g/cm 3以下;所述玻璃的析晶上限温度为1200℃以下,优选为1180℃以下;所述玻璃的折射率温度系数为2.4×10 -6/℃以下,优选为2.3×10 -6/℃以下。
- 根据权利要求1-3任意一项所述的重镧火石玻璃,其特征在于,所述玻璃的折射率(nd)为1.86-1.92,优选为1.86-1.91,更优选为1.87-1.90;阿贝数(vd)为25-30,优选为25-29,更优选为26-29。
- 根据权利要求1-3任意一项所述的重镧火石玻璃,其特征在于,所述玻璃的转变温度(T g)为720℃以下,优选为710℃以下,更优选为705℃以下;所述玻璃的耐水作用稳定性(D W)为2类以上,优选为1类;耐酸作用稳定性(D A)为2类以上,优选为1类。
- 玻璃预制件,采用权利要求1-13任一所述的重镧火石玻璃制成。
- 光学元件,采用权利要求1-13任一所述的重镧火石玻璃制成,或者采用权利要求14所述的玻璃预制件制成。
- 光学仪器,采用权利要求15所述的光学元件制成。
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