Classifications

• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/12—Silica-free oxide glass compositions
  • C03C3/23—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron
  • C03C3/247—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron containing fluorine and phosphorus
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C4/00—Compositions for glass with special properties
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
  • G02B27/0025—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 for optical correction, e.g. distorsion, aberration
  • G02B27/005—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 for optical correction, e.g. distorsion, aberration for correction of secondary colour or higher-order chromatic aberrations

Definitions

• the present invention relates to a fluorophosphate optical glass, and more particularly to a fluorophosphate optical glass having a high refractive index, a low dispersion, a low photoelastic coefficient, and good chemical stability and processability.
• Fluorophosphate optical glass is suitable for use as a lens material for eliminating high-order chromatic aberration in optical design due to its low dispersion and special dispersion.
• low dispersion is usually accompanied by a low refractive index and is not suitable for making a lens with a large refracting power.
• Existing low-dispersion fluorophosphate optical glasses having a relatively high refractive index (nd>1.59) often have problems such as chemical stability, thermal stability, and insufficient processing properties.
• Japanese Laid-Open Patent No. 2-124740 discloses a low dispersion high refractive index fluorophosphate optical glass, but such glass has poor thermal stability, glass has a high liquidus temperature, and crystallization and streaking are liable to occur in production.
• Chinese Patent Application No. 201110129548.2 discloses a fluorophosphate optical glass having good chemical stability, but the refractive index of the glass is insufficient (nd is less than 1.58).
• the technical problem to be solved by the present invention is to provide an optical glass having a refractive index nd greater than 1.59, an Abbe number ⁇ d greater than 67, a low photoelastic coefficient, and good chemical stability and abrasive properties.
• the technical solution adopted by the invention to solve the technical problem is: fluorophosphate optical glass, containing: P 5+ : 30-40%, Al 3+ : 12-20%, Ba 2+ : 30- 40%, Ca 2+ : 1.3-12%, Sr 2+ : 1-10%, La 3+ : 0-5%, Gd 3+ : 0-6%, Y 3+ : 0-10%;
• the percentage content includes: F + : 25-40%, O 2- : 60-75%.
• the percentage of cations further contains: Mg 2+ : 0-5%, Zn 2+ : 0-5%, Si 4+ : 0-3%, B 3+ : 0-5%, Ge 4 + : 0 - 3%, Li + : 0 - 12%, Na + : 0 - 5%, K + : 0 - 5%, Yb 3 + : 0 - 5%, Sb 3 + : 0 - 0.5%, Sn 4+: 0-1%, Ce 4+: 0-1%; the percentage content of anionic further comprising: Cl -: 0-1%, I -: 0-1%, Br -: 0-1%.
• Li + is preferably used.
• the total amount of Cl - +I - +Br - is greater than 0 but less than or equal to 0.8%, preferably greater than 0 but less than or equal to 0.5%.
• Cl - is preferably used.
• the total amount of Sb 3+ +Sn 4+ +Ce 4+ is greater than 0 but less than or equal to 1%, preferably greater than 0 but less than or equal to 0.5%.
• At least one of Sb 3+ , Sn 4+ and Ce 4+ is added together with at least one of Cl ⁇ , I ⁇ and Br ⁇ as a clarifying agent.
• the P 5+ is introduced as a metaphosphate
• the Al 3+ is introduced in one or more of Al(PO 3 ) 3 , AlF 3 and Al 2 O 3 , preferably Al (PO) 3 ) introducing one or more of 3 and AlF 3
• the Ba 2+ is one of Ba(PO 3 ) 2 , BaF 2 , BaCO 3 , BaCl 2 and Ba(NO 3 ) 2 or Introduced in one or more ways, preferably introduced in one or more of BaF 2 and BaCO 3
• the Ca 2+ , Sr 2+ , Mg 2+ are respectively fluoride, metaphosphate and carbonate Introduced in one or more ways
• the La 3+ , Gd 3+ , Y 3+ , Yb 3+ are introduced in one or more of an oxide and a fluoride, preferably in the form of an oxide introduced
• the Sb 3+, Sn 4+, Ce 4+ to oxides and fluorides of one or more way of introduction is preferably introduced in oxide form; said
• the (Sr 2+ + Ca 2+ + La 3+ + Gd 3+ + Y 3+ ) / Ba 2+ is 0.22 - 0.65, preferably 0.25 - 0.50.
• the total amount of La 3+ + Gd 3+ + Y 3+ is 2 to 10%, preferably 3.3 to 8%.
• Al 3+ /P 5+ is less than 0.63.
• the optical glass has a photoelastic coefficient B of less than 0.5 ⁇ 10 -12 Pa.
• the specific dispersion ⁇ P g,F of the optical glass is 0.011 or more, preferably 0.014 or more, more preferably 0.015 or more.
• the optical glass has an abrasion degree F A of less than 450, preferably less than 400, more preferably less than 350.
• An optical element made of the above fluorophosphate optical glass made of the above fluorophosphate optical glass.
• the invention has the beneficial effects that an optical glass having high refraction, low dispersion, excellent special dispersion and good chemical stability, excellent polishing property and excellent thermal stability can be obtained, and the optical glass has a low photoelastic coefficient and is suitable for application.
• the optical glass of the present invention is suitable for a manufacturing method such as precision molding, secondary hot pressing, and cold working, and manufactures high-performance spherical, aspherical, planar lenses, and optical elements such as prisms and gratings.
• cation percentage means the percentage of a certain cationic component to the total cation content
• anionic percentage refers to the percentage of an anionic component to the total anion content.
• P 5+ is a composition constituting the glass network.
• the content is less than 30%, the stability of the glass is not good, and when the content exceeds 40%, it is difficult to obtain the high refractive index required by the present invention.
• the percentage of P 5+ is from 32 to 37.5%.
• the main function of Al 3+ in the present invention is to improve the chemical stability and the grinding processability of the glass.
• the content is less than 12%, the chemical stability of the glass is not good; when the content is more than 20%, the crystallization of the glass The performance deteriorates and the liquidus temperature rises.
• the Al 3+ content is preferably 12-19%.
• the inventors have found that by controlling the Al 3+ /P 5+ ratio, the polishing performance of the glass is remarkably improved, and the Al 3+ /P 5+ of the present invention is less than 0.63, preferably Al 3+ /P 5+ is less than 0.6, Preferably, Al 3+ /P 5+ is less than 0.58.
• Ba 2+ is an essential component of the present invention, and can increase the refractive index and thermal stability of the glass.
• the coexistence of Ba 2+ and P 5+ is the key to obtaining a low photoelastic coefficient.
• the content is less than 30%, the refractive index of the glass is insufficient; when the content is higher than 40%, the chemical stability of the glass is lowered, especially the acid resistance is not good, so the content thereof is limited to 30-40%, preferably the content is 32. - 38%, more preferably 33 - 37.8%.
• Sr 2+ is an essential component of the present invention. Substituting Sr 2+ for partial Ba 2+ can improve the chemical stability of the glass and does not significantly reduce the refractive index of the glass. When the content is less than 1%, the effect is not obvious. When it exceeds 10%, the thermal stability of the glass is lowered, and the content is preferably from 1 to 8%, more preferably from 2 to 8%.
• Ca 2+ can improve the thermal stability of the glass and improve the acid resistance and grinding performance of the glass.
• the content is less than 1.3%, the effect is not obvious; when the content is higher than 12%, the thermal stability and refractive index of the glass are lowered. Therefore, the content thereof is limited to 1.3 to 12%, preferably 1.5 to 8%.
• La 3+ can increase the refractive index of the glass.
• the higher the refractive index of the glass the more advantageous the miniaturization of the optical element in the optical system, so the presence of La 3+ is advantageous.
• the content is more than 5%, the crystallization of the glass deteriorates, so the content thereof is limited to 0 to 5%, preferably 0 to 4%.
• Gd 3+ has the function of increasing the refractive index of glass.
• Gd 3+ has better thermal stability to glass than La 3+ , but when the content is higher than 6%, the thermal stability of the glass is lowered, so The content is limited to 0 to 6%, preferably 1 to 5%.
• Y 3+ also has the effect of increasing the refractive index of the glass.
• the content thereof can be higher than that of La 3+ and Gd 3+ .
• the content is more than 10%, the crystallization of the glass is deteriorated, so the content is limited to 0. - 10%, preferably 1-8%.
• La 3+ , Gd 3+ and Y 3+ are the key to increase the refractive index of the glass while ensuring the thermal stability of the glass under the premise of not significantly reducing the Abbe number, and the total content of La 3+ + Gd 3+ + When Y 3+ is less than 2%, the refractive index increase is not obvious. When the total content exceeds 10%, the crystallization of the glass is remarkably deteriorated, so that the total content of La 3+ + Gd 3+ + Y 3+ is limited to 2 - 10%. Preferably, the content is from 3.3 to 8%.
• the range of (Sr 2+ + Ca 2+ + La 3+ + Gd 3+ + Y 3+ ) / Ba 2+ is defined to be in the range of 0.22 to 0.65, preferably in the range of 0.25 to 0.50.
• Mg 2+ is an optional component of the present invention and has the effects of improving the thermal stability and the grinding property of the glass, but when the content is higher than 5%, the refractive index of the glass is not up to the target, so the content is limited to 0— 5%, preferably 0-3%.
• Zn 2+ is an optional component of the present invention, which can increase the refractive index of the glass and has the effect of lowering the glass transition temperature, but the relatively large dispersion causes the glass Abbe number to decrease, so the present invention limits the content of Zn 2+ to 0. - 5%, preferably in an amount of from 0 to 3%.
• Yb 3+ has the effect of increasing the refractive index of the glass.
• the content is higher than 5%, the thermal stability of the glass is lowered, so the content is limited to 0-5%, because Yb 3+ has intrinsic absorption in the near-infrared band. Therefore, it is preferably not used.
• F - is a key component for making glass have low dispersion and anomalous dispersion. If the content is less than 25%, it is difficult to achieve the desired properties; if the content is more than 40%, it is difficult to obtain a high refractive index of glass, so F - is limited to 25-40%, more preferably 28-35%.
• O 2- is an essential component constituting the glass network structure of the present invention.
• the content is less than 60%, the glass stability is insufficient and it is difficult to achieve the refractive index required for the invention; if the content is higher than 75%, it is difficult to obtain a low Dispersion and anomalous dispersion, thus limiting the content of O 2- to 60-75%, more preferably 65-72%.
• a halogen element is usually used as a clarifying agent.
• Cl - , I - , and Br - may be used as a clarifying agent, but when the amount thereof is too high, the smelting apparatus may be caused ( For example, platinum, platinum alloy vessels, etc. are damaged, so the amount of use thereof is limited to 0-1%, and further preferably, the content is 0-0.5%.
• the total content of Cl - +I - +Br - is defined to be greater than 0 but less than or equal to 1%, further preferably greater than 0 but less than or equal to 0.8%, still more preferably greater than 0 but less than or equal to 0.5%.
• Cl - is preferably used, followed by I - .
• Sb 3+ , Sn 4+ and Ce 4+ can also be used, and their contents are limited to 0 to 0.5%, 0-1%, and 0-1%, respectively.
• the defoaming effect of using a halogen element alone as a clarifying agent is not satisfactory, and the inventors have found through repeated experimental research that by using Sb 3+ , Sn 4+ and Ce 4+ At least one of the halogen elements Cl - , I - , and Br - may be added to obtain a very desirable defoaming effect.
• the present invention defines that the total content of Sb 3+ +Sn 4+ +Ce 4+ is greater than 0 but less than or equal to 1%, further preferably greater than 0 but less than or equal to 0.5%.
• the invention can also use B 3+ in an appropriate amount, but when the content is too high, the volatilization in the smelting production is large, and the glass stability is lowered, so the content thereof is limited to 0-5%, preferably the content is 0-2%, more preferably not used. .
• Si 4+ and Ge 4+ can be used in a small amount in the glass of the present invention, but if the content exceeds 3%, the glass melting temperature is remarkably increased, and the devitrification property of the glass is deteriorated, so that the contents of Si 4+ and Ge 4+ are respectively 0. - 3%, preferably in an amount of from 0 to 1%, more preferably not introduced.
• Li + , Na + , K + three alkali metal ions can reduce the melting temperature and high temperature viscosity of glass and the glass transition temperature, but the excessive content will lead to deterioration of glass crystallization, so the Li + content is limited to 0-12%.
• the content is 0-10%; the content of Na + and K + is limited to 0-5%, respectively, and the preferred content is 0-3%.
• Li + is preferably used.
• the present invention does not use environmentally harmful components such as Pb, As, Cd, Th, etc., and does not use and minimize the components of the raw materials such as Co, Cu, Fe, Ni, Cr, Mn and the like which impair the glass transmittance.
• the aforementioned glass component can be introduced into the batch using the corresponding oxide, carbonate, nitrate, hydroxide, phosphate, metaphosphate and fluoride, and the mixed batch is in platinum. (or platinum alloy) ⁇ is obtained by heating, melting, clarifying and homogenizing. In order to ensure the stability of the glass quality, a raw material containing no moisture (including crystal water and free water) is preferred.
• P 5+ is preferably introduced as a metaphosphate
• Al 3+ may be introduced in one or more of Al(PO 3 ) 3 , AlF 3 and Al 2 O 3 , preferably Al ( One or more of PO 3 ) 3 and AlF 3 are introduced because when Al 3+ is introduced as Al 2 O 3 , the crystallization property of the glass is deteriorated
• Ba 2+ may be Ba(PO 3 ) 2 , Introduced in one or more ways of BaF 2 , BaCO 3 , BaCl 2 and Ba(NO 3 ) 2 , preferably introduced in one or more of BaF 2 and BaCO 3 when Ba (NO 3 ) is introduced 2 , the corresponding oxide weight percentage should not exceed 3%, because when Ba (NO 3 ) 2 content is too high, it will cause the melting temperature to increase significantly
• Ca 2+ , Sr 2+ , Mg 2+ can be respectively Introduced in one or more of its fluorides, metaphosphates, and carbonates
• F - may be introduced from the aforementioned fluoride raw material, and O 2- may be introduced in one or more of a partial phosphate, an oxide, a carbonate and a nitrate, and Cl - , I - , Br - mainly Introduced with a halide, it is preferred to use BaCl 2 , KI and KBr, respectively.
• the content of Ba 2+ and O 2 in the present invention is high, and Ba (CO 3 ) 2 is mainly used to introduce Ba 2+ and O 2- , and the mass percentage thereof is 10% or more, preferably The content of 25% or more, in order to solve the bubble problem caused by the use of Ba(CO 3 ) 2 , the inventors creatively use at least one of Sb 3+ , Sn 4+ and Ce 4+ together with the halogen element Cl ⁇ , At least one of I - and Br - acts as a fining agent, and an ideal defoaming effect is obtained.
• the glass of the invention has a liquidus temperature below 900 ° C.
• the glass liquid has a good molding viscosity and can reduce the volatilization of F, thereby facilitating obtaining high quality without streaks. glass.
• the optical glass After precision annealing, the optical glass usually does not produce birefringence inside. However, if there is a mechanical external force or heating or cooling the glass to cause a temperature difference between the glass, stress will be generated inside the glass, and the optical properties will change to cause birefringence.
• the low photoelastic coefficient means that the glass has a small birefringence when subjected to cold and heat changes and external force impact, and is suitable for manufacturing optical devices having high stability requirements, such as manufacturing optical devices for controlling polarized light.
• the glass of the present invention has a photoelastic coefficient of less than 0.5 ⁇ 10 -12 Pa, and is suitable for manufacturing a substrate and a prism constituting a polarization beam splitter, a spatial light modulator device for performing polarization modulation, a glass substrate for electron optics, and a glass for electro-optical use. Parts, etc.
• the glass of the present invention has a large positive special dispersion ⁇ P g,F , which facilitates the correction of the advanced chromatic aberration of the optical system.
• the relative partial dispersion P g,F is expressed as:
• n g , n F , and n c correspond to refractive indices of g line (435.84 nm), F line (486.13 nm), and c line (656.27 nm), respectively.
• the special dispersion ⁇ P g,F is the difference between the relative partial dispersion P g and F from the normal line, and is expressed by the following formula:
• the glass with a larger ⁇ P g,F is generally more suitable for the correction of high-order chromatic aberration.
• the specific dispersion ⁇ P g,F of the glass of the present invention is 0.011 or more, preferably 0.014 or more, more preferably 0.015 or more.
• Fluorophosphate glass is generally "soft" and has a large wear value. When the glass wears a lot At the time, it often causes difficulty in grinding and polishing, and it is difficult to achieve precise processing of the glass surface, which affects the processing efficiency.
• the glass of the present invention has an abrasion resistance of less than 450, preferably less than 400, more preferably less than 350, so that the glass of the present invention has good abrasive processing properties.
• Glass of the present invention has excellent chemical stability, the powder method using the test method, the role of its water stability class D W 1, D A is the acid on stability of Class 2 or greater, preferably acid on stability of Class 1.
• the optical glass of the present invention is suitable for a manufacturing method such as precision molding, secondary hot pressing, and cold working, and manufactures high-performance spherical, aspherical, planar lenses, and optical elements such as prisms and gratings.
• Tables 1, 2 and 3 list the composition of the examples and comparative examples of the optical glass of the present invention, and also lists the refractive index (nd), Abbe number ( ⁇ d), and special dispersion ( ⁇ P g, of the example glass .
• F transition temperature (Tg), photoelastic coefficient (B), liquidus temperature (LT), attrition (F A ), chemical stability D W and D A , and external transmittances of 80% and 5% Wavelength ratio (represented by ⁇ 80, ⁇ 5, respectively).
• optical glasses of the examples and the comparative examples were each weighed by an oxide, a fluoride, a composite phosphate, a hydroxide, a carbonate, and a nitrate raw material corresponding to the composition components shown in Tables 1-4, and were sufficiently mixed. After adding platinum crucible, melting, clarifying and homogenizing at 900-1200 ° C, cooling to a suitable temperature, pouring the molten glass into the preheated metal mold, and putting the glass together with the metal mold into the annealing furnace After annealing, an experimental sample is obtained, and the relevant parameters of the test glass are sampled on the sample.
• Optical constant and special dispersion Test n d , n g , n F , n c and Abbe number ⁇ d according to the refractive index test method of GB/T 7962.11-2010, and calculate the special dispersion ⁇ P g,F according to the special dispersion formula described above.
• Transition temperature Tg The transition temperature Tg of the glass was tested according to the method specified in GB/T 7962.16-2010.
• Photoelastic coefficient B Using a He-Ne laser (wavelength 632.8 nm), the rated load gravity is applied in the diameter direction of the disk-shaped test sample, and the optical path difference generated at the center of the disk is measured, and the data is calculated. Photoelastic coefficient B.
• the liquidus temperature LT liquid phase temperature is tested by placing 100 ml of glass into a platinum crucible, heating to 1050 ° C to completely melt the glass, then cooling to a predetermined temperature for 2 hours, then pouring the glass into a cast iron or graphite mold. In the middle, after cooling, the glass was examined with a microscope at a magnification of 100 times, and the minimum holding temperature of the crystal was not observed, that is, the liquidus temperature of the glass. Since the present invention contains the F component, the aforementioned high temperature test was carried out under a nitrogen atmosphere. The temperature shown in the column of "liquidus temperature" in Tables 1-4 of the present invention is the lowest experimental temperature of the crystal after 2 hours of incubation, and the actual liquidus temperature of the glass is lower than or equal to the temperature shown in the table.
• Abrasion degree F A is the value obtained by multiplying the wear amount of the sample by the wear amount (volume) of the standard sample (K9 optical glass) by 100 under the same conditions, and is expressed as :
• V and V 0 represent the volumetric wear of the sample to be tested and the standard sample, respectively
• W and W 0 represent the mass wear of the sample to be tested and the standard sample, respectively
• ⁇ and ⁇ 0 represent the density of the sample to be tested and the standard sample, respectively.
• the water resistance stability D W of the glass is divided into six categories, as shown in the following table.
• the acid resistance stability D A of the glass is classified into six categories, as shown in the following table.
• Coloring degree ⁇ 80 / ⁇ 5 The short-wave transmission spectrum characteristics of the glass are represented by the degree of coloration.
• the thickness of the test sample was 10 ⁇ 0.1 mm, and ⁇ 80 and ⁇ 5 respectively correspond to wavelengths corresponding to a glass transmittance (including surface reflection loss) of 80% and 5%, expressed in units of 10 nm.
• the fluorophosphate optical glass of the present invention has a refractive index (nd) of more than 1.59 and an Abbe number (vd) of more than 67, and has excellent special dispersion and good chemical stability and polishing properties, and heat. Excellent stability, so the glass of the invention is suitable for optical system to eliminate high-order chromatic aberration optical design; suitable for precision molding, secondary hot pressing and cold working manufacturing methods, manufacturing high performance spherical, aspherical, planar lens and prism, grating An optical element having a photoelastic coefficient of less than 0.5 ⁇ 10 -12 Pa, which is suitable for applications requiring high refractive index thermal stability of glass.

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