CN115385572A - Phosphate optical glass, preparation method thereof and optical element - Google Patents
Phosphate optical glass, preparation method thereof and optical element Download PDFInfo
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- CN115385572A CN115385572A CN202211080793.3A CN202211080793A CN115385572A CN 115385572 A CN115385572 A CN 115385572A CN 202211080793 A CN202211080793 A CN 202211080793A CN 115385572 A CN115385572 A CN 115385572A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
- C03C3/21—Silica-free oxide glass compositions containing phosphorus containing titanium, zirconium, vanadium, tungsten or molybdenum
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
- C03C3/17—Silica-free oxide glass compositions containing phosphorus containing aluminium or beryllium
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
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Abstract
The invention provides phosphate optical glass, a preparation method thereof and an optical element. The phosphate optical glass comprises the following components by taking the total mass of the phosphate optical glass as 100 percent: ba (PO) 3 ) 2 40-59.9%; al (PO) 3 ) 3 10-20%; naPO 3 5 to 15 percent; baO is 0-15%; al (Al) 2 O 3 0 to 5 percent; na (Na) 2 O is 0 to 10 percent; znO is 0 to 4.9 percent; zrO (ZrO) 2 0 to 5 percent; nb 2 O 5 0 to 3 percent; la 2 O 3 0 to 2.49 percent; sb 2 O 3 0 to 0.1 percent; the refractive index of the phosphate optical glass is 1.55-1.62, and the Abbe number is 55.00-62.97. The phosphate optical glass has the advantages of high cost performance, moderate viscosity, good crystallization performance, excellent transmission performance and excellent chemistryStability and mechanical properties; the glass transition temperature, the expansion coefficient and the density are all low.
Description
Technical Field
The invention relates to phosphate optical glass, a preparation method thereof and an optical element, and belongs to the technical field of optical glass.
Background
In order to meet the requirements of better imaging quality and higher definition of products such as digital cameras, digital video cameras, photographable cameras and the like, the aspheric lens is more and more widely used. The aspheric lens is mostly manufactured by a precision compression molding method, the mold used by the method is made of super-hard alloy materials, the requirement on the precision of the surface shape is extremely high, and the manufacturing cost is also very high. The higher the temperature required for press forming, the greater the likelihood of oxidation and scratching of the mold surface. Therefore, to extend the useful life of the mold, a lower transition temperature is desirable.
The patent disclosed in CN106536436A, CN104803603A, CN110114321A, CN102476916A contains a large amount of B 2 O 3 And B is 2 O 3 The large amount of the metal oxide can greatly reduce the viscosity of the glass liquid, so that the stripes are difficult to eliminate, and the production difficulty is increased.
The patent disclosed in CN106536436A, CN1197042A, CN109415240A contains a large amount of SiO 2 。SiO 2 Can increase the viscosity of the glass liquid and improve the structural strength of the glass network, but can greatly improve the glass transition temperature and the sagging temperature at the same time, is not beneficial to reducing the glass softening temperature, and can also increase the precision molding cost.
Patent publication No. CN104803603A, CN110590157A, CN104803603A, et al, contains Gd 2 O 3 Isorare earth elements, especially Gd 2 O 3 The price of (a) is higher and higher, and the market demand of low cost is not met.
CN101937109A, CN110040954A, CN106536436A contains Li 2 O。Li 2 O can effectively reduce the glass transition temperature and the sagging temperature and improve the melting property of the glass, but the addition of a small amount of O can cause great reduction of viscosity, thereby increasing the production difficulty and aggravating the corrosion to the crucible.
CN104445931A disclosureIn which WO is contained 3 The coloring matter is not beneficial to improving the transmission performance of the glass and the color is obviously deepened.
The patent disclosed in CN110642512A, CN111187003A contains F, which is mainly used for reducing glass dispersion, but is extremely volatile, easily causes great fluctuation of optical properties and generation of volatile stripes, and has high production difficulty and high manufacturing cost.
Disclosure of Invention
Problems to be solved by the invention
The invention aims to solve the technical problem of providing phosphate optical glass with the refractive index of 1.55-1.65, the Abbe number of 55.00-62.97, excellent transmission performance, chemical stability and mechanical performance, low transformation temperature, low expansion coefficient and low density, a preparation method thereof and an optical element.
Means for solving the problems
The invention provides phosphate optical glass, which comprises the following components in percentage by mass of 100 percent of the total mass of the phosphate optical glass:
Ba(PO 3 ) 2 from 40 to 59.9%, preferably from 45 to 59.5%;
Al(PO 3 ) 3 10-20%, preferably 10-18%;
NaPO 3 from 5 to 15%, preferably from 8 to 15%;
BaO is 0 to 15%, preferably 3 to 12%;
Al 2 O 3 from 0 to 5%, preferably from 1 to 3%;
Na 2 o is 0 to 10%, preferably 0 to 8%;
ZnO of 0 to 4.9%, preferably 2 to 3.5%;
ZrO 2 from 0 to 5%, preferably from 1 to 3%;
Nb 2 O 5 from 0 to 3%, preferably from 1 to 2%;
La 2 O 3 from 0 to 2.49%, preferably from 1 to 2%;
Sb 2 O 3 from 0 to 0.1%, preferably from 0 to 0.05%;
the refractive index of the phosphate optical glass is 1.55-1.62, and the Abbe number is 55.00-62.97.
The phosphate optical glass according to the present invention, wherein, by mass, ba (PO) 3 ) 2 Content of (C), al (PO) 3 ) 3 Content of (A) and NaPO 3 Sum of contents of (B) Ba (PO) 3 ) 2 +Al(PO 3 ) 3 +NaPO 3 65.0-96.5%, preferably 68-92%; and/or
Ba(PO 3 ) 2 Content of (C), al (PO) 3 ) 3 Content of (A), naPO 3 Content of (2) and Al 2 O 3 Sum of contents of (B) Ba (PO) 3 ) 2 +Al(PO 3 ) 3 +NaPO 3 +Al 2 O 3 From 65 to 98%, preferably from 68 to 95%.
The phosphate optical glass according to the present invention, wherein, by mass, na 2 The sum of the content of O and the content of BaO, the content of ZnO and Al 2 O 3 Sum of contents of ratio of (Na) 2 O+BaO)/(ZnO+Al 2 O 3 ) Is 26 or less, preferably 20 or less.
The phosphate optical glass according to the present invention, wherein the content of ZnO is equal to that of Na 2 Sum of O content ZnO + Na 2 O is 0 to 12%, preferably 1 to 10%; and/or
La 2 O 3 With ZrO 2 Sum of contents of La 2 O 3 +ZrO 2 Is 0 to 8%, preferably 2 to 7%.
The phosphate optical glass of the present invention does not contain V, mo, cr, mn, fe, co, ni, cu, ag, th, tl, os, be, se, pb, as, cd, F, li 2 O、B 2 O 3 、MgO、CaO、Yb 2 O 3 、Ta 2 O 5 、Y 2 O 3 、Gd 2 O 3 At least one of (1).
The phosphate optical glass according to the present invention has a glass transition temperature of 456 ℃ or lower and a sag temperature of 510 ℃ or lower.
Phosphate optical glass according to the inventionGlass, wherein the phosphate optical glass has a degree of abrasion of 390 or less and a hardness of 330X 10 7 Pa or more, and a density of 3.77g/cm 3 The following.
The phosphate optical glass of the present invention has a moisture resistance stability of grade 1, a water resistance stability of grade 1, and an acid resistance stability D A Or acid resistance stability R A Is more than 3 grades.
The invention also provides a preparation method of the phosphate optical glass, which comprises the following steps: the components are weighed according to the proportion, evenly mixed and smelted, and then poured or leaked injected into a forming die for forming, or directly pressed for forming, or manufactured into an optical element through precision die pressing.
The invention also provides an optical element comprising the phosphate optical glass according to the invention.
ADVANTAGEOUS EFFECTS OF INVENTION
The phosphate optical glass has the advantages of high cost performance, moderate viscosity, good crystallization performance, easy realization of batch production, excellent transmission performance, chemical stability and mechanical performance, low glass transition temperature, expansion coefficient and density, and suitability for precision die pressing and optical element preparation.
The preparation method of the phosphate optical glass is simple and feasible, the raw materials are easy to obtain, and the phosphate optical glass is suitable for mass production.
Detailed Description
The present invention will be described in detail below. The technical features described below are explained based on typical embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples.
Furthermore, in the following detailed description, numerous specific details are set forth in order to provide a better understanding of the present invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In other instances, methods, means, devices and steps which are well known to those skilled in the art have not been described in detail so as not to obscure the invention.
It should be noted that:
in the present specification, the numerical range represented by "a value a to B value" means a range including the endpoint value A, B.
All units used in the present invention are international standard units unless otherwise stated, and numerical values and numerical ranges appearing in the present invention should be understood to include errors allowed in industrial production.
In the present specification, reference to "some particular/preferred embodiments," "other particular/preferred embodiments," "embodiments," and the like, means that a particular element (e.g., feature, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments.
The invention provides phosphate optical glass, which comprises the following components in percentage by mass of 100 percent of the total mass of the phosphate optical glass:
Ba(PO 3 ) 2 from 40 to 59.9%, preferably from 45 to 59.5%;
Al(PO 3 ) 3 10-20%, preferably 10-18%;
NaPO 3 from 5 to 15%, preferably from 8 to 15%;
BaO is 0 to 15%, preferably 3 to 12%;
Al 2 O 3 from 0 to 5%, preferably from 1 to 3%;
Na 2 o is 0 to 10%, preferably 0 to 8%;
ZnO of 0 to 4.9%, preferably 2 to 3.5%;
ZrO 2 from 0 to 5%, preferably from 1 to 3%;
Nb 2 O 5 from 0 to 3%, preferably from 1 to 2%;
La 2 O 3 from 0 to 2.49%, preferably from 1 to 2%;
Sb 2 O 3 from 0 to 0.1%, preferably from 0 to 0.05%;
the refractive index of the phosphate optical glass is 1.55-1.62, and the Abbe number is 55.00-62.97.
In the present invention, the raw material is introduced in various forms such as oxides, carbonates, nitrates, sulfates, phosphates, hydroxides, etc. capable of introducing the compounds in their respective contents. As described below, the contents of the respective components are expressed in weight percent.
Ba(PO 3 ) 2 Is an essential component for forming the network structure of the phosphate optical glass of the present invention, and can improve the chemical stability of the phosphate optical glass. However, when the content thereof is too high, the refractive index of the phosphate optical glass is lowered, the devitrification resistance and the mechanical properties are deteriorated, and particularly, the chemical stability such as acid resistance stability and water resistance stability is lowered and the density is increased; when the content is too low, the tendency of crystallization of the phosphate optical glass increases, so that the phosphate optical glass becomes unstable and resistance to devitrification and chemical stability deteriorate. Thus, ba (PO) is 100% of the total mass of the phosphate optical glass 3 ) 2 The content of (B) is 40 to 59.9%, preferably 45 to 59.5%, and may be, for example, 50 to 59%,55 to 58%, etc.
BaO is not an essential component of the phosphate optical glass of the present invention, and is effective for increasing the refractive index of the phosphate optical glass and improving the melting property of the glass. In addition, baO can improve chemical stability and devitrification resistance of the phosphate optical glass, and is advantageous in improving internal transmittance and mechanical properties of the phosphate optical glass. When the content of BaO is too high, the chemical stability and devitrification property of the phosphate optical glass are remarkably deteriorated and the density is remarkably increased. Accordingly, the content of BaO is 0 to 15%, preferably 3 to 12%, for example: 5-10%, etc. In the present invention, baO is introduced in the form of carbonate, nitrate, sulfate, etc.
Al(PO 3 ) 3 Is an essential component of the phosphate optical glass, can adjust optical constants, enhance the network structure of the phosphate optical glass and obviously improve the tolerance of the phosphate optical glassMoisture stability, water stability and acid stability, and also improve the mechanical properties of phosphate optical glass. When the content thereof is excessively low, the devitrification resistance stability, chemical stability and mechanical properties of the phosphate optical glass are remarkably deteriorated; when the content is too high, the crystallization temperature of the phosphate optical glass is remarkably increased and the melting property is also deteriorated. Therefore, al (PO) is 100% by mass of the phosphate optical glass 3 ) 3 In an amount of 10 to 20%, preferably 10 to 18%, for example: 12-16%, etc.
Al 2 O 3 Is not an essential component of the phosphate optical glass of the present invention, but is an effective ingredient for improving moisture resistance stability, water resistance stability, mechanical properties and the like of the phosphate optical glass. When free oxygen is sufficient, al 2 O 3 Can form alundum tetrahedron, strengthen the network structure of the phosphate optical glass and improve the chemical stability and the mechanical property of the phosphate optical glass. However, when the amount exceeds 5%, the glass transition temperature or sag temperature increases, the stability and high-temperature melting property of the phosphate optical glass deteriorate, the refractive index of the phosphate optical glass decreases, and the resistance to devitrification also deteriorates. Therefore, al is 100% by mass of the phosphate optical glass 2 O 3 The content of (B) is 0 to 5%, preferably 1 to 3%. In the present invention, al 2 O 3 Al may be used 2 O 3 Or Al (OH) 3 Is introduced in the form of (1).
NaPO 3 The phosphate optical glass disclosed by the invention is an essential component, can reduce the melting temperature, glass transition temperature, sag temperature and liquidus temperature of the phosphate optical glass, is favorable for enhancing the network structure of the phosphate optical glass, and improves the chemical stability of the phosphate optical glass. When the content thereof is too high, it is not favorable to obtain the intended optical constants, and the chemical stability and glass forming property of the phosphate optical glass are deteriorated; when the content is too low, the melting property of the phosphate optical glass is deteriorated, and it is not favorable to obtain the desired glass transition temperature, sag temperature, and further, it is not favorable to enhance the network structure of the glass. Therefore, the phosphate optical glassIs 100 percent of NaPO 3 In an amount of 5-15%, preferably 8-15%, for example: 8-12%, etc.
Ba(PO 3 ) 2 、Al(PO 3 ) 3 And NaPO 3 The phosphate optical glass is an essential component for forming a phosphate optical glass network, and when the content is appropriate, not only is the network structure of the phosphate optical glass enhanced, but also various performances such as chemical stability, mechanical property and the like are relatively excellent. By mass, ba (PO) 3 ) 2 Content of (C), al (PO) 3 ) 3 Content of (A) and NaPO 3 Sum of contents of Ba (PO) 3 ) 2 +Al(PO 3 ) 3 +NaPO 3 If the ratio is too low, the network structure is loose, and the crystallization performance, the chemical stability and the mechanical performance are all rapidly deteriorated; but if Ba (PO) 3 ) 2 Content of (C), al (PO) 3 ) 3 Content of (A) and NaPO 3 Sum of contents of (B) Ba (PO) 3 ) 2 +Al(PO 3 ) 3 +NaPO 3 Too high, not only the optical constant is difficult to be expected, but also the degree of abrasion is increased, and chemical stability such as moisture resistance, water resistance, acid resistance and the like is deteriorated. Thus, in the phosphate optical glass of the present invention, ba (PO) 3 ) 2 +Al(PO 3 ) 3 +NaPO 3 From 65.0 to 96.5%, preferably from 68 to 92%, for example: 72-87%, etc.
Ba(PO 3 ) 2 、Al(PO 3 ) 3 、NaPO 3 And Al 2 O 3 Are all components for forming a network structure of the phosphate optical glass, and are important components for improving the crystallization resistance stability, the chemical stability, the mechanical property and the like of the phosphate optical glass. Ba (PO) 3 ) 2 Content of (C), al (PO) 3 ) 3 Content of (A), naPO 3 Content of (C) and Al 2 O 3 Sum of contents of Ba (PO) 3 ) 2 +Al(PO 3 ) 3 +NaPO 3 +Al 2 O 3 Too low, it is not favorable for obtaining desired optical properties, melting properties, physicochemical properties, mechanical properties, etc.; ba (PO) 3 ) 2 Content of (C), al (PO) 3 ) 3 Content of (A), naPO 3 In an amount ofAnd Al 2 O 3 Sum of contents of Ba (PO) 3 ) 2 +Al(PO 3 ) 3 +NaPO 3 +Al 2 O 3 If the temperature is too high, the crystallization temperature of the phosphate optical glass increases, and the melting property and the like deteriorate. Thus, in the phosphate optical glass of the present invention, ba (PO) 3 ) 2 +Al(PO 3 ) 3 +NaPO 3 +Al 2 O 3 From 65 to 98%, preferably from 68 to 95%, for example: 72-92%, 75-88% and the like.
Na 2 O can also increase the resistance to vitrification, lower the glass transition temperature, yield point and liquidus temperature of the phosphate optical glass, and can be added as an optional component for improving the high-temperature melting property of the phosphate optical glass. However, when the amount of the phosphate optical glass is excessively added, not only the stability of the phosphate optical glass is deteriorated, but also the moisture resistance stability, the water resistance stability, the acid resistance stability, and the like are remarkably deteriorated, and the abrasion degree is increased and the refractive index is decreased. Therefore, in the present invention, na is contained in an amount of 100% by mass based on the total mass of the phosphate optical glass 2 The content of O is 0 to 10wt%, preferably 0 to 8wt%, for example: 2-8 wt%, 3-6 wt%, etc. Na (Na) 2 O may be introduced in the form of carbonate, nitrate, sulfate, or the like.
ZnO is an effective component for improving the melting property of the phosphate optical glass, and improving the refractive index and dispersion of the phosphate optical glass, and when the ZnO is properly used, the chemical stability of the phosphate optical glass, such as acid resistance stability and water resistance stability, can be obviously improved, but the ZnO is not an essential component. When the phosphate optical glass contains more free oxygen, znO exists in a zinc-oxygen tetrahedron and enters a phosphorus-oxygen network to serve as a network former, so that the structural stability, the chemical stability and the mechanical property of the phosphate optical glass are improved. When the free oxygen content is relatively small, znO exists as zinc-oxygen octahedron, and acts as an extranet body to destroy the glass network structure. When the content of ZnO is too high, the chemical stability of the phosphate optical glass is deteriorated, the abrasion degree is greatly increased, the hardness is decreased, and the transmittance is lowered, so that the content of ZnO is 0 to 4.9%, preferably 2 to 3.5%, based on 100% by mass of the total phosphate optical glass.
Na 2 O, baO are all optional components of the phosphate optical glass of the present invention, and provide free oxygen to promote the formation of phosphorus-oxygen tetrahedron, aluminum-oxygen tetrahedron and zinc-oxygen tetrahedron, thereby improving network strength, chemical stability, mechanical properties and the like of the phosphate optical glass. By mass when Na 2 The sum of the content of O and the content of BaO, the content of ZnO and Al 2 O 3 Sum of contents of ratio of (Na) 2 O+BaO)/(ZnO+Al 2 O 3 ) When the temperature is too high, the free oxygen is excessive, the proportion of the external network body is increased, the performance of the formed glass is obviously reduced, and the crystallization performance, the chemical stability, the mechanical performance and the like are obviously poor. Therefore, in the phosphate optical glass of the present invention, by mass, na 2 The sum of the content of O and the content of BaO, the content of ZnO and Al 2 O 3 Sum of contents of ratio of (Na) 2 O+BaO)/(ZnO+Al 2 O 3 ) 26 or less, preferably 20 or less, for example: 15 below, 10 below, again: 0.5-7, 0.8-5, etc.
ZnO、Na 2 O is beneficial to improving the melting property of the phosphate optical glass, reducing the glass transition temperature, the sag temperature and the like of the phosphate optical glass. In addition, when the content of ZnO is equal to that of Na 2 Sum of O content ZnO + Na 2 When the amount of O is proper, enough free oxygen can be provided to promote the formation of phosphorus-oxygen tetrahedrons and aluminum-oxygen tetrahedrons, so that the network structure of the glass is enhanced, the chemical stability, the mechanical property and the like of the phosphate optical glass are improved, and the density can be reduced; but if the ZnO content is equal to Na 2 Sum of O content ZnO + Na 2 If O is too high, the content of the network exosomes is increased, but the network structure is damaged, and the opposite effect is achieved. In the phosphate optical glass of the present invention, znO + Na is used for the purpose of improving the optical characteristics of the optical glass 2 The content of O is between 0 and 12%, preferably between 1 and 10%, for example: 2-8%, 3-7%, etc.
ZrO 2 When present in appropriate amounts, the phosphate optical glass of the present invention, which is an optional component, can improve optical constants, resistance to devitrification, mechanical properties and chemical stability, particularly acid stability, water stability and moisture stability. When ZrO 2 In an amount ofWhen the temperature is high, the crystallization property of the phosphate optical glass is deteriorated, and the melting temperature and the glass transition temperature of the phosphate optical glass are sharply increased, whereby ZrO tends to be deteriorated 2 The content of (B) is 0 to 5%, preferably 1 to 3%.
La 2 O 3 When present in appropriate amounts, the phosphate optical glass of the present invention, which is an optional component, can improve optical constants, resistance to devitrification, mechanical properties and chemical stability, particularly acid stability, water stability and moisture stability. When La 2 O 3 When the content of (b) is too high, the crystallization property of the phosphate optical glass is deteriorated, and the melting temperature and the glass transition temperature of the phosphate optical glass are sharply increased, so that La is contained in an amount of 100% by mass of the phosphate optical glass 2 O 3 The content of (B) is 0 to 2.49%, preferably 1 to 2%.
La 2 O 3 、ZrO 2 The proper amount of the La is beneficial to comprehensively improving the chemical stability, the mechanical property and the like of the phosphate optical glass, but the La 2 O 3 With ZrO 2 Sum of contents of La 2 O 3 +ZrO 2 If the content is too high, the melting property of the phosphate optical glass is rapidly deteriorated, the glass transition temperature and the sag temperature are also obviously increased, the water resistance stability, the acid resistance stability and the like are reduced, and the crystallization property and the mechanical property are both deteriorated. In the phosphate optical glass of the present invention, therefore, la 2 O 3 With ZrO 2 Sum of contents of La 2 O 3 +ZrO 2 From 0 to 8%, preferably from 2 to 7%, for example: 3-5%, etc.
Nb 2 O 5 Has the effects of improving refractive index and dispersion, improving chemical stability and crystallization performance of phosphate optical glass, but if Nb is used 2 O 5 Too high content of (A) not only makes it difficult to obtain the desired optical constants, but also markedly increases the density, while destroying the devitrification properties and chemical stability of the phosphate optical glass, and therefore, nb 2 O 5 The content of (B) is 0 to 3%, preferably 1 to 2%.
Sb 2 O 3 Optionally added as a defoaming agent, howeverSb 2 O 3 When the content of (A) is too high, the degree of coloration of the phosphate optical glass increases, and the transparency deteriorates. Thus, sb 2 O 3 The content of (B) is 0 to 0.1%, preferably 0 to 0.05%.
In order to ensure the transmittance of the phosphate optical glass, the phosphate optical glass provided by the invention can not contain compounds or fluorides of Th, pb, as, cd, F and the like which are harmful elements to the environment and human body. Or may not contain Tl, os, be, se or the like, or Yb having an absorption peak in the near infrared band and decreasing the transmittance of the phosphate optical glass 2 O 3 Does not contain expensive Ta 2 O 5 、Y 2 O 3 And Gd 2 O 3 And the like. In addition, when it is not necessary to color the phosphate optical glass of the present invention, the phosphate optical glass of the present invention may also not contain other elements that can be colored, such as: v, mo, cr, mn, fe, co, ni, cu, ag, etc. The phosphate optical glass of the present invention preferably further does not contain Li 2 O、MgO、B 2 O 3 CaO, and the like.
The phosphate optical glass has the glass transition temperature of not higher than 456 ℃, the sagging temperature of not higher than 510 ℃ and the density of not more than 3.77g/cm 3 . The phosphate optical glass has abrasion degree of 390 or less and hardness of 330X 10 7 Pa or above. The moisture resistance stability and the water resistance stability of the phosphate optical glass are both 1 grade, and the acid resistance stability D A Or acid resistance stability R A Is grade 3 or above grade 3. The bubbles of the phosphate optical glass are all 1-grade, and the stripes are all B-grade.
The present invention also provides a method for producing a phosphate optical glass according to the present invention, comprising: the components are weighed according to the proportion, evenly mixed and smelted, and then poured or leaked injected into a forming die for forming or directly pressed for forming.
Specifically, the raw materials are weighed according to a specified proportion, mixed into a batch, smelted in a crucible made of precious metals such as platinum and the like at the temperature of 1200-1300 ℃, after the raw materials are melted into molten glass, the temperature is raised to 1350-1400 ℃, a stirrer made of precious metal materials such as platinum and the like is started to stir and homogenize, and the stirring time is controlled to be 2.5-6 hours. After stirring, heating to 1360-1420 deg.C, keeping the temperature for 5-10h, clarifying to make the bubbles float sufficiently, then cooling to 1050-1200 deg.C, pouring or leaking into the forming mould or molding by compression, finally annealing and processing to obtain the phosphate optical glass or optical element of the present invention.
The present invention also provides an optical element comprising the phosphate optical glass according to the present invention.
Examples
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by manufacturers, and are all conventional products which can be obtained commercially or prepared conventionally.
Performance testing
1. Refractive index n d Abbe number upsilon d
The obtained phosphate optical glass is subjected to a refractive index n according to a test method of GB/T7962.1-2010 d Abbe number upsilon d Measurement of (2), n listed in the Table d 、υ d Data after annealing at-4 ℃.
2. Degree of wear F A
The degree of abrasion was measured according to the test method specified in GB/T7962.19.
3. Knoop hardness HK
The Knoop hardness is measured according to the test method specified in ISO 9385.
4. Glass transition temperature Tg and sag temperature Ts
The measurement was carried out according to the method specified in GB/T7962.16.
5. Density p
The density of the resulting phosphate optical glass was measured according to the test method of GB/T7962.20-2010.
6. Stability to Water D W Acid resistance stability D A
The chemical stability of the obtained phosphate optical glass is subjected to water-resistant stability D according to a test method of JB/T10576-2006 W Acid resistance stability D A And (6) carrying out testing.
7. Moisture stability RC, acid stability RA
The stability of phosphate optical glass against humid atmospheric agents is classified into three classes as shown in the following table, according to the time required for the formation of hydrolytic stains on the polished surface of the glass at a temperature of 50 ℃ and a relative humidity of 85%.
| Rank of | 1 | 2 | 3 |
| Time (H) | >20 | 5～20 | <5 |
The acid resistance stability of the phosphate optical glass was classified into three grades as shown in the following table, depending on the time required for the glass polished surface to develop interference color, or the surface to develop mottle or peeling, under the action of an acetic acid solution at a temperature of 50 ℃ at 0.1N (pH = 2.9).
| Rank of | 1 | 2 | 3 |
| Time (H) | >5 | 1～5 | <1 |
8. Air bubble
100cm for phosphate optical glass bubble grade 3 The total cross-sectional area of bubbles (diameter phi is not less than 0.03 mm) contained in the glass is determined, and the glass is divided into 5 grades, which are shown in the following table. Calculi, crystals and other inclusions are also counted as bubbles. The sectional area of the prolate bubble is calculated by taking the arithmetic mean of the longest axis and the shortest axis as the diameter.
9. Stripe
The stripe degree is checked by a parallel light path stripe instrument consisting of a point light source and a lens, a phosphate optical glass is rotated, a stripe image in the direction of a cut surface of the phosphate optical glass which is most easy to generate stripes is checked, and the stripe image is compared with a standard sample and is divided into the following four grades:
| rank of | Stripe feature |
| A | Fringe-free image |
| B | With fine and dispersed stripes |
| C | With parallel fine stripes |
| D | With parallel and slightly rough stripes |
Examples 1 to 23
Raw materials corresponding to 1-23 example components shown in tables 1-4 are smelted in a crucible made of platinum at the temperature of 1300 ℃, after the raw materials are melted into molten glass, the temperature is raised to 1360 ℃, a stirrer made of platinum materials is started to stir and homogenize, and the stirring time is controlled to be 3 hours. After stirring, heating to 1380 ℃, keeping the temperature for 6 hours, clarifying to enable bubbles to float sufficiently, then cooling to 1200 ℃, pouring or leaking into a forming die or carrying out compression molding, and finally annealing and processing to obtain the phosphate optical glass.
Table 1: glass compositions and performance parameters for examples 1-6
Table 2: glass compositions and Performance parameters for examples 7-12
Table 3: glass compositions and performance parameters for examples 13-18
Table 4: glass compositions and performance parameters for examples 19-23
Comparative example A, B
The raw materials corresponding to the components in comparative example A, B in table 5 were weighed in the prescribed proportions, and prepared by the same preparation method as in examples 1 to 23, to obtain the phosphate optical glass of comparative example A, B.
Table 5: glass composition and Performance parameters for comparative example A, B
As can be seen from tables 1-5, comparative example A does not contain NaPO as compared with examples 1-23 of the present invention 3 Containing an excess of Ba (PO) 3 ) 2 And La 2 O 3 The Abbe number is not in the range of the invention, and the Tg of the obtained phosphate optical glass is as high as 608 ℃, which is not suitable for compression molding, otherwise, the service life of the mold is greatly shortened, and the cost is greatly increased; meanwhile, the introduction of a large amount of macromolecular refractory substances causes the rise of melting and clarifying temperatures and increases the difficulty of eliminating bubbles; comparative example B does not contain Ba (PO) 3 ) 2 、Al(PO 3 ) 3 And NaPO 3 The glass contains excessive BaO and ZnO, the refractive index and the Abbe number are not in the range of the invention, the stability of the glass is greatly damaged, and the specific gravity is larger; in addition, B 2 O 3 The large amount of the additive can greatly reduce the viscosity of the glass liquid, increase the volatilization, and be not beneficial to the elimination of the stripes and the stable control of the refractive index.
The above examples of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A phosphate optical glass, characterized by comprising, based on 100% of the total mass of the phosphate optical glass:
Ba(PO 3 ) 2 from 40 to 59.9%, preferably from 45 to 59.5%;
Al(PO 3 ) 3 10-20%, preferably 10-18%;
NaPO 3 from 5 to 15%, preferably from 8 to 15%;
BaO is 0 to 15%, preferably 3 to 12%;
Al 2 O 3 from 0 to 5%, preferably from 1 to 3%;
Na 2 o is 0 to 10%, preferably 0 to 8%;
ZnO of 0 to 4.9%, preferably 2 to 3.5%;
ZrO 2 from 0 to 5%, preferably from 1 to 3%;
Nb 2 O 5 from 0 to 3%, preferably from 1 to 2%;
La 2 O 3 from 0 to 2.49%, preferably from 1 to 2%;
Sb 2 O 3 from 0 to 0.1%, preferably from 0 to 0.05%;
the refractive index of the phosphate optical glass is 1.55-1.62, and the Abbe number is 55.00-62.97.
2. Phosphate optical glass according to claim 1, characterised in that Ba (PO) 3 ) 2 Content of (C), al (PO) 3 ) 3 Content of (A) and NaPO 3 Sum of contents of Ba (PO) 3 ) 2 +Al(PO 3 ) 3 +NaPO 3 65.0 to 96.5%, preferably 68 to 92%; and/or
Ba(PO 3 ) 2 Content of (C), al (PO) 3 ) 3 Content of (A), naPO 3 Content of (C) and Al 2 O 3 Sum of contents of Ba (PO) 3 ) 2 +Al(PO 3 ) 3 +NaPO 3 +Al 2 O 3 From 65 to 98%, preferably from 68 to 95%.
3. Phosphate optical glass according to claim 1 or 2, characterised in that, by mass, na 2 The sum of the content of O and the content of BaO, the content of ZnO and Al 2 O 3 Sum of contents of ratio of (Na) 2 O+BaO)/(ZnO+Al 2 O 3 ) Is 26 or less, preferably 20 or less.
4. A phosphate optical glass according to any one of claims 1 to 3, characterized in that the content of ZnO is in combination with Na 2 Sum of O content ZnO + Na 2 O is 0 to 12%, preferably 1 to 10%; and/or
La 2 O 3 With ZrO 2 Sum of contents of La 2 O 3 +ZrO 2 Is 0 to 8%, preferably 2 to 7%.
5. A phosphate optical glass according to any one of claims 1 to 4, wherein V, mo, cr, mn, fe, co, ni, cu, ag, th, tl, os, be, se, pb, as, cd, F, li and Ag are not present in the phosphate optical glass 2 O、B 2 O 3 、MgO、CaO、Yb 2 O 3 、Ta 2 O 5 、Y 2 O 3 、Gd 2 O 3 At least one of (1).
6. A phosphate optical glass according to any one of claims 1 to 5, wherein the phosphate optical glass has a glass transition temperature of 456 ℃ or less and a sag temperature of 510 ℃ or less.
7. A phosphate optical glass according to any one of claims 1 to 6, characterized in that the phosphate optical glass has an abrasion degreeNot more than 390, hardness of 330X 10 7 Pa or above, and density of 3.77g/cm 3 The following.
8. The phosphate optical glass according to any one of claims 1 to 7, wherein the phosphate optical glass has a moisture resistance stability of grade 1, a water resistance stability of grade 1, and an acid resistance stability D A Or acid stability R A Is more than 3 grades.
9. A method for producing a phosphate optical glass according to any one of claims 1 to 8, comprising: the components are weighed according to the proportion, evenly mixed and smelted, and then poured or leaked injected into a forming die for forming, or directly pressed for forming, or manufactured into an optical element through precision die pressing.
10. An optical element comprising the phosphate optical glass according to any one of claims 1 to 8.
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|---|---|---|---|---|
| US4990468A (en) * | 1988-10-06 | 1991-02-05 | Sumita Optical Glass, Inc. | Fluorophosphate optical glass |
| WO2010108435A1 (en) * | 2009-03-27 | 2010-09-30 | 成都光明光电股份有限公司 | Fluorophosphate optical glass |
| US20100317504A1 (en) * | 2008-02-08 | 2010-12-16 | National Institute of Advanced Industrial Sciences and Technology | Optical glass |
| CN102476916A (en) * | 2010-11-23 | 2012-05-30 | 湖北新华光信息材料有限公司 | Phosphorus crown optical glass with medium refractive index and high Abbe number |
| CN108675631A (en) * | 2018-06-04 | 2018-10-19 | 湖北新华光信息材料有限公司 | A kind of phosphate optical glass and preparation method thereof and optical element, optical filter |
| CN110698062A (en) * | 2019-10-25 | 2020-01-17 | 中国科学院西安光学精密机械研究所 | Radiation-resistant fluorophosphate glass and preparation method thereof |
-
2022
- 2022-09-05 CN CN202211080793.3A patent/CN115385572B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4990468A (en) * | 1988-10-06 | 1991-02-05 | Sumita Optical Glass, Inc. | Fluorophosphate optical glass |
| US20100317504A1 (en) * | 2008-02-08 | 2010-12-16 | National Institute of Advanced Industrial Sciences and Technology | Optical glass |
| WO2010108435A1 (en) * | 2009-03-27 | 2010-09-30 | 成都光明光电股份有限公司 | Fluorophosphate optical glass |
| CN102476916A (en) * | 2010-11-23 | 2012-05-30 | 湖北新华光信息材料有限公司 | Phosphorus crown optical glass with medium refractive index and high Abbe number |
| CN108675631A (en) * | 2018-06-04 | 2018-10-19 | 湖北新华光信息材料有限公司 | A kind of phosphate optical glass and preparation method thereof and optical element, optical filter |
| CN110698062A (en) * | 2019-10-25 | 2020-01-17 | 中国科学院西安光学精密机械研究所 | Radiation-resistant fluorophosphate glass and preparation method thereof |
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