CN113480170B - Fluorophosphate optical glass and preparation method thereof - Google Patents
Fluorophosphate optical glass and preparation method thereof Download PDFInfo
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- CN113480170B CN113480170B CN202110874864.6A CN202110874864A CN113480170B CN 113480170 B CN113480170 B CN 113480170B CN 202110874864 A CN202110874864 A CN 202110874864A CN 113480170 B CN113480170 B CN 113480170B
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- 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
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Abstract
The invention provides fluorophosphate optical glass and a preparation method thereof. The fluorophosphate optical glass is calculated by taking the total mass of the fluorophosphate optical glass as 100 percentThe acid salt optical glass comprises the following components: al (PO) 3 ) 3 ：20～35％；BaO：25～38％；Al 2 O 3 ：0～5％；AlF 3 ：10～25％；BaF 2 ：15～30％；SrF 2 ：5～15％；CaF 2 ：0～5％；MgF 2 ：0～8％；YF 3 : 0 to 5 percent; the fluorophosphate optical glass has a refractive index range of 1.55-1.60 and an Abbe number range of 75-80. The optical glass has the characteristics of low melting temperature and controlled volatilization in the manufacturing process, and the batch industrial production is possible. The fluorophosphoric glass has high visible light transmittance, and also has good process performance and stability.
Description
Technical Field
The invention relates to fluorophosphate optical glass and a preparation method thereof, belonging to the field of optical glass.
Background
Fluorophosphate optical glass is a novel low-dispersion optical glass material, can eliminate secondary spectrum special dispersion in an optical system, improves resolution ratio and imaging quality of the optical system, has low softening characteristic, can directly and precisely mold an aspheric lens, can well apochromatism, eliminates spherical aberration and aberration which are difficult to eliminate by the spherical lens, can replace a spherical lens group, reduces system volume and quality, and is widely applied to high-precision and high-resolution optical instrument combined lenses such as digital cameras, high-definition monitoring, astronomical telescopes and the like. Particularly, the phosphate glass with the refractive index of more than 1.55 and the Abbe number of more than 75 has high refractive index and Abbe number, and has potential market prospect.
The patent CN105016619A discloses a glass having a refractive index (nd) of more than 1.59 and an Abbe number (upsilond) of more than 67, wherein the cation Ca 2+ The ion content of the catalyst is 1.3-12, so that high-temperature volatilization is serious, and industrial production is not facilitated.
Patent CN110156324A,The glasses disclosed in CN110156323A and CN110156325A have a refractive index (nd) of 1.52 to 1.60 and an Abbe number (. nu.d) of not less than 68. But some examples of their invention are described: the fluorophosphate optical glass has a refractive index of 1.52 to 1.60 and an Abbe number of 68 to 75. Each containing 1 to 10 mol% of Gd 3+ Resulting in a high density of glass. And the density is not higher than 4.7g/cm 3 Most preferably not higher than 4.5g/cm 3 。
Patent CN105036550A discloses a glass having a refractive index (nd) of 1.5 or more and a high abbe number (vd) of 70 or more. Wherein contains (R) + )1 to 35% of monovalent cation and 15 to 40% of B 3+ Causing serious high-temperature volatilization, which is not beneficial to industrialized production.
Patent CN1854100A discloses an optical glass having a refractive index of 1.40 to 1.58 and an Abbe number of 67 to 90, which contains 1 to 10 mol% of Li + Causing severe volatilization at high temperature, while in Li + Accumulation action, increase the devitrification tendency of the glass, and are not beneficial to industrialized production. And during molding due to Li + The radius is small, the migration rate is high, the reaction between the glass and the mold interface is aggravated, and the yield of the molded lens is directly influenced.
Disclosure of Invention
Problems to be solved by the invention
In view of the technical problems in the prior art, the present invention provides an optical glass. The fluorophosphate optical glass has high visible light transmittance, good process performance and stability, and can be used for manufacturing optical elements by secondary mould pressing.
Furthermore, the invention also provides a preparation method of the fluorophosphate optical glass, which is simple and feasible and has easily obtained raw materials.
Means for solving the problems
The invention provides fluorophosphate optical glass, which comprises the following components by taking the total mass of the fluorophosphate optical glass as 100 percent:
Al(PO 3 ) 3 ：20～35％；
BaO：25～38％；
Al 2 O 3 ：0～5％；
AlF 3 ：10～25％；
BaF 2 ：15～30％；
SrF 2 ：5～15％；
CaF 2 ：0～5％；
MgF 2 ：0～8％；
YF 3 ：0～5％；
the fluorophosphate optical glass has a refractive index range of 1.55-1.60 and an Abbe number range of 75-80.
The fluorophosphate optical glass according to the present invention, wherein the Al (PO) 3 ) 3 The content of (A) is 21-33%, the content of BaO is 26-35%, and the content of Al is 2 O 3 Is 0-4%, the AlF 3 The content of (A) is 11-23%, and the BaF 2 Is 16-28%, the SrF 2 The content of (2) is 6-12%, and the CaF 2 The content of (b) is 0-4%, and the MgF 2 Is 0-4%, and the YF 3 The content of (A) is 0-3%.
The fluorophosphate optical glass according to the present invention, wherein the Al (PO) is 3 ) 3 22-30%, the content of BaO is 27-33%, and Al 2 O 3 The content of (a) is 0-3%, and the AlF 3 Is 12-20%, the BaF 2 The content of (a) is 17-25%, and the SrF 2 The content of (2) is 7-10%, the CaF 2 The content of (A) is 1-3%, and the MgF 2 Is 0-2%, and the YF 3 The content of (B) is 0-2%.
The fluorophosphate optical glass according to the present invention, wherein P is calculated as an oxide 2 O 5 With Al 2 O 3 Is not more than 4, P 2 O 5 The mass ratio to BaO is not less than 1.
The fluorophosphate optical glass according to the present invention, wherein,
the mass ratio of the F element to the O element is 0.7-1.5; and/or
The mass ratio of the P element to the Al element is 0.5-1.5; and/or
The mass ratio of the F element to the P element is 1-3.
The fluorophosphate optical glass according to the present invention, wherein BaO and BaF 2 The mass ratio of (A) to (B) is 2.5 or less, preferably 1 to 2, more preferably 1 to 1.8.
The fluorophosphate optical glass according to the present invention, wherein a ratio of a transition temperature to a crystallization upper limit temperature of the fluorophosphate optical glass is 2/3 or more.
The fluorophosphate optical glass according to the present invention, wherein the density of the fluorophosphate optical glass is less than 4.20g/cm 3 And a relative abrasive hardness of less than 440.
The fluorophosphate optical glass provided by the invention has a linear expansion coefficient of not more than 120 x 10 at the temperature of-50-80 DEG C -7 /℃。
The invention also provides a preparation method of the fluorophosphate optical glass, wherein the preparation method comprises the steps of weighing the raw materials of the fluorophosphate optical glass according to the proportion, uniformly mixing, smelting, and then pouring or leaking and injecting the raw materials into a forming die for forming.
ADVANTAGEOUS EFFECTS OF INVENTION
The optical glass has the characteristics of low melting temperature and controlled volatilization in the manufacturing process, and the batch industrial production is possible. The fluorophosphate optical glass has high visible light transmittance, good process performance and stability, and can be used for manufacturing optical elements by secondary mould pressing. In addition, the fluorophosphate optical glass of the present invention can be used for precision press-molding.
Furthermore, the preparation method of the fluorophosphate optical glass is simple and easy to implement, the raw materials are easy to obtain, and the mass production can be realized.
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 "numerical value a to numerical value B" means a range including the end point numerical 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.
Due to P 2 O 5 Has strong water absorption, is very easy to absorb moisture during the storage and the ingredient weighing processes, causes the weighing inaccuracy, and simultaneously has P 2 O 5 The raw material generates large heat flow during mixing with other raw materials and accelerates the volatile POF 3 The formation of products, high demands on and very easily damaging the mixing vessel and causing increased volatilization during smelting, and P 2 O 5 The direct contact with the platinum crucible can make the platinum become brittle, influence the service life of the platinum, increase the content of metal ions in the glass product, and influence the scattering of the ions on an imaging systemAnd (4) quality.
The fluorophosphate optical glass of the present invention makes it possible to use a metaphosphate system as a base glass, and the use of metaphosphate makes it possible to simplify the direct adoption of P in phosphate glass 2 O 5 While avoiding P 2 O 5 Damage to platinum caused by contact with platinum during smelting. The fluorophosphate optical glass of the present invention is glass state Al (PO) 3 ) 3 As a glass forming body, and BaO and Al are introduced 2 O 3 、BaF 2 、SrF 2 And AlF 3 Al (PO) of (A) 3 ) 3 -RF m -Al 2 O 3 The BaO system is used as matrix glass, and good and stable glass can be obtained.
The stable glass state Al (PO) is selected by the invention 3 ) 3 As the main component of the glass, the direct adoption of P in the fluorophosphate optical glass is simplified 2 O 5 While avoiding P 2 O 5 Damage to platinum caused by contact with platinum during smelting. In order to eliminate the defects of high melting temperature and difficult control of volatilization of the known glass, the stable glassy state Al (PO) is selected by the invention 3 ) 3 As a glass forming body, the eutectic point of the components is reduced, so that the glass has the characteristics of low melting temperature and controlled volatilization in the manufacturing process, and the batch industrial production becomes possible. Specifically, the method comprises the following steps:
the invention firstly provides fluorophosphate optical glass which comprises the following components in percentage by mass:
Al(PO 3 ) 3 ：20～35％；
BaO：25～38％；
Al 2 O 3 ：0～5％；
AlF 3 ：10～25％；
BaF 2 ：15～30％；
SrF 2 ：5～15％；
CaF 2 ：0～5％；
MgF 2 ：0～8％；
YF 3 ：0～5％；
the fluorophosphate optical glass has a refractive index range of 1.55-1.60 and an Abbe number range of 75-80.
The present inventors have found that Al (PO) is in a glassy state 3 ) 3 The main components of the glass can reduce volatilization in the melting process, and are beneficial to eliminating glass stripes.
Glassy state Al (PO) 3 ) 3 Is an essential component of the invention and effectively adjusts the optical performance of the glass. The viscosity of the molten glass can be increased, and the formation of the glass can be stabilized, which is an essential component for maintaining the stability of the glass. If Al (PO) is 100% based on the total mass of the fluorophosphate optical glass 3 ) 3 In excess of 35% by mass, the content of fluoride which can be incorporated in the glass composition decreases, resulting in an Abbe number outside the range of the present invention. If Al (PO) 3 ) 3 Less than 20% by mass, the stability of the glass is deteriorated. Thus, Al (PO) 3 ) 3 The mass content of the components is 20-35%, preferably 21-33%, more preferably 22-30%, and particularly preferably 23-28%.
AlF 3 Is an essential component of the invention, and AlF is introduced into the glass 3 The dispersion of the glass can be effectively reduced, and the Abbe number of the glass can be improved. If AlF is 100 percent of the total mass of the fluorophosphate optical glass 3 The content of (C) is less than 10%, and the desired Abbe number range cannot be reached if AlF 3 The content of (b) is more than 25%, the devitrification resistance of the glass is deteriorated, and at the same time, volatilization in the melting process is accelerated, which is not favorable for solving the glass streak. Thus AlF 3 The mass content of (b) is limited to 10 to 25%, preferably 11 to 23%, more preferably 12 to 20%, and particularly preferably 13 to 18%.
BaF 2 The refractive index and Abbe number of the glass can be adjusted in the glass, and the formation of the glass is stabilized. If BaF is 100% of the total mass of the fluorophosphate optical glass 2 Is less than 15%, the Abbe number of the glass is not within the scope of the present invention, if BaF 2 Is more than 30%, the desired fold cannot be obtainedRefractive index, and resistance to devitrification deteriorate. Thus BaF 2 The mass content of (b) is limited to 15 to 30%, preferably 16 to 28%, more preferably 17 to 25%, and particularly preferably 18 to 23%.
SrF 2 It is effective for adjusting optical constants of the glass and stabilizing the formation of the glass in the glass. If SrF is 100% of the total mass of the fluorophosphate optical glass 2 The content of (A) is less than 5%, and the effect is not obvious; if SrF 2 The content of (b) is more than 15%, a desired optical constant cannot be obtained, and devitrification resistance is deteriorated. Thus, SrF 2 The mass content of (B) is limited to 5 to 15%, preferably 6 to 12%, more preferably 7 to 10%.
CaF 2 In the present invention, the melting temperature of the glass is mainly lowered, and Al is promoted 2 O 3 Melting with BaO. If CaF is 100% of the total mass of the fluorophosphate optical glass 2 The content of (b) is more than 5%, the devitrification property of the glass is deteriorated. Thus, CaF 2 The mass content of (b) is limited to 0 to 5%, preferably 0 to 4%, more preferably 1 to 3%, and particularly preferably 2.5%.
MgF 2 In the present invention, the melting temperature of the glass is mainly reduced, and Al is promoted 2 O 3 Melting with BaO. If MgF is present in an amount of 100% by mass based on the total mass of the fluorophosphate optical glass 2 The content of (b) is more than 8%, the devitrification property of the glass is deteriorated. Thus, MgF 2 The mass content of (b) is limited to 0 to 8%, preferably 0 to 4%, more preferably 0 to 2%, and particularly preferably not contained.
YF 3 The refractive index of the glass can be increased if YF 3 When the content of (b) is more than 5%, devitrification of the glass is deteriorated. Thus, YF is 100% of the total mass of the fluorophosphate optical glass 3 The content of (b) is limited to 0 to 5%, preferably 0 to 3%, more preferably 0 to 2%, and particularly preferably not contained.
Al 2 O 3 The invention mainly improves the refractive index of the glass and has the function of improving and strengthening the glass structure. If Al is 100% of the total mass of the fluorophosphate optical glass 2 O 3 The content of (b) is more than 5%, melting property of the glass becomes poor, and glass quota property tends to increase. Thus, Al 2 O 3 The content of (b) is limited to 0 to 5% by mass, preferably 0 to 4% by mass, more preferably 0 to 3% by mass, and particularly preferably 0 to 2.5% by mass.
BaO in the invention mainly improves the refractive index of the glass and has the function of improving the glass frit property. If the content of BaO is less than 25%, the abbe number of the glass is out of the range of the present invention, and if the content of BaO is more than 38%, the desired refractive index cannot be obtained, and the devitrification resistance is deteriorated, based on the total mass of the fluorophosphate optical glass as 100%. Therefore, the content of BaO is limited to 25 to 38%, preferably 26 to 35%, more preferably 27 to 33%, and particularly preferably 28 to 32%.
In the glass composition, BaO and BaF 2 The mass ratio of (2) not only influences the refractive index and Abbe number of the glass, but also directly influences the crystallization performance and the temperature coefficient of the refractive index of the glass. The inventor finds out through a large number of experiments that: with BaO and BaF 2 Mass ratio of (BaO/BaF) 2 ) The glass crystallization performance is improved, but the Abbe number is influenced; in addition, with BaO and BaF 2 Mass ratio of (BaO/BaF) 2 ) The temperature coefficient of the refractive index of the glass decreases as the temperature coefficient increases. To ensure the effect of the invention, BaO/BaF 2 The content ratio may be limited to 2.5 or less, preferably 1 to 2, and more preferably 1 to 1.8.
The fluorophosphate optical glass structure is greatly changed with the difference of fluorophosphate proportion and the difference of cation. When the fluorophosphate optical glass component is based on metaphosphate, the glass network results in phosphorus-oxygen tetrahedron PO 4 Predominantly, with increasing fluoride content, PO occurs in the network structure 4 →PO 3 F→PO n F(4-n)→P 2 O 7 A change in (c). The mass ratio of fluorine element to oxygen element (F/O) has a large influence on the structure of the glass. With the increase of F/O, the temperature coefficient of the refractive index of the glass is reduced, but the grinding performance of the glass is also reduced; that is, the grinding performance of the glass is lowered as the mass ratio (F/O) of fluorine element to oxygen element is increased. In order to ensure that the abrasion degree of the glass does not exceed 440, the quality of fluorine and oxygen elementsThe ratio (F/O) may be defined to be 0.7 to 1.5, preferably 0.8 to 1.3.
The invention discovers through a large number of experiments that: the mass ratio of P element to Al element (P/Al) and the mass ratio of F element to P element (F/P) have a large influence on the refractive index and Abbe number matching of the glass. To ensure the effect of the present invention, the mass ratio of P element to Al element (P/Al) can be limited to 0.5-1.5, and the mass ratio of F element to P element (F/P) is limited to 1-3.
Further, in the present invention, the ratio of the transition temperature to the crystallization upper limit temperature of the fluorophosphate optical glass is 2/3 or more. The density of the fluorophosphate optical glass is lower than 4.20g/cm 3 And a relative abrasive hardness of less than 440. The linear expansion coefficient is not more than 120 multiplied by 10 at the temperature of-50 to 80 DEG C -7 /℃。
The invention also provides a preparation method of the fluorophosphate optical glass, which comprises the following steps: the preparation method comprises the steps of weighing the raw materials of the components of the fluorophosphate optical glass according to the proportion, uniformly mixing, smelting, and then casting or leaking and injecting in a forming die for forming.
Specifically, the fluorophosphate optical glass of the present invention employs Al (PO) in mass production 3 ) 3 、BaF 2 、AlF 3 、CaF 2 、SrF 2 、MgF 2 、YF 3 、BaCO 3 And Al (OH) 3 ) 3 The raw materials are weighed according to the proportion, directly enter a V-shaped mixer for mixing, are added into a melting crucible seal, and an optical glass platinum melting device which is opened only during feeding is melted and then is drawn and formed into a required plate.
Examples
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only 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 conventional products which are commercially available, and are not indicated by manufacturers.
Examples 1 to 21
Glassy Al (PO) with a purity of more than 99% in the proportions given in tables 1-3 3 ) 3 、BaF 2 、AlF 3 、CaF 2 、SrF 2 、MgF 2 、YF 3 、BaCO 3 And Al (OH) 3 ) 3 These glass samples were prepared by weighing and mixing the raw materials uniformly, charging the mixture into a platinum crucible, melting the mixture at 1000 ℃ for about 4 hours, stirring the mixture uniformly, pouring the mixture into a mold, and slowly cooling the mixture.
The refractive index (nd), Abbe number (. nu.d), glass transition temperature (Tg) and linear expansion coefficient (. alpha.) of 50 to 80 ℃ of the glass obtained in examples (examples 1 to 21) of the fluorophosphate optical glass of the present invention are described below -50～80 ) Temperature coefficient of refractive index (dn/dt), and crystallization upper limit temperature (L) T ) A degree of coloration (. lamda.) 80 /λ 5 ) Water resistance (D) w ) The results of the tests such as relative polishing hardness (FA) and the number of Pt-containing foreign matters in the glass are shown in tables 1, 2 and 3.
The specific detection method comprises the following steps:
1. refractive index nd, Abbe number upsilond
Measured according to the test method of GB/T7962.1 standard
2. Transition temperature and linear expansion coefficient of glass
Glass transition temperature (Tg), -linear expansion coefficient (alpha) of 50-80 DEG C -50～80℃ ) The test was carried out using a TMA tester from PE corporation, USA.
3. Upper limit temperature L of crystallization T
The crystallization upper limit temperature L was determined by using a model GM-N16P gradient furnace from Nipponshan T The measurement of (1).
4. Temperature coefficient of refractive index (dn/dt)
According to the national standard GB 7962.04-2010 "test method for colorless optical glass part 4: the minimum deviation angle method in the method described in "temperature coefficient of refractive index" measures the value of the temperature coefficient of the relative refractive index when the temperature of light having a wavelength of 589.29nm (d-line) is changed from 0 ℃ to 20 ℃.
5. Relative grinding hardness (FA)
The relative grinding hardness refers to the grinding hardness of the measured glass relative to the H-K9 standard glass under the same grinding condition. The volume grinding amount of the glass sample and the volume grinding amount of the measured standard glass H-K9 sample are measured, and the ratio of the volume grinding amount to the volume grinding amount of the measured standard glass H-K9 sample is 100 times as the relative grinding hardness FA of the measured glass.
The specific test method of the volume grinding amount of the glass test sample and the measured standard glass H-K9 sample comprises the steps of fixing the glass test sample and the standard glass H-K9 sample with the same size on a cast iron grinding disc of a specific model by using a clamp, respectively applying 1Kg of pressure on the measured sample and the standard sample, then adding a suspension of No. 40 carborundum and water in a fixed proportion, and enabling the grinding disc to rotate at the speed of 60-65 rpm to grind the samples, wherein the grinding time is 3 minutes. And after grinding, testing the grinding weight loss of the standard sample and the tested sample, and converting into the volume grinding amount.
6. Density (rho)
The measurement was carried out according to the method specified in GB/T7962.20-87.
7. Water resistance by powder method D W Acid resistance D by powder method A
Water resistance D of the obtained optical glass according to the test method of JB/T10576-2006 W Acid resistance D A And (6) carrying out testing.
8. Surface method moisture resistance stability R C Surface method acid resistance R A
The stability of the optical glass against the action of humid air is classified into three stages, according to the time required for the formation of hydrolysis spots on the polished surface of the glass, at a temperature of 50 ℃ and a relative humidity of 85%, as shown in Table A below.
TABLE A
| Rank of | 1 | 2 | 3 |
| Time (h) | >20 | 5～20 | <5 |
The acid resistance stability of the optical glass was classified into three classes according to the time required for the occurrence of interference color on the polished surface of the glass, or the appearance of mottle or peeling of the surface under the action of an acetic acid solution at a temperature of 50 ℃ under 0.1N (pH 2.9), as shown in Table B below.
Table B
| Rank of | 1 | 2 | 3 |
| Time (h) | >5 | 1～5 | <1 |
9. Resistance to washing RP (S), resistance to alkalis R OH (S)
Polishing six surfaces to sizeA sample of 40 mm. times.40 mm. times.5 mm was immersed in a sodium hydroxide aqueous solution at a constant temperature of 50 ℃. + -. 3 ℃ and a concentration of 0.01mol/l for 15 hours while stirring sufficiently. In terms of average value of leaching mass per unit area, unit mg/(cm) 2 15h), stabilizing the alkali resistance of the optical glass R OH (S) is divided into five stages, as shown in Table C below.
Watch C
Six-side polished 35mm × 35mm × 8mm samples were immersed in Na having a constant temperature of 50 ℃ + -3 ℃ and a concentration of 0.01mol/L and sufficiently stirred 5 P 3 O 10 Aqueous solution for 1 hour. In terms of average value of leaching mass per unit area, unit mg/(cm) 2 H) the washing resistance stability RP (S) of the optical glasses is divided into five classes, as shown in Table D below.
Table D
10. Number of Pt-containing foreign matters in glass
The glass sample was evaluated for foreign matter under a polarizing microscope of 200 times.
TABLE 1 examples 1 to 7
Table 2: examples 8 to 14
Table 3: examples 15 to 21
Description of tables 1-3: the Pt-containing foreign matters in the glass are calculated by determining the number of the Pt-containing foreign matters in a large plate material and dividing the number of the Pt-containing foreign matters by the volume of the glass.
As can be seen from tables 1-3: the glasses (1-21) of the embodiments of the present invention not only have refractive index (nd) and Abbe number (upsilond) within the required ranges, but also have transition temperature (Tg) and crystallization upper limit temperature (L) T ) Ratio (Tg/L) T ) Not less than 2/3, and density lower than 4.20g/cm 3 Linear expansion coefficient (alpha) in the temperature range of-50 to 80 DEG C -50～80 ) Not more than 120X 10 -7 /° c, relative abrasive hardness (FA) is less than 440.
The invention has low upper limit temperature of crystallization and good process performance, and particularly, the foreign matter number of the platinum smelted by the glass in a platinum crucible is lower than 1 per 100cm 3 The method can be used for mass production and meets the requirements of optical elements.
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 (11)
1. A fluorophosphate optical glass, characterized by comprising the following components by 100% by mass in total of the fluorophosphate optical glass:
Al(PO 3 ) 3 ：20～35％；
BaO：25～38％；
Al 2 O 3 ：0～5％；
AlF 3 ：10～25％；
BaF 2 ：15～30％；
SrF 2 ：5～15％；
CaF 2 ：0～5％；
MgF 2 ：0～8％；
YF 3 ：0～5％；
the fluorophosphate optical glass has a refractive index range of 1.55-1.60 and an Abbe number range of 75-80.
2. Fluorophosphate optical glass according to claim 1, characterized in that the Al (PO) 3 ) 3 The content of (A) is 21-33%, the content of BaO is 26-35%, and the content of Al is 2 O 3 Is 0-4%, the AlF 3 The content of (A) is 11-23%, and the BaF 2 The content of (a) is 16-28%, and the SrF 2 The content of (2) is 6-12%, and the CaF 2 The content of (A) is 0-4%, and the MgF 2 Is 0-4%, and the YF 3 The content of (A) is 0-3%.
3. Fluorophosphate optical glass according to claim 2, characterized in that the Al (PO) 3 ) 3 22-30%, 27-33% of BaO and Al 2 O 3 The content of (a) is 0-3%, and the AlF 3 Is 12-20%, the BaF 2 Is 17-25%, the SrF 2 The content of (2) is 7-10%, the CaF 2 The content of (A) is 1-3%, and the MgF 2 Is 0-2%, and the YF 3 The content of (B) is 0-2%.
4. The fluorophosphate optical glass according to any one of claims 1 to 3, wherein the mass ratio of F element to oxygen element is 0.7 to 1.5; and/or
The mass ratio of the P element to the Al element is 0.5-1.5; and/or
The mass ratio of the F element to the P element is 1-3.
5. The fluorophosphate optical glass according to any one of claims 1 to 3, wherein BaO and BaF 2 Has a mass ratio of 2.5 or less。
6. The fluorophosphate optical glass according to claim 5, wherein BaO and BaF 2 The mass ratio of (A) to (B) is 1 to 2.
7. The fluorophosphate optical glass according to claim 6, wherein BaO and BaF 2 The mass ratio of (A) to (B) is 1 to 1.8.
8. A fluorophosphate optical glass according to any one of claims 1 to 3, characterized in that the ratio of the transition temperature to the crystallization upper limit temperature of the fluorophosphate optical glass is 2/3 or more.
9. Fluorophosphate optical glass according to any one of claims 1 to 3, characterized in that it has a density lower than 4.20g/cm 3 And a relative abrasive hardness of less than 440.
10. A fluorophosphate optical glass according to any one of claims 1 to 3, characterized in that it has a linear expansion coefficient of not more than 120 x 10 at a temperature of-50 to 80 ℃ -7 /℃。
11. A method for preparing fluorophosphate optical glass according to any one of claims 1 to 10, characterized in that the method comprises weighing the raw materials of each component of the fluorophosphate optical glass according to a proportion, mixing uniformly, smelting, and then casting or slip casting in a forming die for forming.
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|---|---|---|---|---|
| US4990468A (en) * | 1988-10-06 | 1991-02-05 | Sumita Optical Glass, Inc. | Fluorophosphate optical glass |
| JP2009256149A (en) * | 2008-04-18 | 2009-11-05 | Hoya Corp | Optical glass, method of producing the same, optical element and method of producing optical element |
| JP2013163632A (en) * | 2011-04-19 | 2013-08-22 | Ohara Inc | Optical glass, optical element, and preform |
| CN105693087A (en) * | 2014-12-10 | 2016-06-22 | Hoya株式会社 | Glass, glass material for pressing moulding,optical member blank and optical membe |
| CN110156324A (en) * | 2019-05-31 | 2019-08-23 | 成都光明光电股份有限公司 | Fluorphosphate glass, gas preform, optical element and the optical instrument with it |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4990468A (en) * | 1988-10-06 | 1991-02-05 | Sumita Optical Glass, Inc. | Fluorophosphate optical glass |
| JP2009256149A (en) * | 2008-04-18 | 2009-11-05 | Hoya Corp | Optical glass, method of producing the same, optical element and method of producing optical element |
| JP2013163632A (en) * | 2011-04-19 | 2013-08-22 | Ohara Inc | Optical glass, optical element, and preform |
| CN105693087A (en) * | 2014-12-10 | 2016-06-22 | Hoya株式会社 | Glass, glass material for pressing moulding,optical member blank and optical membe |
| CN110156324A (en) * | 2019-05-31 | 2019-08-23 | 成都光明光电股份有限公司 | Fluorphosphate glass, gas preform, optical element and the optical instrument with it |
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