CN116332503A - Glass material - Google Patents

Glass material Download PDF

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Publication number
CN116332503A
CN116332503A CN202310408037.7A CN202310408037A CN116332503A CN 116332503 A CN116332503 A CN 116332503A CN 202310408037 A CN202310408037 A CN 202310408037A CN 116332503 A CN116332503 A CN 116332503A
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percent
glass material
glass
sio
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Inventor
毛露路
郝良振
马赫
匡波
张祖义
聂小兵
王东俊
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CDGM Glass Co Ltd
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CDGM Glass Co Ltd
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Priority to CN202310408037.7A priority Critical patent/CN116332503A/en
Publication of CN116332503A publication Critical patent/CN116332503A/en
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • 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
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
    • 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
    • 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
    • C03C4/02—Compositions for glass with special properties for coloured glass
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Ceramic Engineering (AREA)
  • Glass Compositions (AREA)

Abstract

The invention provides a glass material, which comprises the following components in percentage by weight: siO (SiO) 2 ：40～68％；B 2 O 3 ：1～15％；Al 2 O 3 ：0.5～8％；ZnO：5～20％；Na 2 O：6～16％；MnO 2 +V 2 O 3 +Fe 2 O 3 +CuO+CeO 2 +NiO+Co 2 O 3 +Cr 2 O 3 : 1-18%. Through reasonable component design, the glass material obtained by the invention has lower transmittance in the range from visible light to near infrared band, excellent chemical stability and lower high-temperature viscosity, and is suitable for platinum ware production.

Description

Glass material
The present application is a divisional application of the invention patent application named "glass material" with application number 202111272115.2 and application date 2021, 10 and 29.
Technical Field
The present invention relates to a glass material, and more particularly, to a high-uniformity glass material having a low transmittance in the visible to near infrared band.
Background
Molecular diagnosis has the advantages of short detection time, high sensitivity, strong specificity and the like, and becomes an important development direction in the fields of precise medical treatment and personalized treatment in recent years. The Polymerase Chain Reaction (PCR) technology is a key technology in the field of molecular diagnosis, and the technology core is to accurately and quantitatively analyze fluorescence generated in the reaction process, for example, in a microfluidic gene detection chip, the more accurate the extraction of fluorescence signals generated by a micro unit, the higher the detection precision of the PCR.
The accuracy of detecting the fluorescent signal depends on a high uniform black background, and if the black is formed by adopting a film coating technology, the fluorescent signal is strongly interfered by the light reflected by the film layer, so that the black background material is required to uniformly absorb the external light. In addition, there is a need for black background materials having excellent acid resistance and water resistance, especially in recent years for the development of array chips for biological detection, and if the materials are poor in acid resistance and water resistance, substances in the materials are corroded and precipitated by culture solutions, especially alkali metal ions and transition metal ions precipitate to interfere with fluorescence of active substances, thereby reducing fluorescence detection accuracy.
In the prior art, the black glass generally adopts refractory materials as smelting vessels, and if the high-temperature viscosity is too high, a high-homogeneity product can not be basically obtained, and a black background with high homogeneity can not be realized; meanwhile, the light transmittance in certain wave bands is high, and the requirements of full black background cannot be met.
Disclosure of Invention
The invention aims to solve the technical problem of providing a glass material with low high-temperature viscosity, excellent chemical stability and low transmittance in the range from visible light to near infrared.
The technical scheme adopted for solving the technical problems is as follows:
(1) The glass material comprises the following components in percentage by weight: siO (SiO) 2 ：40～70％；B 2 O 3 ：1～15％；Al 2 O 3 ：0.5～8％；ZnO：5～20％；Na 2 O：6～16％；MnO 2 +V 2 O 3 +Fe 2 O 3 +CuO+CeO 2 +NiO+Co 2 O 3 +Cr 2 O 3 ：1～18％。
(2) The glass material according to (1), which comprises the following components in weight percent: tiO (titanium dioxide) 2 :0 to 6 percent; and/or P 2 O 5 :0 to 2 percent; and/or ZrO 2 : 0-8%; and/or Ln 2 O 3 : 0-10%; and/or Li 2 O: 0-5%; and/or K 2 O: 0-8%; and/or RO: 0-10%; and/or clarifying agent: 0 to 1 percent of RO is one or more of MgO, caO, srO, baO and Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 One or more of the clarifying agents is Sb 2 O 3 、SnO 2 、Na 2 SiF 6 、K 2 SiF 6 One or more of the following.
(3) Glass material comprising SiO in its composition 2 、B 2 O 3 ZnO and alkali metal oxide, the components of which are expressed in weight percent and contain MnO 2 +V 2 O 3 +Fe 2 O 3 +CuO+CeO 2 +NiO+Co 2 O 3 +Cr 2 O 3 :1 to 18%, and the 300 to 800nm light transmittance of the glass material with the thickness of less than 2mm is less than 2%.
(4) The glass material according to (3), which comprises the following components in percentage by weight: siO (SiO) 2 : 40-70%; and/or B 2 O 3 : 1-15%; and/or Al 2 O 3 : 0.5-8%; and/or ZnO: 5-20%; and/or Na 2 O:6 to 16 percent; and/or TiO 2 :0 to 6 percent; and/or P 2 O 5 :0 to 2 percent; and/or ZrO 2 : 0-8%; and/or Ln 2 O 3 : 0-10%; and/or Li 2 O: 0-5%; and/or K 2 O: 0-8%; and/or RO: 0-10%; and/or clarifying agent: 0 to 1 percent of RO is one or more of MgO, caO, srO, baO and Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 One or more of the clarifying agents is Sb 2 O 3 、SnO 2 、Na 2 SiF 6 、K 2 SiF 6 One or more of the following.
(5) The glass material according to any one of (1) to (4), wherein the components are represented by weight percent: (B) 2 O 3 +Al 2 O 3 )/SiO 2 Is 0.3 or less, preferably (B) 2 O 3 +Al 2 O 3 )/SiO 2 Is 0.25 or less, more preferably (B) 2 O 3 +Al 2 O 3 )/SiO 2 0.05 to 0.2.
(6) The glass material according to any one of (1) to (4), wherein the components are represented by weight percent: k (K) 2 O/(Na 2 O+Li 2 O) is 0.03 to 1.0, preferably K 2 O/(Na 2 O+Li 2 O) is 0.05 to 0.8, more preferably K 2 O/(Na 2 O+Li 2 O) is 0.1 to 0.5.
(7) The glass material according to any one of (1) to (4), wherein the components are represented by weight percent: znO/SiO 2 0.08 to 0.45, preferably ZnO/SiO 2 From 0.1 to 0.4, more preferably ZnO/SiO 2 0.12 to 0.3.
(8) The glass material according to any one of (1) to (4), wherein the components are represented by weight percent: tiO (titanium dioxide) 2 /(Fe 2 O 3 +CeO 2 ) From 0.2 to 6.0, preferably TiO 2 /(Fe 2 O 3 +CeO 2 ) From 0.3 to 4.0, more preferably TiO 2 /(Fe 2 O 3 +CeO 2 ) 0.4 to 2.0.
(9) The glass material according to any one of (1) to (4), wherein the components are represented by weight percent: na (Na) 2 O+K 2 O+Li 2 O is less than or equal to 25%, preferably Na 2 O+K 2 O+Li 2 O is less than or equal to 23%, more preferably Na 2 O+K 2 O+Li 2 O is less than or equal to 20 percent; and/or Cr 2 O 3 /(Fe 2 O 3 +CuO) is 3.0 or less, preferably Cr 2 O 3 /(Fe 2 O 3 +CuO) is 2.0 or less, more preferably Cr 2 O 3 /(Fe 2 O 3 +cuo) is 1.0 or less.
(10) The glass material according to any one of (1) to (4), comprising, in weight percent: siO (SiO) 2 :45 to 68%, preferably SiO 2 : 47-65%; and/or B 2 O 3 :1 to 12%, preferably B 2 O 3 : 2-10%; and/or MnO 2 +V 2 O 3 +Fe 2 O 3 +CuO+CeO 2 +NiO+Co 2 O 3 +Cr 2 O 3 :2 to 15%, preferably MnO 2 +V 2 O 3 +Fe 2 O 3 +CuO+CeO 2 +NiO+Co 2 O 3 +Cr 2 O 3 : 3-10%; and/or Al 2 O 3 :0.8 to 7%, preferably Al 2 O 3 :1 to 5 percent; and/or ZnO: 7-16%, preferably ZnO: 8-15%; and/or Na 2 O:7 to 14%, preferably Na 2 O: 8-13%; and/or TiO 2 :0 to 5%, preferably TiO 2 :0 to 4 percent; and/or P 2 O 5 :0 to 1 percent; and/or ZrO 2 :0 to 6%, preferably ZrO 2 ：0.55 percent; and/or Ln 2 O 3 :0 to 8%, preferably Ln 2 O 3 :0 to 4 percent; and/or Li 2 O:0.5 to 4%, preferably Li 2 O:0.7 to 3 percent; and/or K 2 O:0.5 to 6%, preferably K 2 O:1 to 6 percent; and/or RO: 0-8%, preferably RO:0 to 6 percent; and/or clarifying agent: 0 to 0.8%, preferably a clarifying agent: 0 to 0.5 percent, the RO is one or more of MgO, caO, srO, baO and Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 One or more of the clarifying agents is Sb 2 O 3 、SnO 2 、Na 2 SiF 6 、K 2 SiF 6 One or more of the following.
(11) The glass material according to any one of (1) to (4), wherein the components are represented by weight percent: cuO:0.5 to 6%, preferably CuO:1 to 5%, more preferably CuO:1.5 to 4 percent; and/or Fe 2 O 3 :0 to 3%, preferably Fe 2 O 3 :0.05 to 2%, more preferably Fe 2 O 3 :0.1 to 1.5 percent; and/or MnO 2 :0 to 3%, preferably MnO 2 : from 0 to 2%, more preferably MnO 2 :0 to 1 percent; and/or V 2 O 3 :0 to 3%, preferably V 2 O 3 :0 to 2%, more preferably V 2 O 3 :0 to 1 percent; and/or CeO 2 :0 to 2%, preferably CeO 2 : from 0 to 1.5%, more preferably CeO 2 :0 to 1 percent; and/or NiO:0.1 to 5%, preferably NiO:0.5 to 4%, more preferably NiO:0.8 to 3 percent; and/or Co 2 O 3 :0.1 to 5%, preferably Co 2 O 3 :0.5 to 4%, more preferably Co 2 O 3 :0.8 to 3 percent; and/or Cr 2 O 3 :0 to 4%, preferably Cr 2 O 3 :0 to 3.5%, more preferably Cr 2 O 3 ：0～3％。
(12) The glass material according to any one of (1) to (4), wherein the glass material has a light transmittance of 2mm or less at 300 to 800nm of 2% or less, preferably 1.5% or less, more preferably 1% or less, and even more preferably 0.8% or less.
(13) The glass material according to any one of (1) to (4), wherein the SCI value of the glass material is 4.0 or less, preferably 3.5 or less, more preferably 3.0 or less; and/or the SCE value of the glass material is 5.0 or less, preferably 4.0 or less, more preferably 3.0 or less; and/or the glass material has a chromaticity uniformity of 0.7 to 1.3, preferably 0.75 to 1.25, more preferably 0.8 to 1.2; and/or the glass material has a water action resistance stability leaching percentage of 0.10% or less, preferably 0.06% or less, more preferably 0.03% or less; and/or the glass material has an acid resistance stability leaching percentage of 0.5% or less, preferably 0.35% or less, more preferably 0.19% or less; and/or the viscosity of the glass material at 1400 ℃ is 200 dPascals or less, preferably 150 dPascals or less, more preferably 80 dPascals or less; and/or Cr of glass material 6+ The content is 1000ppm or less, preferably 500ppm or less, more preferably 100ppm or less, still more preferably 50ppm or less, and still more preferably 10ppm or less.
(14) A glass preform made of the glass material according to any one of (1) to (13).
(15) A glass element produced from the glass material according to any one of (1) to (13) or the glass preform according to (14).
(16) An instrument comprising the glass material according to any one of (1) to (13) and/or the glass element according to (15).
The beneficial effects of the invention are as follows: through reasonable component design, the glass material obtained by the invention has lower transmittance in the range from visible light to near infrared band, excellent chemical stability and lower high-temperature viscosity, and is suitable for platinum ware production.
Drawings
FIG. 1 is a graph showing spectral transmittance of a glass material according to example 19 of the present invention.
Detailed Description
The following describes embodiments of the glass material of the present invention in detail, but the present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the object of the present invention. In the repeated explanation, explanation is omitted appropriately, but the gist of the invention is not limited thereto. Hereinafter, the glass material of the present invention may be simply referred to as glass.
[ glass Material ]
The ranges of the respective components (ingredients) of the glass material of the present invention are described below. In the present invention, unless otherwise specified, the content and the total content of each component are all expressed in weight percent (wt%), that is, the content and the total content of each component are expressed in weight percent with respect to the total amount of the glass substance converted into the composition of oxide. The term "composition converted into oxide" as used herein means that when oxides, composite salts, hydroxides, and the like used as raw materials of the glass material composition of the present invention are melted and decomposed and converted into oxides, the total weight of the oxide is taken as 100%.
Unless otherwise indicated in a particular context, the numerical ranges set forth herein include upper and lower limits, and "above" and "below" include the endpoints, and all integers and fractions within the range, and are not limited to the specific values set forth in the defined range. The term "and/or" as used herein is inclusive, e.g. "a and/or B", meaning either a alone, B alone, or both a and B.
SiO 2 Is a main component forming a glass network, and if the content exceeds 70%, glass melting is difficult, bubbles, inclusions, streaks and the like are difficult to eliminate, and it is difficult to obtain a black background of high uniformity, i.e., excellent chromaticity uniformity. If the content is lower than 40%, the water resistance and acid resistance of the glass are difficult to meet the design requirements, the confinement property of a glass network to coloring ions is reduced, the glass is easy to crystallize in the production process, white and gray precipitates appear in the glass, and the chromaticity uniformity is difficult to meet the design requirements. Thus, siO 2 The content of (2) is 40 to 70%, preferably 45 to 68%, more preferably 47 to 65%.
B in a proper amount 2 O 3 Can be reinforced with SiO 2 The glass network is mainly a glass network, the water resistance and acid resistance of the glass are further improved, the melting temperature and high-temperature viscosity of the glass can be reduced, and for the borosilicate glass, the lower the high-temperature viscosity is, the gas of the glass isThe easier bubbles, inclusions, streaks, etc. are eliminated, if B 2 O 3 The content of (2) is less than 1%, and the effect is not obvious. If B 2 O 3 The content of B is higher than 15%, due to insufficient oxygen in the glass system 2 O 3 Instead, the glass is converted into a loose structure, and the water resistance and the acid resistance of the glass are reduced. Thus B 2 O 3 The content of (2) is limited to 1 to 15%, preferably 1 to 12%, more preferably 2 to 10%.
Proper amount of Al 2 O 3 Can strengthen the glass network, improve the chemical stability of the glass, reduce the thermal expansion coefficient of the glass, be favorable to reducing the precipitation of coloring ions in the glass, and if the content is lower than 0.5%, the effect is not obvious. If Al is 2 O 3 The content exceeds 8%, the high-temperature viscosity of the glass rises rapidly, and the design requirement is difficult to reach. Thus, al 2 O 3 The content of (2) is limited to 0.5 to 8%, preferably 0.8 to 7%, more preferably 1 to 5%.
Small amount of P 2 O 5 Can obviously improve the chemical strengthening performance of the glass in the glass, is beneficial to improving the strength of the glass, but P 2 O 5 The glass can promote the formation of glass microcrystals in glass, especially when the content of transition metal ions is higher than 2%, the crystallization resistance of the glass can be rapidly reduced, and when the content of transition metal ions is serious, crystallization particles and crystallization bands are filled in the glass, so that a uniform black background cannot be formed. Thus, P 2 O 5 The content of (C) is 0 to 2%, preferably 0 to 1%, more preferably P-free 2 O 5 。
The proper amount of ZnO can obviously enhance the network tightness of the glass, improve the water resistance and acid resistance of the glass, reduce the thermal expansion coefficient and the transition temperature of the glass, and if the content of ZnO is less than 5%, the effect is not obvious. If the content is more than 20%, the Abbe number of the glass is reduced, and it is difficult to meet the design requirements. The surface tension of the glass in the melting process is increased, bubbles are not easy to discharge, and the bubble degree is difficult to reach the design requirement. Therefore, the content of ZnO is controlled to 5 to 20%, preferably 7 to 16%, more preferably 8 to 15%.
TiO in an appropriate amount 2 The glass can form complex coloring with transition metal oxide to enhance light absorption of 300-500 nm, thereby reducing the use amount of the transition metal oxide and further reducing the precipitation of the transition metal oxide. On the other hand, a suitable amount of TiO 2 Can strengthen the network structure of the glass and reduce the precipitation of alkali metal ions. If TiO 2 The content of (2) is higher than 6%, the reflectivity of the glass is increased sharply, the SCI value is difficult to meet the design requirement, the stability of the glass is reduced, and the crystallization risk is increased. Thus, tiO 2 The content of (2) is limited to 0 to 6%, preferably 0 to 5%, more preferably 0 to 4%.
ZrO 2 The glass solution can reduce the capability of corroding a furnace body, prolong the service life of a melting furnace, reduce the precipitation of alkali metal ions and transition metal ions, and if the content exceeds 8%, insoluble substances are easy to appear in the glass, so that the crystallization resistance of the glass is reduced, and the high-temperature viscosity is rapidly increased. Thus, zrO 2 The content of (2) is 0 to 8%, preferably 0 to 6%, more preferably 0.5 to 5%.
Ln 2 O 3 (Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 One or more of them) can significantly improve the strength of the glass in the glass, reduce the high-temperature viscosity of the glass, and more easily obtain the glass with high uniformity if Ln 2 O 3 More than 10% and the SCI value of the glass exceeds the design requirements. Thus Ln 2 O 3 The content of (2) is 0 to 10%, preferably 0 to 8%, more preferably 0 to 4%.
Li 2 O、Na 2 O、K 2 O belongs to alkali metal oxide, and the content and the relative content have obvious influence on the light absorption curve, high-temperature viscosity, glass transition temperature, thermal expansion coefficient, water resistance, weather resistance and the like of the glass.
From the action of a single alkali metal oxide, li 2 The ability of O to lower the glass transition temperature and high temperature viscosity is strongest, and if its content exceeds 5%, the glass tends to be devitrified easily, and more importantly, if its content exceeds 5%, the acid resistance of the glass is rapidly lowered. Because ofThis, li 2 The content of O is limited to 0-5%. In some embodiments, if Li 2 The O content is less than 0.5%, the high temperature viscosity of the glass rises rapidly, and a higher temperature is required to remove bubbles during smelting, which causes a significant decrease in CuO tinting ability. Therefore, li is preferred 2 The O content is 0.5 to 4%, more preferably 0.7 to 3%.
Proper amount of Na 2 O can improve the melting performance of the glass, reduce the high-temperature viscosity of the glass, and if the content is lower than 6%, the melting performance, the high-temperature viscosity and the thermal expansion coefficient of the glass are difficult to meet the design requirements, and the water resistance and the weather resistance of the glass are rapidly reduced; if the content is higher than 16%, the thermal expansion coefficient of the glass rapidly increases, and the water resistance and weather resistance of the glass are reduced, so that the design requirement is difficult to achieve. Thus, na 2 The content of O is limited to 6 to 16%, preferably 7 to 14%, more preferably 8 to 13%.
K in a proper amount 2 O can form an alkali neutralization effect with Na ions and Li ions in the glass, so that a glass network is further reinforced, precipitation of alkali metal ions and transition metal ions in a solution is reduced, and if the content of the alkali metal ions and the transition metal ions is higher than 8%, precipitation of the alkali metal ions and the transition metal ions is further promoted. Thus, K is 2 The content of O is limited to 0 to 8%, preferably 0.5 to 6%, more preferably 1 to 6%.
Co 2 O 3 The glass belongs to transition metal oxide, can obviously reduce the light transmittance of 450-620 nm in the glass, and if the content is lower than 0.1%, the transmittance of the glass is higher than the design requirement, and if the content is higher than 5%, the crystallization resistance of the glass is rapidly reduced, the chemical stability of the glass is reduced, and the precipitation amount of the glass in the solution is rapidly increased. Thus Co 2 O 3 The content of (2) is limited to 0.1 to 5%, preferably 0.5 to 4%, more preferably 0.8 to 3%.
The inventors have found from a number of experimental studies that, in some embodiments, co 2 O 3 Is closely related to the coloring ability of the glass network former, when (B) 2 O 3 +Al 2 O 3 )/SiO 2 When the value of (2) is greater than 0.3, co 2 O 3 The coloring ability of (2) is significantly lowered. Therefore, (B) is preferable 2 O 3 +Al 2 O 3 )/SiO 2 The value of (B) is 0.3 or less, more preferably (B) 2 O 3 +Al 2 O 3 )/SiO 2 The value of (B) is 0.25 or less, more preferably (B) 2 O 3 +Al 2 O 3 )/SiO 2 The value of (2) is 0.05-0.2.
The alkaline earth metal oxide RO (one or more of RO is MgO, caO, srO, baO) can enhance the stability of the glass, reduce the crystallization risk of the glass in the production process, reduce the high-temperature viscosity of the glass and improve the bubble degree of the glass. If the RO content exceeds 10%, the reflectivity of the glass increases rapidly, and the alkaline earth metal oxide exceeding 10% greatly reduces the acid resistance of the glass, and spots are easily generated under the attack of some electrolyte solutions, thereby reducing the uniformity of the black background. Therefore, the RO content is limited to 0 to 10%, preferably 0 to 8%, more preferably 0 to 6%. On the other hand, alkaline earth metal oxides also cause Co 2 O 3 Change in tinting strength, RO content exceeding 10%, co 2 O 3 The coloring ability of (c) decreases. The inventors have found that CaO in alkaline earth metal oxides is relative to Co 2 O 3 Since the glass preferably contains CaO, baO and, if the conditions allow, mgO and/or SrO, the glass preferably contains CaO, baO and, if the conditions allow, srO.
The light transmittance of the NiO in the glass can be obviously reduced by 450-750 nm, if the content of the NiO is lower than 0.1%, the light transmittance of the glass is higher than the design requirement, and if the content of the NiO is higher than 5%, the crystallization resistance of the glass is rapidly reduced, the chemical stability of the glass is reduced, and the precipitation amount in the solution is rapidly increased. Therefore, the content of NiO is 0.1 to 5%, preferably 0.5 to 4%, more preferably 0.8 to 3%.
The inventors have found from a number of experimental studies that, in some embodiments, K is present in the glass 2 O, and satisfy K 2 O/(Na 2 O+Li 2 O) of 0.03 to 1.0, preferably 0.05 to 0.8, more preferably 0.1 to 0.5, the absorption capacity of NiO at 450 to 750nm is greatly enhanced, and the excessive reduction can be significantly achievedThe use of a transition metal oxide reduces the amount of glass that is leached.
The appropriate amount of CuO can reduce the light transmittance of 200-450 nm and 600-900 nm, if the content is lower than 0.5%, the light transmittance of the glass is higher than the design requirement, and if the content is higher than 6%, the glass has reduced crystallization resistance and reduced water resistance and acid resistance. Therefore, the content of CuO is limited to 0.5 to 6%, preferably 1 to 5%, more preferably 1.5 to 4%.
The inventors have found from a number of experimental studies that, in some embodiments, when ZnO/SiO 2 When the value of (C) is greater than 0.45, the glass needs to be smelted at a higher temperature to meet the requirement of bubble degree, and the coloring capability of CuO is weakened at a higher temperature, if ZnO/SiO 2 The value of (2) is less than 0.08, the chemical stability of the glass is reduced, and the ability to occlude alkali metal ions and transition metal ions is reduced. Therefore, znO/SiO is preferable 2 The value of (2) is 0.08 to 0.45, more preferably 0.1 to 0.4, still more preferably 0.12 to 0.3.
Fe in an appropriate amount 2 O 3 When the content is more than 3%, the chemical stability of the glass is lowered, and the amount of precipitate in an acid or aqueous solution is rapidly increased. Thus Fe 2 O 3 The content of (2) is 0 to 3%, preferably 0.05 to 2%, more preferably 0.1 to 1.5%.
CeO in an appropriate amount 2 Can reduce the light transmittance of 200-450 nm, and if the content is higher than 2%, the crystallization resistance of the glass is drastically reduced, and crystallization is started even above the molding temperature. Thus, ceO 2 The content of (2) is limited to 0 to 2%, preferably 0 to 1.5%, more preferably 0 to 1%.
The inventor finds that TiO exists in the glass simultaneously through a plurality of experimental researches 2 、CeO 2 、Fe 2 O 3 When Fe is 2 O 3 、CeO 2 The coloring capability is greatly enhanced within the wave band of 200-450 nm; further, especially under the condition of oxidizing atmosphere smelting, tiO is preferable 2 /(Fe 2 O 3 +CeO 2 ) Between 0.2 and 6.0, more preferably TiO 2 /(Fe 2 O 3 +CeO 2 ) Between 0.3 and 4.0Further preferably TiO 2 /(Fe 2 O 3 +CeO 2 ) When the light transmittance reaches the design standard, fe is obviously enhanced to 200-450 nm when the light transmittance is between 0.4 and 2.0 2 O 3 、CeO 2 The usage amount of the catalyst can be reduced by more than 50%, which is beneficial to reducing the precipitation of transition metal oxides.
MnO 2 、V 2 O 3 Can enhance the coloring of the glass in the wave band of 200-800 nm, but MnO 2 The tinting strength of (2) is sensitive to process conditions, and under the condition that the content of the tinting strength is more than 3%, the spectrum change is larger under different process conditions, so that the consistency of products is affected. Thus MnO 2 The content of (2) is limited to 3% or less, preferably 2% or less, and more preferably 1% or less. More than 3% of V 2 O 3 The problems also exist, and the glass becomes brittle and the subsequent processing difficulty becomes large, thus V 2 O 3 The content of (2) is limited to 3% or less, preferably 2% or less, and more preferably 1% or less.
Cr in an appropriate amount 2 O 3 When the glass is added, the light transmittance of 300-500 nm and 600-740 nm can be reduced, and when the content exceeds 4%, cr is easy to appear in the glass 6+ Ions, which are strong carcinogens, do not meet the ROSH regulations. Thus, cr 2 O 3 The content of (2) is 4% or less, preferably 3.5% or less, and more preferably 3% or less. In some embodiments, it is further preferred that Cr is not contained 2 O 3 。
The inventors have found that Cr 6+ The probability of occurrence under a reducing atmosphere is low, however, the reducing atmosphere has fatal damage to the metal vessels used for smelting. The inventors found through a number of experiments that when Cr is present in the composition 2 O 3 When it contains alkali metal oxide and Fe in proper amounts 2 O 3 CuO can avoid Cr 2 O 3 The components are oxidized into Cr during high-temperature smelting in an oxidizing atmosphere 6+ . Further, in some embodiments, when Na is satisfied 2 O+K 2 O+Li 2 O is less than or equal to 25%, preferably Na 2 O+K 2 O+Li 2 O≤23%, more preferably Na 2 O+K 2 O+Li 2 When O is less than or equal to 20 percent, and meets the requirement of Cr 2 O 3 /(Fe 2 O 3 +CuO) of 3.0 or less, preferably Cr 2 O 3 /(Fe 2 O 3 +CuO) of 2.0 or less, more preferably Cr 2 O 3 /(Fe 2 O 3 When +CuO) is 1.0 or less, cr is less likely to occur in the glass even under oxidizing atmosphere conditions 6+ 。
In order to obtain black background, reduce the precipitation of transition metal oxide, improve the crystallization resistance of glass, preferably MnO 2 、V 2 O 3 、Fe 2 O 3 、CuO、CeO 2 、NiO、Co 2 O 3 、Cr 2 O 3 Total MnO content of equal transition metal oxides 2 +V 2 O 3 +Fe 2 O 3 +CuO+CeO 2 +NiO+Co 2 O 3 +Cr 2 O 3 Is 1 to 18%, more preferably MnO 2 +V 2 O 3 +Fe 2 O 3 +CuO+CeO 2 +NiO+Co 2 O 3 +Cr 2 O 3 Is 2 to 15%, more preferably MnO 2 +V 2 O 3 +Fe 2 O 3 +CuO+CeO 2 +NiO+Co 2 O 3 +Cr 2 O 3 3 to 10 percent.
Sb 2 O 3 、SnO 2 、Na 2 SiF 6 、K 2 SiF 6 And the like, which can be used as a fining agent to improve the defoaming ability of the glass, the content of the fining agent is 1% or less, preferably 0.8% or less, more preferably 0.5% or less, when the fining agent is present in total or alone.
The term "not containing" or "0%" as used herein means that the compound, molecule, element or the like is not intentionally added as a raw material to the glass of the present invention; however, it is within the scope of the present invention that certain impurities or components may be present as raw materials and/or equipment for producing the glass that are not intentionally added, and that may be present in minor or trace amounts in the final glass.
The properties of the glass material of the present invention will be described below.
< 300-800 nm light transmittance >
The light transmittance of the glass material with the thickness of less than 2mm is tested according to the method specified in GB/T7962.12-2010.
In some embodiments, the glass material having a light transmittance of 2mm or less at 300 to 800nm is 2% or less, preferably 1.5% or less, more preferably 1% or less, and still more preferably 0.8% or less. The thickness of the glass material is preferably 0.2 to 2mm, more preferably 0.5 to 1.8mm, still more preferably 1 to 1.5mm, still more preferably 0.2mm or 0.5mm or 0.8mm or 1mm or 1.5mm.
< SCI value >
Chromaticity (Specular Component Include abbreviated herein as SCI) was tested using a color difference meter according to the international commission on illumination method.
In some embodiments, the glass material has a SCI value of 4.0 or less, preferably 3.5 or less, more preferably 3.0 or less.
< SCE value >
Chromaticity (Specular Component Enclude herein abbreviated SCE) was tested using a color difference meter according to the international commission on illumination, protocol.
In some embodiments, the glass material has an SCE value of 5.0 or less, preferably 4.0 or less, and more preferably 3.0 or less.
< chroma uniformity >
The sample is processed into 40mm multiplied by 30mm multiplied by 1.5mm specification, the sample is divided into 15 areas with the specification of 8mm multiplied by 5mm multiplied by 1.5mm according to the length-width direction after polishing, the SCE value is tested according to the SCE standard method, and the SCE value with the largest absolute value is taken and divided by the average value of 15 times of SCE value measurement.
In some embodiments, the glass material has a chromaticity uniformity of 0.7 to 1.3, preferably 0.75 to 1.25, more preferably 0.8 to 1.2.
< stability against Water action >
The stability to water action of the glass materials was tested according to the method specified in GB/T17129.
In some embodiments, the glass material has a water resistance stability leaching percentage of 0.10% or less, preferably 0.06% or less, more preferably 0.03% or less.
< stability against acid action >
The acid resistance stability of the glass materials was tested according to the method specified in GB/T17129.
In some embodiments, the glass material has an acid resistance stability leaching percentage of 0.5% or less, preferably 0.35% or less, and more preferably 0.19% or less.
< high temperature viscosity >
The high temperature viscosity of the glass material was measured using a THETA Rheotronic II high temperature viscometer using a spin method and the numerical unit was dPaS (poise), with a smaller value indicating a lower viscosity.
In some embodiments, the viscosity of the glass material at 1400 ℃ is 200dPas or less, preferably 150dPas or less, more preferably 80dPas or less.
<Cr 6+ Content of>
Cr in glass material 6+ The content of (C) was measured according to the method prescribed in IEC 62321-7.
In some embodiments, cr of the glass material 6+ The content is 1000ppm or less, preferably 500ppm or less, more preferably 100ppm or less, still more preferably 50ppm or less, and still more preferably 10ppm or less.
[ method of production ]
The manufacturing method of the glass material comprises the following steps: the glass of the present invention may be produced with conventional materials and processes including, but not limited to, using carbonates, nitrates, phosphates, metaphosphates, pyrophosphates, hydroxides, oxides, etc. as materials, after compounding in conventional manner, the compounded charge is charged into a melting furnace (such as a platinum or platinum alloy crucible, gold or alloy crucible containing gold) at 1200-1400 deg.c for melting, and after clarification and homogenization, a homogeneous molten glass free of bubbles and undissolved matter is obtained, which is cast and annealed in a mold. Those skilled in the art can appropriately select the raw materials, the process methods, and the process parameters according to actual needs.
[ glass preform and glass element ]
The glass preform can be produced from the produced glass material by using, for example, a direct drop molding method, a grinding method, or a press molding method such as hot press molding. That is, the glass preform may be produced by directly precision drop molding a molten glass into a glass precision preform, or by mechanical processing such as grinding and polishing, or by producing a preform for press molding from glass, and then performing hot press molding and polishing on the preform. The means for producing the glass preform is not limited to the above-described means.
As described above, the glass material of the present invention is useful for producing various glass elements, and among them, it is particularly preferable to form a preform from the glass material of the present invention, and use the preform for performing hot press molding, precision press molding, and the like to produce glass elements such as lenses, prisms, sheets, and the like.
In some embodiments, the glass materials described herein can be manufactured into glass elements including, but not limited to, sheets by various processes including, but not limited to, slot draw, float, roll, and other sheet forming processes known in the art. Alternatively, the glass material may be formed by a float or roll process as is known in the art.
The glass material of the present invention may be used to manufacture a glass element of a sheet by grinding or polishing, but the manufacturing of the glass element is not limited to these methods. The glass material of the present invention can be produced at a certain temperature by a method such as a hot bending process or a press molding process to form glass elements of various shapes, but is not limited to these methods.
The glass elements described herein can have any thickness that is reasonably useful.
[ Instrument ]
The glass material and the glass element formed by the glass material can be used for manufacturing instruments such as photographic equipment, projection equipment, display equipment, detection equipment, vehicle-mounted equipment, monitoring equipment and the like.
The glass material of the present invention can be also applied to a transmittance cut-off, a black decorative material, and the like.
< example of glass Material >
In order to further clearly illustrate and describe the technical solutions of the present invention, the following non-limiting examples are provided.
In this example, glass materials having compositions shown in tables 1 to 2 were obtained by using the above-described glass material production method. The characteristics of each glass were measured by the test method of the present invention, and the measurement results are shown in tables 1 to 2, and the thickness of the glass sample having the highest transmittance of 300 to 800nm in examples 1 to 20 below was 1.5mm.
Table 1.
Figure BDA0004182225970000131
Figure BDA0004182225970000141
Table 2.
Figure BDA0004182225970000142
Figure BDA0004182225970000151
/>
Figure BDA0004182225970000161
The spectral transmittance graph of the glass material of example 19 is shown in fig. 1.

Claims (12)

1. The glass material is characterized by comprising the following components in percentage by weight: siO (SiO) 2 ：40～68％；B 2 O 3 ：1～15％；Al 2 O 3 ：0.5～8％；ZnO：5～20％；Na 2 O：6～16％；MnO 2 +V 2 O 3 +Fe 2 O 3 +CuO+CeO 2 +NiO+Co 2 O 3 +Cr 2 O 3 ：1～18％。
2. The glass material according to claim 1, wherein the composition, expressed in weight percent, further comprises: tiO (titanium dioxide) 2 :0 to 6 percent; and/or P 2 O 5 :0 to 2 percent; and/or ZrO 2 : 0-8%; and/or Ln 2 O 3 : 0-10%; and/or Li 2 O: 0-5%; and/or K 2 O: 0-8%; and/or RO: 0-10%; and/or clarifying agent: 0 to 1 percent of RO is one or more of MgO, caO, srO, baO and Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 One or more of the clarifying agents is Sb 2 O 3 、SnO 2 、Na 2 SiF 6 、K 2 SiF 6 One or more of the following.
3. A glass material comprising SiO in the composition 2 、B 2 O 3 ZnO and alkali metal oxide, the components of which are expressed in weight percent and contain MnO 2 +V 2 O 3 +Fe 2 O 3 +CuO+CeO 2 +NiO+Co 2 O 3 +Cr 2 O 3 :1 to 18%, and the 300 to 800nm light transmittance of the glass material with the thickness of less than 2mm is less than 2%.
4. A glass material according to claim 3, characterized in that it comprises, in weight percent: siO (SiO) 2 : 40-68%; and/or B 2 O 3 : 1-15%; and/or Al 2 O 3 : 0.5-8%; and/or ZnO: 5-20%; and/or Na 2 O:6 to 16 percent; and/or TiO 2 :0 to 6 percent; and/or P 2 O 5 :0 to 2 percent; and/or ZrO 2 : 0-8%; and/or Ln 2 O 3 ：0～10％The method comprises the steps of carrying out a first treatment on the surface of the And/or Li 2 O: 0-5%; and/or K 2 O: 0-8%; and/or RO: 0-10%; and/or clarifying agent: 0 to 1 percent of RO is one or more of MgO, caO, srO, baO and Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 One or more of the clarifying agents is Sb 2 O 3 、SnO 2 、Na 2 SiF 6 、K 2 SiF 6 One or more of the following.
5. The glass material according to any one of claims 1 to 4, wherein the components are expressed in weight percent, wherein: (B) 2 O 3 +Al 2 O 3 )/SiO 2 Is 0.3 or less, preferably (B) 2 O 3 +Al 2 O 3 )/SiO 2 Is 0.25 or less, more preferably (B) 2 O 3 +Al 2 O 3 )/SiO 2 0.05 to 0.2; and/or K 2 O/(Na 2 O+Li 2 O) is 0.03 to 1.0, preferably K 2 O/(Na 2 O+Li 2 O) is 0.05 to 0.8, more preferably K 2 O/(Na 2 O+Li 2 O) is 0.1 to 0.5; and/or ZnO/SiO 2 0.08 to 0.45, preferably ZnO/SiO 2 From 0.1 to 0.4, more preferably ZnO/SiO 2 0.12 to 0.3; and/or TiO 2 /(Fe 2 O 3 +CeO 2 ) From 0.2 to 6.0, preferably TiO 2 /(Fe 2 O 3 +CeO 2 ) From 0.3 to 4.0, more preferably TiO 2 /(Fe 2 O 3 +CeO 2 ) 0.4 to 2.0; and/or Na 2 O+K 2 O+Li 2 O is less than or equal to 25%, preferably Na 2 O+K 2 O+Li 2 O is less than or equal to 23%, more preferably Na 2 O+K 2 O+Li 2 O is less than or equal to 20 percent; and/or Cr 2 O 3 /(Fe 2 O 3 +CuO) is 3.0 or less, preferably Cr 2 O 3 /(Fe 2 O 3 +CuO) is 2.0 or less, more preferably Cr 2 O 3 /(Fe 2 O 3 +cuo) is 1.0 or less.
6. The glass material according to any one of claims 1 to 4, wherein the composition comprises, in weight percent: siO (SiO) 2 :45 to 68%, preferably SiO 2 : 47-65%; and/or B 2 O 3 :1 to 12%, preferably B 2 O 3 : 2-10%; and/or MnO 2 +V 2 O 3 +Fe 2 O 3 +CuO+CeO 2 +NiO+Co 2 O 3 +Cr 2 O 3 :2 to 15%, preferably MnO 2 +V 2 O 3 +Fe 2 O 3 +CuO+CeO 2 +NiO+Co 2 O 3 +Cr 2 O 3 : 3-10%; and/or Al 2 O 3 :0.8 to 7%, preferably Al 2 O 3 :1 to 5 percent; and/or ZnO: 7-16%, preferably ZnO: 8-15%; and/or Na 2 O:7 to 14%, preferably Na 2 O: 8-13%; and/or TiO 2 :0 to 5%, preferably TiO 2 :0 to 4 percent; and/or P 2 O 5 :0 to 1 percent; and/or ZrO 2 :0 to 6%, preferably ZrO 2 :0.5 to 5 percent; and/or Ln 2 O 3 :0 to 8%, preferably Ln 2 O 3 :0 to 4 percent; and/or Li 2 O:0.5 to 4%, preferably Li 2 O:0.7 to 3 percent; and/or K 2 O:0.5 to 6%, preferably K 2 O:1 to 6 percent; and/or RO: 0-8%, preferably RO:0 to 6 percent; and/or clarifying agent: 0 to 0.8%, preferably a clarifying agent: 0 to 0.5 percent, the RO is one or more of MgO, caO, srO, baO and Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 One or more of the clarifying agents is Sb 2 O 3 、SnO 2 、Na 2 SiF 6 、K 2 SiF 6 One or more of the following.
7. The glass material according to any one of claims 1 to 4, wherein the components are expressed in weight percent, wherein: cuO:0.5 to 6%, preferably CuO:1 to 5%, more preferably CuO:1.5 to 4 percent; and/or Fe 2 O 3 :0 to 3%, preferably Fe 2 O 3 :0.05 to 2%, more preferably Fe 2 O 3 :0.1 to 1.5 percent; and/or MnO 2 :0 to 3%, preferably MnO 2 : from 0 to 2%, more preferably MnO 2 :0 to 1 percent; and/or V 2 O 3 :0 to 3%, preferably V 2 O 3 :0 to 2%, more preferably V 2 O 3 :0 to 1 percent; and/or CeO 2 :0 to 2%, preferably CeO 2 : from 0 to 1.5%, more preferably CeO 2 :0 to 1 percent; and/or NiO:0.1 to 5%, preferably NiO:0.5 to 4%, more preferably NiO:0.8 to 3 percent; and/or Co 2 O 3 :0.1 to 5%, preferably Co 2 O 3 :0.5 to 4%, more preferably Co 2 O 3 :0.8 to 3 percent; and/or Cr 2 O 3 :0 to 4%, preferably Cr 2 O 3 :0 to 3.5%, more preferably Cr 2 O 3 ：0～3％。
8. The glass material according to any one of claims 1 to 4, wherein the glass material has a light transmittance of 2% or less at 300 to 800nm, preferably 1.5% or less, more preferably 1% or less, and even more preferably 0.8% or less.
9. The glass material according to any of claims 1 to 4, wherein the glass material has a SCI value of 4.0 or less, preferably 3.5 or less, more preferably 3.0 or less; and/or the SCE value of the glass material is 5.0 or less, preferably 4.0 or less, more preferably 3.0 or less; and/or the glass material has a chromaticity uniformity of 0.7 to 1.3, preferably 0.75 to 1.25, more preferably 0.8 to 1.2; and/or the glass material has a water action resistance stability leaching percentage of 0.10% or less, preferably 0.06% or less, more preferably 0.03% or less; and/or the glass material has an acid resistance stability leaching percentage of 0.5% or less, preferably 0.35% or less, more preferably 0.19% or less; and/or the viscosity of the glass material at 1400 ℃ is 200 dPascals or less, preferably 150 dPascals or less, more preferably 80 dPascals or less; and/or Cr of glass material 6+ The content is 1000ppm or less, preferably 500ppm or less, more preferably 100ppm or lessThe one-step amount is preferably 50ppm or less, more preferably 10ppm or less.
10. Glass preform, characterized in that it is made of a glass material according to any one of claims 1 to 9.
11. Glass element, characterized in that it is made of a glass material according to any one of claims 1 to 9 or a glass preform according to claim 10.
12. An instrument comprising a glass material according to any one of claims 1 to 9 and/or a glass element according to claim 11.
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