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CN101289276B - High-refraction and high- dispersion optical glass and method of manufacture - Google Patents

High-refraction and high- dispersion optical glass and method of manufacture Download PDF

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Publication number
CN101289276B
CN101289276B CN2008103022384A CN200810302238A CN101289276B CN 101289276 B CN101289276 B CN 101289276B CN 2008103022384 A CN2008103022384 A CN 2008103022384A CN 200810302238 A CN200810302238 A CN 200810302238A CN 101289276 B CN101289276 B CN 101289276B
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optical glass
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CN101289276A (en
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匡波
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CDGM Glass Co Ltd
Chengdu Guangming Optoelectronics Co Ltd
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Chengdu Guangming Optoelectronics Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/062Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/068Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/12Silica-free oxide glass compositions
    • C03C3/14Silica-free oxide glass compositions containing boron
    • C03C3/15Silica-free oxide glass compositions containing boron containing rare earths
    • C03C3/155Silica-free oxide glass compositions containing boron containing rare earths containing zirconium, titanium, tantalum or niobium

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
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Abstract

The present invention provides a high-refraction and high-dispersion optical glass which comprises 6 percent to 12 percent of B2O3, 2 percent to 8 percent of SiO2, 0 percent to 6 percent of GeO2, 20 percent to 55 percent of La2O3, 0 percent to 12 percent of Gd2O3, 10 percent to 18 percent of TiO2, 5 percent to 20 percent of Nb2O5, 0 percent to 8 percent of WO3, , 1 percent to 10 percent of ZrO2, 0 percent to 10 percent of Ta2O5, 0 percent to 8 percent of Lu2O3, 0 percent to 1 percent of Li2O, and 0 percent to 15 percent of BaO. The optical glass of the present invention contains no environment-harmful substances such as lead, arsenic, cadmium and the alike, and Nd is more than or equal to 1.95 while Vd is less than or equal to 35; in addition, the L.T of the optical glass is lower than 1300 DEG C and the optical glass is applicable to the industrial mass production.

Description

High-refractive and high-dispersive optical glass and manufacture method thereof
Technical field
The present invention relates to the high-refractive and high-dispersive optical glass and the manufacture method thereof of a kind of specific refractory power Nd 〉=1.95, Abbe number Vd≤35.
Background technology
In recent years, all kinds of photovoltaic such as digital camera, Digital Video, CCTV (watch-dog) etc. pursue small volume and less weight, multifunctional high-performanceization day by day, and therefore the demand to the used optical glass having high refractive index of imaging len increases day by day.Traditional a large amount of PbO of high dioptrics glass use improves the specific refractory power of glass, but plumbous harmful to environment, and contains the poor chemical stability of the glass of more amount PbO, and therefore except special applications, opticglass has not used lead composition usually.
USP4439531 and USP4584279 disclose two kinds of optical glass having high refractive indexes respectively, but these two kinds of glass melting temperature are very high and glass liquidus temperature (L.T) all is higher than 1300 ℃, are not suitable for producing in batches.
Te Kaiping 9-278480 discloses a kind of B 2O 3-GeO 2-La 2O 3-TiO 2-ZrO 2-Nb 2O 5The glass of high refractive index of system, but contain the GeO of more amount in this glass 2, GeO 2Be-kind of expensive raw material, so its product does not have economy.
CN200610149827.4 discloses a kind of B 2O 3-GeO 2The glass of high refractive index of system contains the GeO of a large amount of costlinesses equally in this glass system 2, economy is not strong.
The disclosed opticglass of CN200610139840.1 need be heat-treated near transition temperature and be reduced the painted of glass, has increased production process and the inconsistent situation of color inside and outside the glass may occur in heat treatment process.
Summary of the invention
Technical problem to be solved by this invention provides environmentally harmful materials such as a kind of not leaded, arsenic, cadmium, and the high-refractive and high-dispersive optical glass of Nd 〉=1.95, Vd≤35, this opticglass have lower production cost and be fit to industrial production in enormous quantities.
The present invention also will provide a kind of manufacture method of above-mentioned opticglass.
The technical scheme that technical solution problem of the present invention is adopted is: high-refractive and high-dispersive optical glass, its chemical composition consists of by weight percentage: B 2O 3: 6-12%, SiO 2: 2-8%, GeO 2: 0-6%, La 2O 3: 20-55%, Gd 2O 3: 0-12%, TiO 2: 10-18%, Nb 2O 5: 5-20%, WO 3: 0-8%, ZrO 2: 1-10%, Ta 2O 5: 0-10%, Lu 2O 3: 0-8%, Li 2O:0-1%, BaO:0-15%.
The manufacture method of high-refractive and high-dispersive optical glass, this method may further comprise the steps: 1) raw materials weighing and thorough mixing; 2) adopt neutral atmosphere or the fusing of weak oxide atmosphere at 1290-1400 ℃, blast CO 2Gas carries out homogenizing, the cooling of clarification back; 3) obtain product after cast and the annealing.
The invention has the beneficial effects as follows: environmentally harmful materials such as opticglass of the present invention is not leaded, arsenic, cadmium; Nd 〉=1.95, Vd≤35; GeO in this opticglass 2, Nb 2O 5, Ta 2O 5, Lu 2O 3Content Deng the high price raw material is lower, has lower production cost; And the L.T of glass is lower than 1300 ℃, is fit to industrial production in enormous quantities.
Embodiment
The present invention passes through experimental study repeatedly, adopts B 2O 3(SiO 2)-La 2O 3(Gd 2O 3)-TiO 2(Nb 2O 5)-ZrO 2System.
B 2O 3Being that glass network generates oxide body, is the necessary composition that constitutes glass network, especially in the group of the lanthanides glass of high refractive index, and B 2O 3It is the main component that obtains stabilized glass.Work as B 2O 3When content was lower than 4% (weight percent content, as follows), the melting properties of glass degenerated, and devitrification resistance can be undesirable; Work as B 2O 3Content is higher than 16%, and the specific refractory power of glass does not reach design objective, therefore with B 2O 3Content is defined as 4-16%, and preferred content is 6-12%.
SiO 2Also be that the network that forms glass generates oxide body, add a certain amount of SiO 2Can increase the high temperature viscosity of glass, improve the devitrification resistance and the chemical stability of glass.But work as SiO 2Content surpass at 15% o'clock, the specific refractory power of glass descends, the devitrification resistance variation, therefore raw material fusing difficulty is defined as 0-15% with its content during production, preferred content is 2-8%.
GeO 2Effect and SiO 2Basic identical, but its effect that improves glass refraction is more obvious.In the present invention if its content is higher than 10%, cause that then glass coloring deepens, crystallization property worsens simultaneously, so its content is defined as 0-10%, and preferred content 0-6% is because GeO 2Be expensive raw material,, preferably do not use from cost consideration.
Consider B from obtaining stable opticglass of the present invention 2O 3, SiO 2And GeO 2Total content be no more than 9-22%, more preferably total content is 10-17%.
La 2O 3Be the main component of high refraction low-dispersion lanthanide optical glass, be used to increase the specific refractory power of glass and the chromatic dispersion of not obvious raising glass, in this compositional system, La 2O 3With B 2O 3Mix when existing, can improve the devitrification resistance energy of glass, improve the stability of glass.Work as La 2O 3Content acted on not obvious less than 20% o'clock; When its content surpassed 55%, the crystallization property of glass worsened, so its content is 20-55%.
Gd 2O 3Effect and La 2O 3Similar, promptly on the glass optical property, play the effect of the chromatic dispersion of the specific refractory power that increases glass and not obvious raising glass, on physical and chemical performance, play glass chemistry stability and the anti-devitrification ability improved.Use a certain amount of Gd 2O 3Replace La 2O 3, can suitably improve the anti-devitrification ability of glass, but can cause the increase of specific gravity of glass.But work as Gd 2O 3Content is higher than at 20% o'clock, and the anti-devitrification ability of glass is worsened, so Gd 2O 3Content be defined as 0-20%, preferred content is 0-12%.
In the present invention, for guaranteeing the optical property of glass, require La 2O 3And Gd 2O 3Total content be no less than 30%, but work as La 2O 3And Gd 2O 3Total content be higher than at 60% o'clock, the bad stability of glass, therefore anti-devitrification ability drop is with La 2O 3And Gd 2O 3Total content be defined as 30-60%.
TiO 2Be important component of the present invention, very effective for the specific refractory power and the chromatic dispersion that improve glass, play increase glass high temperature viscosity, improve the effect of devitrification of glass performance, and can improve the chemical stability of glass, reduce specific gravity of glass.When its content is lower than 8%, be difficult to obtain optical constant required for the present invention, when its content is higher than 20%, glass coloring aggravation, so TiO 2Content is preferably 10-18%.
Nb 2O 5Be the effective constituent that improves glass refraction, an amount of anti-devitrification ability and the degree of staining that helps improving glass of introducing if its content is higher than, can cause the anti-devitrification ability of glass to reduce at 30% o'clock, and the transmitance of glass is declined to a great extent.Nb 2O 5Also be a kind of raw material than higher price, therefore its content be defined as 0-30%, the preferred content scope is 5-20%.
WO 3Have the effect that improves glass refraction and chromatic dispersion and improve the devitrification of glass performance, but experiment shows that when its content surpassed 8%, the anti-devitrification ability of glass reduced and causes painted aggravation, so its content is defined as 0-8%.
ZrO 2Have the glass of improvement devitrification resistance, improve the effect of chemical stability, in group of the lanthanides glass, also play and improve the effect that specific refractory power reduces chromatic dispersion.But its content is lower than at 1% o'clock, does not reach above-mentioned effect, when content is higher than 10%, causes that glass transition temperature rises, and causes that simultaneously the glass devitrification resistance worsens.
Ta 2O 5Be the high refractive index component, in high refractive index borate group of the lanthanides glass, have the effect that improves stability, glass, when its content greater than 18% the time, the glass melting degradation, so its content is defined as 0-18%, preferred content 0-10% considers Ta 2O 5Be a kind of valuable raw material, preferably do not use.
Y 2O 3Same La 2O 3It equally is the low chromatic dispersion composition of high refraction, the composition that can be used as the optical constant of adjusting glass is introduced, has the effect that improves glass chemistry stability, but its content surpasses 8%, can cause that glass transformation temperature raises, devitrification resistance can worsen, and therefore its content is defined as 0-8%, does not more preferably add.
Yb 2O 3Effect and Y 2O 3Similar, when its content surpasses 10%, can cause that the glass devitrification resistance can worsen, therefore its content is defined as 0-10%, consider Yb 2O 3Have by the effect that absorbs at the 800nm place, thereby preferably do not add.
Lu 2O 3Can improve the specific refractory power of glass, improve the anti-devitrification ability of glass, when its introducing amount greater than 15% the time, glass melting degradation, so its desired contents is 0-15%, preferred content is 0-8%, considers Lu 2O 3Be a kind of high price raw material, more preferably do not use.
Bi 2O 3Be the composition that improves glass refraction and chromatic dispersion, and can reduce the softening temperature of glass, but its usage quantity is when too much, the crystallization that can cause glass worsens, painted significantly increase, and proportion rises, therefore its content is 0-20%, and considers from improving the glass transmitance, does not preferably add.
Li 2O reduces the transition temperature of glass and the effective constituent of softening temperature, Li 2O also has stronger fluxing action.When its content was higher than 1%, the devitrification resistance of glass sharply descended, so Li 2The content range of O is 0-1%, does not preferably use.
Na 2O has the effect that reduces glass transformation temperature, but its content surpasses at 1% o'clock, can increase the tendency towards devitrification of glass, significantly reduces the specific refractory power of glass simultaneously, so Na of the present invention 2O content is 0-1%, does not more preferably use.
K 2O, Cs 2O effect and Na 2O is similar, and it divides other to use content to be 0-1%, does not preferably use.
In order not cause devitrification of glass, Li 2O, Na 2O, K 2O and Cs 2The total content of O preferably is no more than 2%, considers from the purpose that obtains glass of high refractive index, does not preferably introduce.
Al 2O 3Can improve the chemical stability of glass, increase the glass high temperature viscosity, but when its content is higher than 2%, cause that the devitrification resistance of glass descends, increase the fusion difficulty of admixtion, Al 2O 3Preferably do not use.
Containing more TiO 2Glass in use BaO, can improve the transmitance of glass, simultaneously BaO has higher specific refractory power in alkaline-earth metal, can obtain glass of high refractive index.But BaO content exceeds at 20% o'clock, and devitrification of glass tendency increases, and the specific refractory power of glass is difficult to surpass 1.95, so its content is 0-20%, preferred 0-15%.
ZnO helps reducing the temperature of fusion and the softening temperature of glass, and the effect of adjusting the glass optical property is arranged.When its content was higher than 10%, the tendency towards devitrification of glass increased, thereby the content of ZnO is defined as 0-10%.
The CaO composition can improve the chemical stability of glass, and fluxing action is arranged, but its content is higher than at 10% o'clock, and the tendency towards devitrification of glass increases, and specific refractory power is difficult to reach the requirement of invention.
Effect and the CaO of MgO and SrO are similar, can improve the uniformity of glass.The MgO preferred content is 0-10%, and the SrO preferred content is 0-10%, and MgO and SrO more preferably do not use.
Sb 2O 3And SnO 2All use as defrother, preferred content is respectively 0-0.5%, considers Sb 2O 3And SnO 2May cause that platinum as production unit to glass coloring, does not therefore more preferably use.
Consider environmentally safe, the present invention does not use PbO, As 2O 3Reach compositions such as CdO.
Because the specific refractory power height of opticglass of the present invention has used TiO 2, Nb 2O 5, WO 3Deng raw material one or more, Ti, Nb, elements such as w may have a plurality of valence states in glass, suppress the appearance of unfavorable element valence, make glass have good degree of staining and interior transmitance, are the keys that the present invention has practical value.
In addition, high-quality opticglass adopts platinum dish to carry out melting production usually, platinum can dissolve in the glass in high melt, platinum ion can produce visible light in glass and absorb and scattering, thereby influence the transmitance of glass, therefore reducing the dissolving of platinum in glass also is to improve glass coloring degree and transmitance important means.
Manufacture method of the present invention is: according to oxide compound, oxyhydroxide, carbonate, the nitrate raw material of moiety correspondence, weighing in proportion, add in the platinum dish behind the thorough mixing, after 1290-1400 ℃ of following fusing, clarification, homogenizing, pour into a mould after being cooled to proper temperature, put into and obtain product of the present invention after annealing furnace Xu Leng anneals.The characteristics of the inventive method are: fusing opticglass of the present invention in neutral atmosphere or weak oxide atmosphere, and in glass, blast CO 2Gas carries out homogenizing, clarification, can suppress the unfavorable valence state of valence variation element and occur, and reduces the platinum amount of fusing in the glass, makes the degree of staining of glass and transmitance obtain bigger raising, thereby makes glass of the present invention have more excellent color.The inventive method blasts CO in melten glass 2Gas can also shorten the settling time of glass, enhances productivity.
Table one and table two listed 12 embodiment of opticglass of the present invention and 4 comparative examples become to be grouped into, specific refractory power (Nd), Abbe number (Vd), liquidus temperature (L.T), transition temperature (Tg) and the transmitance that has listed file names with glass is the wavelength ratio (representing with λ 70, λ 5 respectively) of 70% and 5% correspondence.
From table one and table two as can be seen: opticglass Nd of the present invention 〉=1.95, Vd≤35, L.T<1300 ℃, the chemical stability excellence, devitrification resistance and degree of staining are good, and be with low cost, is fit to produce in batches.
Table one
Figure GDA0000023104470000051
Figure GDA0000023104470000061
Table two
Figure GDA0000023104470000071
Annotate: the parameter of mark * is by obtaining after the thermal treatment.

Claims (4)

1. high-refractive and high-dispersive optical glass is characterized in that, its chemical composition consists of by weight percentage: B 2O 3: 6-12%, SiO 2: 2-8%, GeO 2: 0-6%, La 2O 3: 20-55%, Gd 2O 3: 0-12%, TiO 2: 10-18%, Nb 2O 5: 5-20%, WO 3: 0-8%, ZrO 2: 1-10%, Ta 2O 5: 0-10%, Lu 2O 3: 0-8%, Li 2O:0-1%, BaO:0-15%.
2. high-refractive and high-dispersive optical glass as claimed in claim 1 is characterized in that B 2O 3, SiO 2And GeO 2The total content sum be: 10-17%.
3. high-refractive and high-dispersive optical glass as claimed in claim 1 is characterized in that its chemical composition consists of by weight percentage: B 2O 3: 6-12%, SiO 2: 2-8%, La 2O 3: 20-55%, Gd 2O 3: 0-12%, TiO 2: 10-18%, Nb 2O 5: 5-20%, WO 3: 0-8%, ZrO 2: 1-10%, BaO:0-15%.
4. the manufacture method of the described high-refractive and high-dispersive optical glass of claim 1 is characterized in that, this method may further comprise the steps: 1) raw materials weighing and thorough mixing; 2) adopt neutral atmosphere or the fusing of weak oxide atmosphere at 1290-1400 ℃, blast CO 2Gas carries out homogenizing, the cooling of clarification back; 3) obtain product after cast and the annealing.
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