CN101130450B - Lead-free optical glass of the hard flint and lanthanum hard flint position - Google Patents
Lead-free optical glass of the hard flint and lanthanum hard flint position Download PDFInfo
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- CN101130450B CN101130450B CN2007101357533A CN200710135753A CN101130450B CN 101130450 B CN101130450 B CN 101130450B CN 2007101357533 A CN2007101357533 A CN 2007101357533A CN 200710135753 A CN200710135753 A CN 200710135753A CN 101130450 B CN101130450 B CN 101130450B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
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Abstract
The present invention relates to optical glass for optical element/illuminance etc. of imaging, sensor, microscopy, medical treatment technology, digital projection, photo-etching, wafer/chip technology as well as telecommunication, optical communication engineering and vehicle industry, the refractive index of the optical glass nd is more than or equal to 1.82 and less than or equal to 2.00 and/or the Abbe figure vd is more than or equal to 18 as well as less than or equal to 28, the optical glass has excellent chemical stability and crystal stability.
Description
Technical field
The present invention relates to the preformed member of purposes, optical element or this type of optical element of production, this type of glass of a kind of opticglass, this type of glass and optics or the optical module that comprises this type of optical element.
Background technology
The conventional opticglass of the optical position that this paper advocates (extremely hard flint and the hard flint position of lanthanum) contains PbO usually, in order to realize required optical property, that is, and preferred index n
dBe 1.82≤n
d≤ 2.00, and/or Abbe number ν
dBe 18≤ν
d≤ 28, but especially for realizing high refractive index.Therefore, these glass are not very stable aspect chemical.
In addition, As
2O
3Be commonly used for finings.Due in recent years with glass ingredient PbO and As
2O
3Be considered as environment harmful, so the most manufacturers of opticinstrument and product to tend to have a preference for use leaded and do not contain the glass of arsenic.In order to use in the high price range product, the glass with chemical stability of increase also becomes more and more important always.
The known hard flint with high refractive index and low Abbe number or the lead-free glass of the hard flint position of lanthanum contain a large amount of TiO usually in silicate substrate
2, this has caused extreme crystallization unstable, and the glass that can not process in the molded step of secondary that therefore causes being everlasting.And contain TiO
2Glass also be difficult to mechanically process.
The conventional machining of the optical module that the glass that alternative use up to now has piece or ingot forms carries out, production method is more and more important at present, wherein can when finishing, glass melting directly obtain direct pressing spare, that is the optical module of the precision compacting that, approaches as far as possible with final profile and/or be used for the preformed member (so-called " accurate material piece ") of compacting again." accurate material piece " typically refers to the glass part of the complete fire polishing of preferred warp, semi-free or free forming, and it can obtain via various production methods.
For this reason, the needs to " short " glass (that is, the glass of viscosity with temperature acute variation) have been reported more and more in the situation of fusing and molding process technology.This method has the processing advantage, namely may reduce molded number of times in the precision modulding process near final geometrical shape, and therefore reduces the closed number of times of mould.In this way, increase output on the one hand, and save on the other hand moulding stock, this has very positive effect to whole production cost.In addition, due to comparatively fast solidifying of obtaining whereby, therefore also may process to have with corresponding longer glassy phase ratio and be easier to crystalline glass, and will avoid or at least obviously minimizing may cause the using pre-nucleating (pre-nucleation) of problem in the molded step of secondary after a while.
For the same reason, the glass that may the temperature-viscograph in absolute term comprises the low temperature in molded scope.By lower process temperature, this also helps increases die life, and by not containing faster the cooling of stress, also helps low using pre-nucleating rate.This also provides wider possible more economical moulding stock, and this is especially remarkable near the precision modulding of final geometrical shape.
In view of the present invention, with the prior art of considering be: JP 92027180 B (Hoya Corp.), US 2004-053768A (Alcatel), US 2005-0202952 (Hoya Corp.) and WO 03/062162 (Ohara).
May produce thus the glass that has similar optical position or have suitable chemical composition, but it is carrying out demonstrating when directly comparing significant shortcoming with glass according to the present invention:
JP 92027180 B disclose optics tellurous acid phosphate glass, and it may have similar optical position.Because the tellurium that network forms and the certainty of lead oxides, described glass extends to equally glass in batches except it and also shows the temperature-viscograph that is not suitable for precision modulding (glass length) the high toxicity of starting materials.
US 2004-053768 A discloses the glass ingredient of Raman active fiber core glass.These glass ingredients are forced based on high silicate basis (30-90Mol%), and only contain in a preferred embodiment 4 compositions.Except only very little obtainable specific refractory power, those glass are showed very high absolute viscosity and the length that can not process via precision modulding.In addition, have high silicate content and seldom the glass of other composition tend to crystallization, this is difficult to dispose in the secondary precision modulding process of optical module/parts (lens, prism and other).
US 2005-0202952 discloses a kind of glass system for precision modulding according to glass of the present invention, and with glassy phase ratio of the present invention, it shows the shortcoming of higher crystallization tendency.Reason is based on the pressure silicate content up to 4Mol%.In principle, SiO
2(with Bi
2O
3And/or GeO
2Compare) cause the solubility problem in phosphate matrix, the effect (known from different glass systems) that makes its network form becomes on the contrary, and especially in secondary precision modulding process, but promote crystallization in same melt during elementary precision modulding.In addition, produced astigmatism, gluey precursor before crystallization, described precursor reduces the transmission of glass significantly at least.In addition, SiO
2Reduce attainable specific refractory power and dispersion.
WO 03/062162 discloses niobium barium phosphate glass.According to the example of mentioning, utilize SiO at least
2And/or B
2O
3Bright these stabilization that makes of opposing devitrification.For these glass, must consider that glassy phase following and according to the present invention compares the shortcoming that has: if SiO
2For the phosphate glass system, will cause so the shortcoming about crystallization, optical position and transmission of having discussed in US 2005-0202952.Because the cause of the crucible residence time forbids applying B in the high quality optical phosphate glass
2O
3: in conjunction with refractory materials being had rodent glass very much, because the cause of its phosphate matrix is applying B
2O
3(especially with Li
2The O combination) in situation, this effect obviously increases especially, and greatly shortens the crucible residence time.The extra glue of crucible material in melt shifts the transmission that acutely is reduced on whole wavelength region.If the crucible material is platinum, platinum alloy or associated alloys, the dissolving content of metal ion will further reduce transmission by specific absorption so.The spectral range of being everlasting locate to observe this effect for responsive " blue limit " always.In addition, compulsory B
2O
3Content makes the attainable optical position of glass be limited to low-refraction and dispersion.For the technical glass of especially advocating according to this prior art, it is unimportant that specific refractory power and transmission reduce effect, and this and this type of effect forms sharp contrast for the importance that opticglass according to the present invention has.
Summary of the invention
Therefore, the purpose of this invention is to provide the described problem of avoiding above-mentioned prior art and the opticglass that promotes required optical characteristics.These glass should preferably can be processed by accurate drawing method, and have low transition temperature.In addition, it should easily melt and process, and has sufficient crystalline stability for the molded step of secondary and/or the manufacturing in the factory of operation continuously.And need a kind of range of viscosities 10
7.6To 10
13The short as far as possible glass of dPas.
Realize above purpose by the embodiments of the invention described in claims.
In particular, provide a kind of opticglass, it comprises following composition (with the % by weight of oxide compound calculating):
Glass according to the present invention has 1.82≤n
d≤ 2.00, be preferably 1.84≤n
d≤ 1.98 and 1.88≤n more preferably
d≤ 1.94 specific refractory power (n
d), and/or 18≤ν
d≤ 28, be preferably 19≤ν
d≤ 26 and 19≤ν more preferably
d≤ 24 Abbe number (ν
d).
Description of drawings
Nothing
Embodiment
Unless indicate in addition in the corresponding position, otherwise representation " does not contain X " or " not containing component X " means that glass does not contain in fact this component X, that is, this composition is present in glass as impurity at most, yet it is not added in glass component as separate constituent.X represents any composition, for example B
2O
3
Term " optical position " expectation refers to the position of glass in Abbe figure, and it is by the n of glass
dAnd ν
dValue defines.
Basic glass system is niobium bismuth phosphate glass, phosphoric acid salt with act on regulate the required niobium of the optical position of wanting and the solvent of bismuth oxide compound.
Glass contains phosphoric acid salt, i.e. P
2O
5Ratio at least 12 % by weight, preferably at least 14 % by weight, more preferably at least 16 % by weight.P
2O
5Ratio to be limited to be at most 35 % by weight, preferably mostly be most 32 % by weight, especially preferably mostly be most 30 % by weight.Under the phosphoric acid salt level higher than about 35 % by weight, can not add more high refractive index compositions to the glass that is under the level that is enough to obtain high refractive index.
In addition, described glass contains at least three kinds for increasing the composition of specific refractory power; In particular, described glass contains Nb at least
2O
5, Bi
2O
3And BaO.
As the main or one-level composition that is used for realizing the optical position of wanting and especially high refractive index, the Nb that glass contains
2O
5Ratio be at least 30 % by weight, preferably be at least 33 % by weight, and more preferably at least 35 % by weight, and mostly be 50 % by weight most, preferably mostly be most 49 % by weight, more preferably mostly be most 48 % by weight.Nb more than 50 % by weight
2O
5Content will make Nb
2O
5No longer consoluet risk in matrix, and may therefore cause crystallization of melt.
In order to ensure Nb
2O
5Solubleness in glass matrix, Nb
2O
5With P
2O
5Ratio also should be arranged in specified range.Nb
2O
5/ P
2O
5Ratio (in % by weight) preferably is 4.5 to the maximum, more preferably is 3.5 to the maximum, most preferably is 3.0 to the maximum.Nb
2O
5/ P
2O
5Ratio was higher than 4.5 o'clock, and it is unstable that glass becomes; May due to layering and/or crystallization, " devitrification is bright " occur.Nb
2O
5/ P
2O
5Ratio (take % by weight) is preferred minimum is approximately 0.7, and more preferably minimum is 0.9, and especially preferably minimum is 1.2.Consider the bright stability of devitrification, in fact need very low or remarkable lower Nb
2O
5/ P
2O
5Ratio, but will need much higher absolute phosphate content, make and can not introduce enough high refractive index composition (for example, TiO
2, ZrO
2And BaO) in order to realize desired specific refractory power position herein, and/or the network modifying agent, especially be bivalent metal oxide MO (that is, be alkaline earth metal oxide MgO, CaO, BaO herein) in case the adjusting material short.
This is preferably additionally to show that the extra high refractive index composition of network Formation and characteristics (is preferred Bi why
2O
3And GeO
2) add to according to glass of the present invention in order to realize the reason of desired specific refractory power position.Even therefore at equal higher Nb
2O
5/ P
2O
5Also can make material settling out under ratio.
As the second main component or the secondary composition that are used for realizing the specific refractory power position of wanting, except Nb
2O
5Outside, also contain high refractive index Bi according to glass of the present invention
2O
3, its ratio is at least 2 % by weight, preferably is at least 4 % by weight, and mostly is 13 % by weight most, is preferably and mostly is 11 % by weight most.Work as Bi
2O
3Content can not be realized desired high refractive index during less than 2 % by weight.In addition, has it as the Bi of the characteristic of network former
2O
3Promote the extra generation of network structure.These promote again the stability of antagonism crystallization tendency during the precision modulding process, described crystallization tendency can be observed in not having the niobium phosphate glass of extra network former.In the situation that content less than 2 % by weight, can not be realized this effect.On the other hand, content is incited somebody to action too Strengthens network more than 13 % by weight, makes the ill effect relevant to the temperature-viscosity characteristic to occur.The described glass long property that will become, and therefore lose the qualification that it is used for precision modulding.
As the 3rd main component or three grades of compositions of being used for realizing the specific refractory power position of wanting, except Nb
2O
5And Bi
2O
3Outside, also contain in addition network according to glass of the present invention and form GeO
2, its ratio is at least 0.1 % by weight, preferably is at least 0.5 % by weight, and mostly is 7 % by weight most, is preferably and mostly is 1 % by weight most.In the situation that ratio less than 0.1 % by weight, can not realize this effect, also can not realize having the optical position of high refractive index and high dispersion (little Abbe number).On the other hand, content is incited somebody to action Strengthens network to a great extent more than 7 % by weight, makes the ill effect relevant to the temperature-viscosity characteristic to occur.The described glass long property that will become, and therefore lose the qualification that it is used for precision modulding.
Although Nb
2O
5Be dissolved in matrix no longer fully under higher than the ratio of 50 % by weight in and may cause crystallization of melt, but surprisingly up to the Nb of 50 % by weight
2O
5With the GeO up to 7 % by weight
2And/or up to the Bi of 13 % by weight
2O
3Even mixture under this high level still well the dissolving.
As be used for realizing or other composition of optical position is wanted in meticulous adjusting, glass according to the present invention contains high refractive index but is not composition BaO and the WO of network stabilization
3These compositions help to regulate the viscosity temperature curve (short-nature glass) that is applicable to precision modulding in itself via its network amendment feature.
The ratio of the alkaline earth metal oxide BaO that wherein uses is at least 7 % by weight, preferably is at least 9 % by weight, and at most＜17 % by weight, preferably mostly is most 16 % by weight, and more preferably mostly is most 15 % by weight.In the situation that BaO content is less than 7 % by weight, no matter how many niobium, bismuth and germanium oxide contents be, all can not realize high refractive index.Especially can not realize needing to be used for " steepness " of precision modulding glass.Be that in 17 % by weight or more situation, the unstable networks effect that occurs will very strong at BaO content on the other hand, make in melt and the firsts and seconds precision modulding in unacceptably high crystallization will occur and be inclined to.
Adopt Tungsten oxide 99.999 (WO in glass according to the present invention
3), its ratio is at least 2 % by weight, preferably is at least 4 % by weight, and mostly is 14 % by weight most, preferably mostly is most 12 % by weight.With the barium oxide equivalence, except regulating desired optical position (high refractive index of high dispersion place), the ratio in this scope is suitable for regulating the steepness that needs to be used for precision modulding exclusively.
The TiO of other high refractive index composition of conduct that marginally adds
2And ZrO
2Susceptible of proof is conducive to according to glass of the present invention.And then the ratio of every kind of compound is limited to maximum 7 % by weight, and preferred maximum 5 % by weight.But preferably, according to most embodiment of the present invention, composition TiO
2And ZrO
2The summation of content be limited to maximum 7 % by weight.It is also required limiting these compositions, in order to do not increase the crystallization tendency of glass and do not increase hardness (for example, with Knoop hardness number or abrasiveness as feature).Increase on this hardness will prove and be unfavorable for very much cold-trimming process (for example, grinding and polishing).Because the hardness that increases, treatment time and/or tool wear will increase, and therefore the cost of processing and assembly will rise.Therefore, according to a preferred embodiment of the invention, glass does not contain TiO
2And/or ZrO
2, preferably do not contain this two kinds of compositions.
For the purpose that reduces according to the crystallization susceptibility of glass of the present invention, can add content is maximum 6 % by weight, a small amount of ZnO of preferred maximum 4 % by weight, and this prevents or hinders the formation of crystalline structure.Yet the ZnO level greater than 6 % by weight has reduced specific refractory power, makes and can not realize desired optical position.
Can be with alkalimetal oxide Li
2O, Na
2O, K
2O and Cs
2O adds glass according to the present invention to and adjusts (for example in order to make glass be suitable for ion-exchange) to be used for special special use, adjusts to be used for temperature-viscosity curve or the meticulous of optical position.The overall proportion of alkalimetal oxide is preferably lower than 10 % by weight, more preferably maximum 8 % by weight.10 % by weight or more level cause than the unacceptable violent impact on the direction of low-refraction, higher thermal expansion and/or " than slow-setting glass ", and the crystallization that causes due to the mobility of ions that increases.
Contain Li according to some embodiment of glass of the present invention
2O, maximum 4 % by weight of its ratio, preferred maximum 2 % by weight, and maximum 1 % by weight most preferably.Yet, do not contain Li according to some embodiment of glass of the present invention
2O。Lithium Oxide 98min content more than 4 % by weight is general and non-required, and causes melt that the aggressiveness of refractory materials is improved.This causes the refractory materials strong erosion to enter glass, and shortens equipment life.If platinum is as high temperature material, this causes the transmission loss of blue color spectrum edge, and when using stupalith, this cause in melt by entering of heterojunction nucleus and the firsts and seconds molding process in the crystallization susceptibility improve.
For the meticulous adjusting of viscosity temperature curve, can have content according to glass of the present invention and mostly be 6 % by weight most, preferably mostly be most each in the bivalent metal oxide (that is, MgO, CaO, SrO and/or ZnO) of the MO of group of 4 % by weight.The preferred amount of these oxide compounds is 8 % by weight altogether." being forced to the type mixture " of using this method to obtain makes and can reduce by agonistic behavior the crystallization susceptibility of glass.
If any, the existing amount of fluorochemical is only 6 % by weight at the most, preferred 4 % by weight at the most, and more preferably 2 % by weight at the most.Can there be the very fluorochemical of a small amount of (ppm), in order to cover colour effect.Glass does not preferably contain this composition.
This upper limit that surpasses MO and F will have detrimentally affect (too short glass) to the viscosity temperature curve, and depart from desired optical position owing to significantly reducing specific refractory power and increase Abbe number.
Also preferably do not contain B according to the particular example of glass of the present invention
2O
3B
2O
3Glass there is detrimentally affect, when especially making up with the platinum melting unit.B
2O
3Cause in essence the increase of glass intermediate ion mobility, this causes the bright susceptibility of devitrification that improves.During with fusing combination in platinum crucible, this effect exacerbates, because due to its erosion to crucible material, B
2O
3Increased entering of heterogeneous platinum core.In addition, the platinum of increase has entered transmission, the especially transmission in blue spectral range also deteriorated.
Because glass according to the present invention is responsive to redox reaction, therefore make condition turn to reductive condition can cause glass because the colloidal particle of gained cause strongly painted when fusing.For offsetting this effect and the melt of avoiding over reduction, glass according to the present invention contains Sb
2O
3, its ratio is at least 0.1 % by weight, preferably is at least 0.2 % by weight, and mostly is 2 % by weight most, preferably mostly is most 0.8 % by weight.Therefore, this composition only time strategic point is used as finings, and mainly in order to guarantee the oxidisability melting condition.Yet, due to Sb
2O
3Has intrinsic absorptivity, so should not surpass the level of 2 % by weight.Sb
2O
3Level is higher, and the absorption edge in blue spectral range is stronger to the transfer of upper wavelength, and the aberration when making the visual range imaging may be along with Sb
2O
3The amount increase and occur.Preferred embodiment does not contain this composition.
Except Sb
2O
3Outside, can contain other conventional finings on a small quantity according to glass of the present invention.The total amount of the finings that these add in addition preferably mostly is most 1 % by weight, consists of 100 % by weight thereby this tittle further adds the composition of residue glass ingredient to.Following composition can be used as other finings (in addition to remaining the % by weight of glass ingredient):
As
2O
30-1 and/or
SnO 0-1 and/or
SO
4 2-0-1 and/or
NaCl 0-1 and/or
F
- 0 - 1
For regulate more neatly special optical position in attainable optical position scope, also can contain the La of group according to glass of the present invention
2O
3, Y
2O
3, Gd
2O
3, Ta
2O
5, Yb
2O
5In one or more oxide compounds, its overall proportion is maximum 5 % by weight, preferably mostly is most 2 % by weight.The La of this group
2O
3, Y
2O
3, Gd
2O
3, Ta
2O
5, Yb
2O
5The total content increase of middle composition surpasses 5 % by weight and will cause transmission loss (due to Y
2O
3, La
2O
3, Gd
2O
3, Yb
2O
5) and/or the bright susceptibility of devitrification that increases (due to La
2O
3).
According to most embodiment of opticglass, preferably do not contain painted and/or optical activity (for example laser is active) composition according to glass of the present invention.According to a particular embodiment of the invention, when when acting on the substrate glasses of optical filter or solid laser, the ratio of painted and/or optical activity (for example laser the is active) composition that can still contain according to glass of the present invention mostly is 5 % by weight most.
According to most embodiment, the preferred oxygen-freeization aluminium of glass according to the present invention.Yet according to a particular embodiment of the invention, glass also is applicable to ion exchange process.According to this embodiment, glass preferably contains Al
2O
3The low Al of maximum 6 % by weight
2O
3Ratio promotes the formation of structure in material, and this also is conducive to ion-exchange by increasing mobility of ions.Yet, make Al
2O
3Content increase to surpass 6 % by weight will cause the bright susceptibility of devitrification that increases and non-required glass " length ", not be therefore preferred.The ratio of the silver suboxide that also can contain according to the glass of this embodiment is 5 % by weight, is preferably 2 % by weight.Yet, silver suboxide content is increased surpasses the loss that 5 % by weight will cause the glass transmission.
According to one embodiment of present invention, glass does not contain environmentally harmful composition, for example lead and/or arsenic.
According to another embodiment of the present invention, also preferably do not contain other composition of not mentioning in right claim and/or this explanation according to glass of the present invention, that is, according to this embodiment, glass is grouped into by described one-tenth in essence.In the case, representation " in essence by ... form " mean that other composition exists as impurity at most, but can not have a mind to add to glass ingredient as separate constituent.
According to one embodiment of present invention, according to glass of the present invention preferably by account for glass from 90 % by weight to 95%, more preferably 98 % by weight, most preferably the described composition mentioned above of 99 % by weight is formed.
According to an embodiment, " do not contain pollutent " according to glass of the present invention, that is, it does not contain the compound of introducing as impurity by melting process in essence.In particular, glass does not contain relevant SiO
2Pollutent, and also do not contain the metal crucible material (especially for Pt
0/I, Au, Ir or these metals alloy) pollutent of resistates.Representation " do not contain pollutent " and mean these compositions as composition do not add to glass in batches in, or the corrosion of crucible during by molten glass and introducing in glass as impurity.Representation " does not contain relevant SiO
2Pollutent " mean that glass contains the SiO of maximum 0.1 % by weight
2, preferably mostly be most 500ppm.
Representation " pollutent that does not contain metal crucible material resistates " means that glass contains maximum 100ppm, preferably mostly is most this metallic crucible material residues of 60ppm.The crystalline stability that has the transmission of remarkable increase and increase largely according to the glass of this embodiment.The crystalline stability that increases is based in the case and lacks heterogeneous SiO
2And/or metallic crystal core, it enters melt by the crucible material from indivedual selections usually.By lacking scattering colloid Pt
0Particulate and scattering silicate particulate and based on the micro-crystallization of above-mentioned substance have avoided the transmission in whole frequency band range to reduce.Absorb the Pt of its whole band spectrum
IOr the shortage of metalloid ion also causes improved transmission.Can be by the glass of suitable process control acquisition according to this embodiment.In particular, fusion crucible or melting channel must be fully cooling so that the coating formation of glass on the surface of melting channel, and glass melting thing itself in itself not can with the Surface Contact of crucible or groove, and coating is in order to protect crucible or groove not to be subjected to impurity effect.
All glass according to the present invention all have the Tg of maximum 660 ℃, all are crystallization-stables, and can process well.
All glass according to the present invention all have on the cooling measurement sample of the rate of cooling of about 7K/h more than or equal to 130 * 10
-4Irregular relative partial dispersion Δ P
G, F, that is, its optical color that highly is applicable in color imaging system is proofreaied and correct.
All glass according to the present invention all have less than or equal to 4.7g/cm
3Specific density ρ.Due to its relatively low carrying quality, therefore be particularly useful for the mobile/handheld unit by its optical element of making and/or optical module.
All glass according to the present invention all have in from 20 to 300 ℃ of scopes maximum 11 * 10
-7The thermalexpansioncoefficientα of/K.Therefore, they are significantly different from known phosphate glass, known phosphate glass due to it approximately 14 * 10
-7High thermal expansion in/K zone, thereby the problem of thermal stresses is arranged in reprocessing and package technique.
And all glass according to the present invention also have good chemical stability and for the stability of crystallization, i.e. crystalline stability.In addition, it is with near the good meltability of final geometrical shape and workability, famous because tooling cost reduces the lower production cost that obtains, good ion exchange property and good environment friendly flexibly.
By using according to glass of the present invention, realized the adjusting of optical position, viscosity temperature curve and processing temperature, make and namely use responsive precision machinery also can guarantee molded near the Height assignment of final geometrical shape.In addition, realized the correction of crystalline stability and viscosity temperature curve, made and easily to carry out further thermal treatment to glass, for example compacting or compacting or ion exchange process again.
In addition, the present invention relates to a kind of method for the production of opticglass, it is included in the step of setting up oxidizing condition in melt.
According to an embodiment according to method of the present invention, the composition (being at least in particular 0.2 % by weight) that will have at least the effect ratio adds in batch to be melted as nitrate.For instance, in the nitrate situation, " 0.2 % by weight " means that the respective metal oxide compound of 0.2 % by weight is recalculated as being the corresponding nitrate of identical molar ratio, and this ratio is added in the melt batch as nitrate.Nitrate is oxidation finings itself in the redox clarification system, therefore when using AS
2O
3And/or Sb
2O
3Preferred the use during clarification.
Can equally oxidizing gas be introduced melt in order to set oxidizing condition in melt, the gas (for example air or purity oxygen) that contains aerobic is preferred.
In addition, fusion crucible or melting channel can be fully cooling so that the coating formation of glass on the surface of melting channel, and glass melting thing itself in itself not can with the Surface Contact of crucible or groove, and coating is in order to protect crucible or groove not to be subjected to impurity effect.
The phosphoric acid salt ratio namely, is not with free P in preferably adding in batches as composite phosphate
2O
5Form but as having the compound of other composition (for example, as for example Ba (H
2PO
4)
2Phosphoric acid derivatives) add phosphoric acid salt.
In addition, the present invention relates to glass according to the present invention in imaging, sensor, microscopy, medical skill, digital projection, telecommunications, optical communication engineering/information transmission, automobile industry optical element/illumination, photoetching, step unit, excite state molecular laser, wafer, computer chip and unicircuit and contain the purposes of Application Areas of the electronic installation of this type of circuit and chip.
In addition, the present invention relates to comprise optical element according to glass of the present invention.In the case, optical element can specificly be lens, prism, light guide bar, array, optical fiber, gradient assembly, optical window and compact assembly.According to the present invention, term " optical element " also comprises the preformed member of this optical element, for example expects piece, accurate material piece and analogue.
In addition, the present invention relates to a kind of method for the production of optical element or optical module, it comprises following steps:
Compacting is according to opticglass of the present invention.
The compacting of glass is preferably accurate pressing process.
According to an embodiment, be optical module by again suppressing glass processing.
Term used according to the invention " accurate compacting " refers to a kind of drawing method, and the surface of the optical module of wherein producing no longer needs finishing or polishing after the precision compacting, but has the sufficient surface quality of essence.
In conventional drawing method, the surface does not have sufficient optical quality after compacting, and pressure containing part must (for example) carry out polishing before further using.
As the beginning material, can directly process the glass that is used for drawing method from melt.In the situation that term " precision modulding " is just used in the precision compacting.
As the alternative method of suppressing from the glass melting thing, can reheat the frit block that solidifies; Pressing process is the secondary molding process in the case, and it is also referred to as compacting again.This requirement of again suppressing to glass is very strict.These glass must be than directly processing from melt and not having second-heating to have basically higher crystalline stability to the glass of processing temperature.
For compacting again, the preformed member that can make the materials piece or be sawn into.So-called accurate material piece also is preferred for accurate compacting, that is, the frit block that solidifies, its weight is corresponding to the final weight of the optical module that will produce, and its shape also preferred class be similar to the net shape of the optical module that will produce.In the situation that these accurate material pieces, compacting can not stay the outstanding burr of the excess stock that must remove in further procedure of processing again.
In addition, the present invention relates to produce optics with this element, for example optical element/illumination, photoetching, step unit, excite state molecular laser, wafer, computer chip and the unicircuit in sensor, microscopy, medical skill, digital projection, telecommunications, optical communication engineering/information transmission, automobile industry and contain the electronic installation of this type of circuit and chip.
In addition, the present invention relates to comprise for example being used for optical element/illumination, photoetching, step unit, excite state molecular laser, wafer, computer chip and the unicircuit of imaging sensor, microscopy, medical skill, digital projection, telecommunications, optical communication engineering/information transmission, automobile industry and containing the optics of the electronic installation of this type of circuit and chip of optical element mentioned above.
Below will explain in more detail the present invention by a series of examples.Yet the invention is not restricted to described example.
Example
Table 2 contains 13 one exemplary embodiment in the preferred ingredient scope, and two Comparative Example.The following glass of describing in example of making:
Weigh up starting material (being preferably corresponding carbonate) and the phosphoric acid salt ratio (being preferably composite phosphate) of oxide compound, add one or more finingss (Sb for example
2O
3), and subsequently it is mixed well.Glass in batches in discontinuous batch melting unit in approximately fusing under 1200 ℃, subsequently by refining (1250 ℃) and homogenize.Under the about casting temp of 1000 ℃, glass can be cast and be processed into desired size.Experience shows, in jumbo continuous device, temperature can reduce at least about 100K, and can pass through method of moulding (for example, accurate compacting) with materials processing one-tenth near final geometrical shape.
Table 1: the fusing example of the 100kg glass that calculates (according to example 4, table 2)
| Oxide compound | In % by weight | Starting materials | Weight (kg) |
| P 2O 5 Nb 2O 5 Bi 2O 3 GeO 2 BaO | 22.0 41.5 6.0 2.0 12.5 | P 2O 5 Ba(H 2PO 4) 2 Nb 2O 5 Bi 2O 3 GeO 2 Ba(H 2PO 4) 2 | (9.75 referring to BaO) 41.56 6.00 2.00 27.89 |
| Li 2O K 2O Cs 2O | 1.5 2.0 2.5 | Li 2CO 3 K 2CO 3 KNO 3 Cs 2CO 3 | 3.73 2.21 1.07 2.88 |
| ZnO TiO 2 WO 3 | 0.5 2.5 7.0 | ZnO TiO 2 WO 3 | 0.50 2.50 7.00 |
| Sb 2O 3 | 0.5 | Sb 2O 3 | 0.30 |
| Amount to | 100.0 | 107.39 |
As example 4, specify the characteristic of the glass that obtains in this way in table 2.
Table 2: fusing example 1-5 (in % by weight)
| Example | 1 | 2 | 3 | 4 | 5 |
| P 2O 5 Nb 2O 5 Bi 2O 3 GeO 2 | 12.0 50.0 13.0 6.0 | 14.0 48.0 11.0 7.0 | 16.0 49.0 9.0 2.0 | 22.0 41.5 6.0 2.0 | 30.0 35.0 6.0 1.0 |
| Li 2O Na 2O K 2O Cs 2O | 2.0 | 1.5 2.0 2.5 | |||
| MgO CaO SrO BaO ZnO | 7.0 | 1.5 16.5 | 1.0 2.0 15.0 2.0 | 12.5 0.5 | 9.0 |
| TiO 2 ZrO 2 | 2.5 | 5.0 | |||
| WO 3 | 12.0 | 2.0 | 2.0 | 7.0 | 14.0 |
| Sb 2O 3 | 0.3 | 0.3 | |||
| Amount to | 100.0 | 100.3 | 100.0 | 100.3 | 100.0 |
| n d[7K/h] ν d[7K/h] | 1.9586 19.4 | 1.9344 21.2 | 1.9671 20.0 | 1.9130 21.2 | 1.8877 20.6 |
| P g.F[7K/h] ΔP g.F(10 -4) [7K/h] | 0.6474 337 | 0.6379 282 | 0.6406 289 | 0.6363 280 | 0.6446 349 |
| α 20-300(10 -6×K -1) Tg(℃) ρ(g/cm 3) | 8.8 496 4.46 | 7.9 633 4.42 | 6.8 660 4.37 | 7.1 596 4.14 | 7.9 517 3.99 |
Continued 2: fusing example 6-10 (in % by weight)
| Example | 6 | 7 | 8 | 9 | 10 |
| P 2O 5 Nb 2O 5 Bi 2O 3 GeO 2 | 32.0 33.0 2.0 0.5 | 35.0 30.0 4.0 0.1 | 16.0 43.0 8.0 1.0 | 20.0 37.0 7.0 0.5 | 23.0 48.0 2.0 2.0 |
| Li 2O Na 2O K 2O Cs 2O | 6.0 | 4.0 | 1.0 6.0 | 1.0 6.0 | |
| MgO CaO SrO BaO ZnO | 1.5 16.0 | 12.0 | 15.0 | 4.0 16.0 4.0 | 6.0 9.0 1.0 |
| TiO 2 ZrO 2 | 5.0 | 7.0 | 7.0 | 2.5 | |
| WO 3 | 4.0 | 7.9 | 10.0 | 2.0 | 2.0 |
| Sb 2O 3 | 0.3 | 0.3 | |||
| Amount to | 100.3 | 100.0 | 100.0 | 100.0 | 100.3 |
| n d[7K/h] ν d[7K/h] | 1.9194 23.0 | 1.9030 20.3 | 1.9239 23.4 | 1.9780 20.5 | 1.8953 23.8 |
| P g.F[7K/h] ΔP g.F(10 -4) [7K/h] | 0.6155 133 | 0.6406 316 | 0.6251 218 | 0.6324 249 | 0.6280 235 |
| α 20-300(10 -6× K -1) Tg(℃) ρ(g/cm 3) | 6.5 632 4.16 | 5.4 625 3.78 | 18.8 411 4.46 | 10.8 479 4.63 | 20.7 464 4.31 |
Continued 2 fusing example 11-13, and Comparative Example A, B (in % by weight)
| Example | 11 | 12 | 13 | A | B |
| P 2O 5 Nb 2O 5 Bi 2O 3 GeO 2 | 27.0 40.0 4.0 4.0 | 24.0 33.0 13.0 0.1 | 13.0 32.0 11.0 2.5 | 14.0 37.0 5.0 3.0 | 18.0 34.9 3.0 0.1 |
| Li 2O Na 2O K 2O Cs 2O | 0.5 0.5 4.0 | 1.5 | 0.5 1.5 1.0 | 0.5 4.0 2.5 3.0 | 6.0 4.0 |
| MgO CaO SrO BaO ZnO | 7.0 | 1.0 16.5 5.9 | 0.5 6.0 16.0 1.5 | 4.0 4.0 10.0 | 6.0 2.0 17.0 |
| TiO 2 ZrO 2 | 1.0 | 1.5 1.0 | 3.0 4.0 | 2.0 | |
| WO 3 | 13.0 | 4.0 | 12.0 | 6.0 | 7.0 |
| Sb 2O 3 | |||||
| Amount to | 100.3 | 100.0 | 100.0 | 100.0 | 100.0 |
| n d[7K/h] ν d[7K/h] | 1.8448 23.2 | 1.8922 23.3 | 1.9694 21.3 | 1.9239 23.4 | 1.8953 23.8 |
| P g.F[7K/h] ΔP g.F(10 -4) [7K/h] | 0.6298 249 | 0.6302 251 | 0.6353 272 | 0.6251 218 | 0.6280 235 |
| α 20-300(10 -6×K -1) Tg(℃) ρ(g/cm 3) | 9.0 530 4.17 | 9.3 550 4.23 | 10.5 416 4.49 | 18.8 411 4.46 | 20.7 464 4.31 |
All glass of example 1 to 13 all have content lower than the SiO of 0.1 % by weight
2With the metallic crucible material residues of content lower than 100ppm.It is famous with high crystalline stability and good transparency.
Comparative Example A and B show glass ingredient, for this, because the high flow capacity material content is positioned at according to (alkalimetal oxide is higher than 10 % by weight) outside compositional range of the present invention, so in fact obtain heterogeneous refining quality, but pass through the cooling of component, small devitrification occurs bright, make to produce transparent glass ceramic material.Yet, be possible to the measurement of optical data.By checking progressively the thermal property value that raises (in the case, for example thermal expansivity), it is obvious especially that phase transition becomes.
Has common optical data according to the opticglass of glass of the present invention and known this position.Yet its with chemical stability and machinability preferably, due to the starting material that reduce and processing cost obtain than lower production cost, the sufficient crystalline stability that obtains because it is short and good environment friendly and famous.By supported by example (table 2) according to glass of the present invention, realize the adjusting to crystalline stability and temperature-viscosity curve, make and can easily carry out further thermal treatment (compacting or compacting again) to glass.
Claims (18)
1. lead-free opticglass, it comprises the following component in the % by weight of oxide compound:
2. glass according to claim 1, wherein said glass does not contain B
2O
3And/or do not contain relevant SiO
2Pollutent and/or the pollutent of metal crucible material residues.
3. glass according to claim 1 and 2, wherein TiO
2+ ZrO
2Total content be no more than 7 % by weight.
4. glass according to claim 1 and 2, wherein the amount that exists in glass of single alkali metal oxide compound is at most 6 % by weight; Described single alkali metal oxide compound is Li
2O, K
2O or Cs
2O。
5. glass according to claim 1 and 2, wherein the summation of oxide M gO, CaO, SrO and ZnO mostly is 8 % by weight most, and/or each the existing amount in these oxide compounds is at most 6 % by weight.
6. glass according to claim 1 and 2, wherein alumina content amounts to and mostly is 6 % by weight most.
7. glass according to claim 1 and 2, wherein zinc oxide content amounts to and mostly is 6 % by weight most.
8. glass according to claim 1 and 2, wherein Ag
2O content amounts to and mostly is 5 % by weight most.
9. glass according to claim 1 and 2, wherein oxide compound La
2O
3, Y
2O
3, Gd
2O
3, Ta
2O
5, Yb
2O
5Total content be at most 5 % by weight.
10. glass according to claim 1 and 2, wherein said glass does not contain Pt and/or SiO
2
11. glass according to claim 1 and 2, wherein said glass comprise that at least a following composition is as finings (in % by weight):
12. glass according to claim 1 and 2 is characterized in that its refractive index n
dBe 1.82≤n
d≤ 2.00, and/or Abbe number v
dBe 18≤v
d≤ 28.
13. a production is the method for the described glass of arbitrary claim in 12 according to claim 1, according to described method, oxidizing condition is set in melt.
14. the purposes of the described glass of arbitrary claim in 12 according to claim 1, it is used for being selected from the optical element of lens, prism, light guide bar, array, optical fiber, gradient assembly and optical window.
15. the purposes of the described glass of arbitrary claim in 12 according to claim 1, its for the production of optics or optical module with optical element/illumination, photoetching, step unit, excite state molecular laser, wafer, computer chip and the unicircuit that is used for sensor, microscopy, medical skill, digital projection, telecommunications, optical communication engineering/information transmission, automobile industry and the electronic installation that contains this type of circuit and chip.
16. an optical element, it comprises lens, prism, light guide bar, array, optical fiber, gradient assembly and optical window, and described optical element comprises according to claim 1 the described glass of arbitrary claim in 12.
17. the method for the production of optical element, it comprises the following steps:
Compacting is the described glass of arbitrary claim in 12 according to claim 1.
18. an optics or optical module, the electronic installation that it is used for optical element/illumination, photoetching, step unit, excite state molecular laser, wafer, computer chip and the unicircuit of imaging, sensor, microscopy, medical skill, digital projection, telecommunications, optical communication engineering/information transmission, automobile industry and contains this type of circuit and chip, described optics or optical module comprise according to claim 1 the described glass of arbitrary claim in 12.
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|---|---|---|---|
| DE102006037828 | 2006-08-12 | ||
| DE102006037828.8 | 2006-08-12 | ||
| DE102007008300A DE102007008300B4 (en) | 2006-08-12 | 2007-02-16 | Lead-free optical glass of heavy flint and Lanthanschwerflintlage and its production and use |
| DE102007008300.0 | 2007-02-16 |
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| CN2007101357533A Expired - Fee Related CN101130450B (en) | 2006-08-12 | 2007-08-10 | Lead-free optical glass of the hard flint and lanthanum hard flint position |
| CNA2007101357529A Pending CN101130448A (en) | 2006-08-12 | 2007-08-10 | Method and system for producing glass, in which chemical reduction of glass components is avoided |
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| JP5056332B2 (en) * | 2007-10-15 | 2012-10-24 | コニカミノルタアドバンストレイヤー株式会社 | Optical glass and optical element |
| CN101734855B (en) * | 2009-12-30 | 2012-12-12 | 成都光明光电股份有限公司 | Optical glass, prefabricated part for mold pressing and optical element |
| CN103025675B (en) * | 2010-07-26 | 2015-10-14 | 旭硝子株式会社 | Alkali-free protective glass composition and use the light extraction component of this glass composition |
| DE102012100233B4 (en) * | 2012-01-12 | 2014-05-15 | Schott Ag | Highly solar-resistant high-transmission glasses, their use and process for their preparation |
| JP5719797B2 (en) * | 2012-04-06 | 2015-05-20 | ＡｖａｎＳｔｒａｔｅ株式会社 | Glass plate manufacturing method and glass plate manufacturing apparatus |
| FR2991759B1 (en) * | 2012-06-12 | 2014-06-20 | Saint Gobain Isover | GLASS FUSION INSTALLATION |
| JP5552551B2 (en) * | 2012-06-29 | 2014-07-16 | ＡｖａｎＳｔｒａｔｅ株式会社 | Glass substrate manufacturing method and glass substrate manufacturing apparatus |
| CN103626395B (en) * | 2013-11-28 | 2016-01-06 | 中国建筑材料科学研究总院 | A kind of preparation method of high-boron-silicon glass, high-boron-silicon glass and application thereof |
| CN103964673B (en) * | 2014-05-10 | 2016-03-30 | 蚌埠玻璃工业设计研究院 | The easy attack sites method of cooling of a kind of Flat Glass Furnace pool wall |
| CN105502934B (en) * | 2015-11-27 | 2018-07-03 | 湖北新华光信息材料有限公司 | A kind of optical glass and preparation method thereof |
| DE102016109974A1 (en) * | 2016-05-31 | 2017-11-30 | Schott Ag | Process for producing a glass product and glass product obtained according to the method |
| JP6795472B2 (en) * | 2017-08-28 | 2020-12-02 | ファナック株式会社 | Machine learning device, machine learning system and machine learning method |
| WO2020117651A1 (en) * | 2018-12-07 | 2020-06-11 | Corning Incorporated | High-refractive index phosphate glass |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6333282B1 (en) * | 1999-08-20 | 2001-12-25 | Sumita Optical Glass, Inc. | Optical glass for precision molding |
| CN1339411A (en) * | 2000-08-17 | 2002-03-13 | 保谷株式会社 | Method for preparing glass and equipment for smelting glass |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6333282B1 (en) * | 1999-08-20 | 2001-12-25 | Sumita Optical Glass, Inc. | Optical glass for precision molding |
| CN1339411A (en) * | 2000-08-17 | 2002-03-13 | 保谷株式会社 | Method for preparing glass and equipment for smelting glass |
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| Title |
|---|
| JP昭61-40839A 1986.02.27 |
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