CN104445927B - Ultraviolet cutoff glass - Google Patents
Ultraviolet cutoff glass Download PDFInfo
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- CN104445927B CN104445927B CN201410634544.3A CN201410634544A CN104445927B CN 104445927 B CN104445927 B CN 104445927B CN 201410634544 A CN201410634544 A CN 201410634544A CN 104445927 B CN104445927 B CN 104445927B
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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
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
-
- 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
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
- C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
- C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
- C03C3/118—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron containing aluminium
-
- 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
- C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
- C03C4/085—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths for ultraviolet absorbing glass
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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)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The invention provides ultraviolet cutoff glass and a manufacture method thereof. The ultraviolet cutoff glass does not contain lead, cadmium and arsenic, and comprises the following compounds in percentage by weight: 40-55 percent of SiO2, 21-32 percent of B2O3, 1-7 percent of Al2O3, 5-15 percent of sigma R2O (R is Na＜+＞ or K＜+＞), 2-9 percent of Nd2O3, 0.1-1 percent of CuO, 0.05-0.8 percent of Ni2O3, 0.5-5 percent of RX (R is Na＜+＞ or K＜+＞, X is F＜-＞, Cl＜-＞, Br＜-＞ or I＜-＞), 0.1-1 percent of Fe and 0-0.5 percent of Sb2O3, wherein the sum of all components is more than 99.5 percent. Under a testing condition that the sample thickness of the ultraviolet cutoff glass is 1mm, the transmittance below 410nm is 0, the transmittance at 450nm is T450 which is more than 70 percent, the transmittance at 585nm is T585 which is less than 30 percent, and the transmittances at 450nm, 500nm and 540nm meet the condition that T540 is more than T500, and T500 is more than T450; the visible light transmittance is over 70 percent, the glass is dark brown and can be used for comprehensively protecting ultraviolet radiation.
Description
Technical field
The present invention relates to a kind of ultraviolet cutoff glass and its manufacture method, further relate to the optical glass lens being produced from
And optical component.
Background technology
Ultraviolet radiation refers to solar radiation between 200nm～400nm for the wavelength, generally includes following three classes：UV-
A wavelength is 315nm～380nm, and UV-B wavelength is 280nm～315nm, UV-C wavelength 200nm～280nm.Reach earth surface
Sunray (290nm～2000nm) middle-ultraviolet lamp account for 13%, wherein UV-A account for 97%, UV-B account for 3%, UV-C close to
0.Ultraviolet is very important to the adverse effect of human body, and ultraviolet energy causes burns, wherein, referred to as tanned section of UV-A section,
It accumulates over a long period to the injury of skin and causes；UV-B section is referred to as turn to red because of sun burn section, and penetration power, up to epidermal area, can make skin shine
Wound, clinical manifestation is erubescence, causalgia is obvious, may occur in which vesicle, starts to peel after 1 week, and this is that people prevent from tanning severely
Main wave band.With growth in the living standard, people more pay attention to image and health, and protectiving ultraviolet radiates, avoids skin
Also more and more stronger by tanned or even sunburn demand.
A kind of glass is disclosed, it contains the SiO that content is more than 60% in patent documentation CN103641309A2Be less than
2% B2O3, this undoubtedly can make glass melting be more difficult to, increase power consumption, and it is not meltable to be easier appearance on sidewall of crucible during melting
The block changed, makes the component in entrance glass unstable, the stability of impact product.The document also discloses that ultraviolet-cutoff
Key substance be CuO, its content be less than 0.06%, can be seen that less than 0.06% CuO from the H103 resin of embodiment
It is 0 that content can not make the spectral transmittance of below 410nm.In addition, not containing Nd in glass disclosed in the document2O3And Ni2O3Become
Point, but introduce CeO2Composition, leads to its glass to be difficult to assume burgundy, and because does not contain Nd in glass disclosed in it2O3
Composition, thus do not enable wavelength for transmitance T at 585nm585＜ 30%.
In addition although CN1128737A, CN1204306A, CN1249279A, CN1425621A, CN1810689A,
Institute in the patent documentations such as CN1603264A, CN101074146A, CN101155763A, CN 101624262A, CN101074146B
Disclosed glass falls within filter vitaglass, but their filtering principles are then to make use of CeO2、V2O5And TiO2To ultraviolet
Absorption, and CeO2、V2O5And TiO2The filtration of ultraviolet can not possibly be realized simultaneously with transmitance under 410nm all
For the T under 0 and 450nm450The sharp cut-off feature of ＞ 70%.Glass disclosed in these patent documentations either filtering principles,
Glass composition, application and the aspect such as purposes, the through performance and color ultraviolet cutoff all with the present invention being described below
Glass is clearly distinguished from.
Content of the invention
Problems to be solved by the invention
It is an object of the invention to provide a kind of ultraviolet cutoff glass, it is capable of full protection ultraviolet radiation, and
And there is preferable heat stability and chemical stability, can be used for lenses, glass pane and other needs to carry out ultraviolet protection
Environment in.In addition, the present invention is also provided by the optical glass lens of this ultraviolet cutoff glass manufacture and optical component.
For solution to problem
The present invention provide a kind of ultraviolet cutoff glass it is characterised in that：Described ultraviolet cutoff glass is not leaded, cadmium,
Arsenic, and following compound is contained with percentage by weight：SiO2：40～55%；B2O3：21～32%；Al2O3：1～7%；∑R2O：
5～15%, wherein R are Na+Or K+；Nd2O3：2～9%；CuO：0.1～1%；Ni2O3：0.05～0.8%；RX：0.5～5%,
Wherein R is Na+Or K+, X is F-、Cl-、Br-Or I-；Fe：0.1～1%；Sb2O3：0～0.5%, that above each group is divided and be more than
99.5%.
The ultraviolet cutoff glass of the invention described above, is further characterized in that：Thick in the sample of described ultraviolet cutoff glass
Spend for, under the test condition of 1mm, the transmitance of below 410nm is all 0, transmitance T at 450nm450＞ 70%, in 585nm
Transmitance T at place585＜ 30%, and the transmitance at 450nm, 500nm and 540nm meets T540＞ T500＞ T450.
The ultraviolet cutoff glass of the invention described above, is further characterized in that：Thick in the sample of described ultraviolet cutoff glass
Spend under the test condition of 1mm it is seen that light transmission rate is more than 70%.
The ultraviolet cutoff glass of the invention described above, is further characterized in that：Described ultraviolet cutoff glass is burgundy.
The present invention also provides a kind of optical glass lens, and it is made up of the ultraviolet cutoff glass of the invention described above.
The present invention also provides a kind of optical component, and it is made up of the ultraviolet cutoff glass of the invention described above.
The effect of invention
The present invention passes through to adjust the composition of glass and content in particular range, so that the ultraviolet cutoff glass of gained is existed
Thickness of sample is under the test condition of 1mm, is all 0 in the spectral transmittance of below 410nm, the spectral transmittance at 450nm
T450＞ 70%, transmitance T at 585nm585＜ 30%, and the transmitance satisfaction at 450nm, 500nm and 540nm
T540＞ T500＞ T450It is seen that light transmission rate is more than 70%, and glass is burgundy, thus realizing full protection ultraviolet spoke
Penetrate.Additionally, the ultraviolet cutoff glass of the present invention also has preferable heat stability and chemical stability.
Brief description
Fig. 1 is the spectral transmittance curve chart of the ultraviolet cutoff glass of embodiments of the invention 1～3.
Fig. 2 is the spectral transmittance curve chart of the ultraviolet cutoff glass of embodiments of the invention 4～6.
Fig. 3 is the spectral transmittance curve chart of the glass of comparative example A～D of the present invention.
Specific embodiment
For describing ultraviolet cutoff glass and its manufacture method of the invention described above in detail, the application provides specifically real as follows
Apply scheme, but the invention is not restricted to this.
During the ultraviolet cutoff glass manufacturing the present invention, select the component of glass based on following factors and contain
Amount.
SiO2It is the network generation body of glass, be to maintain the required composition of chemical durability of glass.If SiO2Content is less than
40%, then the chemical stability variation of glass, easily leave water during the use and long-term preservation of manufactured type part
Corrode vestige.But, if its content is more than 55%, so that glass melting is more difficult to, increase power consumption, and on sidewall of crucible during melting
It is easier the block occurring being difficult to melt, make the component in entrance glass unstable, the stability of impact product.So,
SiO2The content of component is limited to 40～55%, preferably 45～53%.
B2O3It is also that glass network generates body, if B2O3Content is less than 21%, can make prepared glass transition temperature (Tf) become
Height, increases the difficulty of follow-up die mould technique.But, if B2O3Content is more than 32%, then affected by its volatility and increase preparation all
The difficulty of matter glass, and the chemical stability variation of glass.So, B2O3The content of component is limited to 21～32%, preferably exists
22～29%.
Al2O3It is the effective ingredient improving chemical durability of glass, if its content is less than 1%, can not playing stably property
Effect, but if its content is higher than 7%, then makes the high temperature viscosity of glass become larger, the softening temperature (T of glassf) also gradually
Uprise, thus increasing the difficulty of follow-up die mould technique.So, Al2O3The content of component is limited to 1～7%, preferably 2～5%.
Na2O and K2O, as alkali metal oxide, has similar action in glass manufacture, and its Main Function is as hydrotropy
Agent reduces glass transition temperature (Tg) and softening temperature (Tf), and be the adjustment indispensable composition of glass expansion coefficient.
Additionally, Na2O and K2O can replace mutually within the specific limits.Na2O and K2The total content ∑ R of O2When O is less than 5%, its effect of fluxing
Fruit is not good, but works as Na2O and K2The total content ∑ R of O2When O is higher than 15%, the heat stability of glass and chemical stability are deteriorated.Institute
With ∑ R2O is advisable 5～15%, preferably 8～13%.
Nd2O3It is the indispensable required component of glass of the present invention.Nd2O3There is at 585nm and 530nm strong absorption
Peak, the glass of the present invention is because Nd2O3Introducing and make T585＜ 30%.Research finds, Nd3+Absorption peak intensity at 585nm and
Suddenly, this absorption band effectively absorbs the sodium yellow in the middle of HONGGUANG and the main wavestrip of green glow, can improve red, green, blue three mass-tone
Color contrast, reduce dazzle, alleviate visual fatigue, and Nd3+Another absworption peak 530nm also there is similar effect.
Work as Nd2O3Content be less than 2% when, it can not preferably play above-mentioned effect, but content be higher than 9% when, then can reduce glass
Visible light transmissivity.So, Nd2O3The content of component is limited to 2～9%, preferably 3～7%.
(R is Na to CuO and RX+Or K+, X is F-、Cl-、Br-Or I-) it is that the spectral transmittance realizing below 410nm is all 0
Key component, under conditions of the two is even into glass, through later-stage secondary heat treatment, can form Cu in glassmXnMicro-crystallization
Body, the straight-line dimension of this microcrystal, in 410nm, thus can stop or cutoff wavelength is much smaller than the light wave of 410nm and passes through,
But do not interfere with the light wave that wavelength is much larger than 410nm to pass through.Can not when CuO content is less than 0.1%, RX content less than 0.5%
Preferably play above-mentioned effect, but when CuO content is more than 1%, RX content and is more than 5%, the tendency towards devitrification of glass gradually increases.
Therefore, the content of CuO component is limited to 0.1～1%, and the preferably content in 0.2～0.7%, RX component is limited to 0.5～5%,
Preferably 1～4%.
Ni2O3It is the component introducing to adjust glass colour, its content can be controlled in the range of 0.05～0.8%, excellent
It is selected in the range of 0.05～0.4%.
The effect of Fe is to manufacture reducing atmosphere in glass, is introduced with pulverulence in production, its reducing atmosphere providing
Can be by part Cu in glass2+It is reduced to Cu+, and Cu+Form Cu in glass after being to ensure that later-stage secondary heat treatmentmXnMicro- knot
Amount of crystals and the neccessary composition of species.Above-mentioned effect can not preferably be played when Fe content is less than 0.1%, but work as Fe content
Cu in glass is then made during more than 1%+Content is excessive, leads to glass redness overweight, and can reduce the visible light transmissivity of glass.
So, the content of Fe component is limited to 0.1～1%, preferably 0.2～0.5%.
Sb2O3It is the component added as defrother, its content can play a role below 0.5%.Therefore, Sb2O3Group
The content divided is limited to 0～0.5%, preferably 0～0.2%.
For ensureing the spectral transmittance performance of the present invention, the optical glass that the present invention provides is not artificially introduced except above component
The element that other in addition can colour, for example：V, Mo, Cr, Mn, Co and Ag.Meanwhile, it is not artificially introduced containing following harmful yet
The compound of element, for example：Th, Cd, Tl, Os, Be and Se.
The specific embodiment 1-6 of the present invention given below and comparative example A-D is to further describe the present invention, but the present invention is not
It is limited to this.
Embodiment 1-6
Weigh by the weight proportion shown in Tables 1 and 2 and mix each compound, and thus obtained batch is put into
In smelting apparatus, after taking suitable stirring, clarification, temperature reduction technology to carry out melting at 1150 DEG C～1380 DEG C, melting is obtained
The vitreous humour cast obtaining or leakage note, in mould, thus obtain the ultraviolet cutoff glass of the present invention.
Comparative example A-D
Except using each component of the comparative example A-D shown in table 2 and the component of weight proportion replacement embodiment 1-6 and weight
Beyond proportioning, to manufacture glass with embodiment 1-6 identical mode.
Using Beijing Pu Xi General Corporation produce TU-1900 type ultraviolet spectrophotometer measure respectively above-described embodiment with
Transmitance under 410nm, 450nm, 500nm, 540nm, 585nm for the glass of comparative example, first to uv-spectrophotometric during test
Meter energising preheating, after its self-inspection finishes, is placed on being processed into the thick sample card of 1mm in the sample cell of ultraviolet spectrophotometer simultaneously
Close hatch door, the software design patterns test wavelength section that the equipment of reusing carries simultaneously is scanned, and completes automatic measurement, test result with
Curve and the output of numerical value two ways.The test of visible light transmissivity adopts the TQY-2 type that Central China optical instrument factory produces spherical
Photometer is carried out, and is placed on being processed into the thick sample card of 1mm in spheric photometer sample cell and closes hatch door, in display during test
Read test result on screen.Measurement result is as shown in Table 1 and Table 2.
Table 1
Table 2
Note：In table 1～2, each constituent content is to be represented with percentage by weight (Wt%), ∑ R2O=Na2O+K2In O, RX, R is
Na+Or K+, X is F-、Cl-、Br-Or I-), test sample thickness is 1mm.
The ultraviolet cutoff glass of embodiment of the present invention 1-6 be can be seen that in 410nm by above-mentioned measurement result and Fig. 1-2
Following spectral transmittance is 0, the spectral transmittance T at 450nm450＞ 70%, transmitance T at 585nm585＜
30%, and the transmitance at 450nm, 500nm and 540nm meets T540＞ T500＞ T450, in described ultraviolet cutoff glass
Thickness of sample be 1mm test condition under it is seen that light transmission rate is more than 70%, and glass be burgundy, thus realizing
Full protection ultraviolet radiation.Additionally, the ultraviolet cutoff glass of the present invention also has preferable heat stability and chemically stable
Property：The liquidus temperature (Lt) of the glass of embodiment 1-6 is below 950 DEG C, and tests according to the method for JB/T10576-2006,
Its resistance to water (DW) it is 1 grade, acid resistance (DA) it is more than 3 grades.
On the contrary, by above-mentioned measurement result and Fig. 3 can be seen that comparative example A-D form and content all can not fall completely within
In the composition and content range of ultraviolet cutoff glass of the invention described above.Comparative example A-D is not introduced into can meeting the present invention sharp
RX the and CuO composition of cutoff characteristic, their filtering principles make use of CeO2、V2O5And TiO2Absorption to ultraviolet, from
Comparative example A-D in table 1 and 2 can be seen that CeO2、V2O5And TiO2Filtration to ultraviolet can not realize 410nm simultaneously
Under T410For the T under 0 and 450nm450The sharp cut-off feature of ＞ 70%, works as TiO2、V2O5、Fe2O3、CeO2Increase to a certain amount of
Afterwards, T450Already below 70%, but T410Do not enable transmitance cut-off yet, the performance of protectiving ultraviolet radiation is bad.In addition, it is right
Ratio C is not introduced into Nd2O3Composition is it is impossible to meet T of the present invention585The subject invention of ＜ 30%.And work as T585During ＜ 30%, obtained
The color contrast of red, green, blue three mass-tone of glass can be improved, and there is minimizing dazzle, alleviate visual fatigue
Effect.Therefore, the performance parameter of the glass being obtained by comparative example A-D, such as T410、T450、T585Or visible light transmissivity also with
Embodiment of the present invention 1-6 significantly different, glass assumes brown or kermesinus.
The ultraviolet cutoff glass that the present invention provides is except can be because it is burgundy, acceptable in addition to filters ultra violet line
Prevent the stimulation to eyes for the high light of other wave bands, and the ultraviolet cutoff glass that the present invention provides also has sufficiently low liquid
Phase temperature (Lt)：Below 950 DEG C, therefore described glass is carrying out die mould, annealing and heat treatment to the liquidus temperature (Lt) of glass
During not milkiness, not crystallize.
The ultraviolet cutoff glass of the present invention is applied to processing and the die mould of sphere and aspherical lens, and lenses,
Glass pane and other need in the environment carry out ultraviolet protection.
The ultraviolet cutoff glass of the present invention is incubated 0.5～5 hour at 590 DEG C～650 DEG C, carries out at second heat
Reason, then optical glass lens or optical element be can be made into by cutting, grinding and surface polishing.Furthermore it is also possible to directly pass through
Die mould technology the ultraviolet cutoff glass of the present invention is pressed into after optical glass lens or optical element and carries out at second heat again
Reason, to improve heat stability and chemical stability further.
Industrial applicability
The ultraviolet cutoff glass of the present invention is 0 in the spectral transmittance of below 410nm, the spectral transmission at 450nm
Rate T450＞ 70%, transmitance T at 585nm585＜ 30%, and the transmitance satisfaction at 450nm, 500nm and 540nm
T540＞ T500＞ T450, described ultraviolet cutoff glass thickness of sample be 1mm test condition under it is seen that light transmission rate exists
More than 70%, and glass is burgundy, thus realizing full protection ultraviolet radiation.Additionally, the ultraviolet cutoff of the present invention
Glass also has preferable heat stability and chemical stability, can be made into optical glass lens or optical element, for lenses,
Glass pane and other need in the environment carry out ultraviolet protection.
Claims (7)
1. a kind of ultraviolet cutoff glass it is characterised in that：Described ultraviolet cutoff glass is not leaded, cadmium, arsenic, and with weight hundred
Divide ratio containing following compound：SiO2：40～55%；B2O3：21～32%；Al2O3：1～7%；∑R2O：5～15%, wherein R
For Na+Or K+；Nd2O3：2～9%；CuO：0.1～1%；Ni2O3：0.05～0.8%；RX：0.5～5%, wherein R are Na+Or K+, X is F-、Cl-、Br-Or I-；Fe：0.1～1%；Sb2O3：0～0.5%, that above each group is divided and be more than 99.5%.
2. ultraviolet cutoff glass according to claim 1 it is characterised in that：Sample in described ultraviolet cutoff glass
Thickness is that under the test condition of 1mm, the transmitance of below 410nm is all 0, transmitance T at 450nm450＞ 70%,
Transmitance T at 585nm585＜ 30%, and the transmitance at 450nm, 500nm and 540nm meets T540＞ T500＞ T450.
3. ultraviolet cutoff glass according to claim 1 and 2 it is characterised in that：In described ultraviolet cutoff glass
It is seen that light transmission rate is more than 70% under the test condition for 1mm for the thickness of sample.
4. ultraviolet cutoff glass according to claim 1 and 2 it is characterised in that：Described ultraviolet cutoff glass is dark
Brown.
5. ultraviolet cutoff glass according to claim 3 it is characterised in that：Described ultraviolet cutoff glass is secretly brown
Color.
6. a kind of optical glass lens, its ultraviolet cutoff glass described in any one of Claims 1 to 5 is made.
7. a kind of optical component, its ultraviolet cutoff glass described in any one of Claims 1 to 5 is made.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410634544.3A CN104445927B (en) | 2014-11-12 | 2014-11-12 | Ultraviolet cutoff glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410634544.3A CN104445927B (en) | 2014-11-12 | 2014-11-12 | Ultraviolet cutoff glass |
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| CN104445927A CN104445927A (en) | 2015-03-25 |
| CN104445927B true CN104445927B (en) | 2017-02-15 |
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| CN107739158A (en) * | 2017-10-31 | 2018-02-27 | 桂林加宏汽车修理有限公司 | A kind of UV resistance window material |
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| JP2544035B2 (en) * | 1991-08-14 | 1996-10-16 | セントラル硝子株式会社 | High iron content / high reduction rate frit glass and blue heat ray absorbing glass using the same |
| JP3698558B2 (en) * | 1998-07-30 | 2005-09-21 | セントラル硝子株式会社 | UV absorbing glass |
| CN101054268A (en) * | 2007-05-24 | 2007-10-17 | 卢秀强 | Coating glass with function of sunlight control low radiation, ultraviolet radiation stopping and photocatalysis sterilization, and preparation method thereof |
| CN101157522B (en) * | 2007-09-26 | 2010-12-15 | 武汉理工大学 | Visible light anti-reflection and ultraviolet radiation cut-off bifunctional coated glass and preparation method thereof |
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