CN115818957A - High-photosensitivity low-elasticity-modulus optical glass and preparation method and application thereof - Google Patents
High-photosensitivity low-elasticity-modulus optical glass and preparation method and application thereof Download PDFInfo
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- 206010034972 Photosensitivity reaction Diseases 0.000 title claims abstract description 87
- 239000005304 optical glass Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 230000036211 photosensitivity Effects 0.000 claims abstract description 57
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 26
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 20
- 229910052796 boron Inorganic materials 0.000 claims abstract description 14
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 13
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 10
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 10
- 239000011521 glass Substances 0.000 claims description 120
- 239000013307 optical fiber Substances 0.000 claims description 73
- 239000000835 fiber Substances 0.000 claims description 66
- 239000011162 core material Substances 0.000 claims description 50
- 238000005253 cladding Methods 0.000 claims description 31
- 238000002834 transmittance Methods 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 18
- 238000001228 spectrum Methods 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 238000012360 testing method Methods 0.000 claims description 13
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
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- 229910005793 GeO 2 Inorganic materials 0.000 description 3
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- HJTAZXHBEBIQQX-UHFFFAOYSA-N 1,5-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1CCl HJTAZXHBEBIQQX-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 206010070834 Sensitisation Diseases 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
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- 238000000137 annealing Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
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Classifications
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 invention relates to optical glass with high photosensitivity and low elastic modulus as well as a preparation method and application thereof. The optical glass comprises the following components in percentage by mass: 50 to 60 percent of SiO 2 ，9～10％B 2 O 3 ，0～7％Ge 2 O 3 ，4～7％Al 2 O 3 ，5～12％PbO，5～10％BaO，5～6％K 2 O，4～6％Na 2 O; wherein, B 2 O 3 And Al 2 O 3 The sum of the contents is less than or equal to 16 percent; b is 2 O 3 The sum of the content of PbO and PbO is less than or equal to 22 percent; siO 2 2 And Ge 2 O 3 The sum of the contents is less than or equal to 62 percent; in terms of molar content, na 2 O and K 2 Sum of O content and B 2 O 3 The content ratio is 0.9-1.4; na (Na) 2 O and K 2 Sum of O content, minus Al 2 O 3 Content, difference thereof and B 2 O 3 The content ratio is 0.4-0.8. The invention aims to solve the technical problem of how to improve the photosensitivity of the optical glass and reduce the elastic modulus of the optical glass to ensure that the photosensitivity is 5 multiplied by 10 ‑3 ～10×10 ‑3 The elastic modulus is 60-70GPa, and the comprehensive performance of the optical glass is good, so that the optical glass is more practical.
Description
Technical Field
The invention belongs to the technical field of optical glass manufacturing, and particularly relates to high-photosensitivity low-elasticity-modulus optical glass and a preparation method and application thereof.
Background
The fiber grating has the remarkable advantages of high sensitivity, high precision, low loss, easiness in distributed measurement, low power consumption, light weight and the like, becomes a key device in the fields of fiber sensing, fiber laser, fiber communication and the like, is widely applied in the fields of aerospace, ship heavy industry, petroleum power, national defense safety, high-speed rail and rail traffic, bridges, civil engineering and the like, plays an important role in the aspects of sensing control of various high-end equipment, health monitoring of major infrastructure and the like, and is a key technology for realizing photoelectric detection sensing, improving the equipment performance and guaranteeing the safety of a key structure.
According to the working principle of the fiber grating, photosensitivity and fiber deformation are important factors for determining the testing precision and sensitivity of the fiber grating, and the fiber material prepared from the high-photosensitivity low-elasticity-modulus glass can realize high-precision and high-sensitivity acceleration, pressure, deformation, temperature and other measurements after the grating is engraved.
In the existing fiber grating sensing technology, an optical fiber material taking quartz glass as a fiber core is mainly used. Since the intrinsic photosensitivity of silica glass is very small, about 10 -5 The order of magnitude, and its elastic modulus is high, about 73GPa, and the deformation quantity is small.
It has been reported that the ultraviolet photosensitivity of silica-based optical fiber can be improved to some extent by doping silica glass with a small amount of Ge/B element, hydrogen-carrying sensitization, high-temperature heat treatment, etc., but the photosensitivity can only reach 5X 10 -5 (ii) a level of (d); although the elastic modulus of the quartz glass material can be reduced through Ge/B codoping, the adjustment range of the elastic modulus is small, and the elastic modulus can reach the level of 72.5Gpa at the lowest, so that the application requirement of the fiber grating is still difficult to meet.
Meanwhile, the quartz-based optical fiber has the problems of insufficient photosensitivity, photosensitivity degradation at high temperature, difficult preparation of an optical fiber preform, high cost and the like, and cannot meet the application requirements of high-sensitivity, high-precision and high-stability optical fiber sensing.
Disclosure of Invention
The invention mainly aims to provide optical glass with high photosensitivity and low elastic modulus as well as a preparation method and application thereof, and aims to solve the technical problems of improving the photosensitivity of the optical glass and reducing the elastic modulus of the optical glass to ensure that the photosensitivity of the optical glass is 5 multiplied by 10 -3 ～10×10 -3 Elastic modulus of 60-70GPa, and the combination of optical glassThe performance is good, thereby being more suitable for practical use.
The purpose of the invention and the technical problem to be solved are realized by adopting the following technical scheme. The invention provides an optical glass with high photosensitivity and low elastic modulus, which comprises the following components in percentage by mass: 50-60% SiO 2 ，9～10％ B 2 O 3 ，0～7％ Ge 2 O 3 ，4～7％ Al 2 O 3 ，5～12％ PbO，5～10％ BaO，5～6％ K 2 O，4～6％ Na 2 O; wherein, B 2 O 3 And Al 2 O 3 The sum of the contents is less than or equal to 16 percent; b 2 O 3 The sum of the content of PbO and PbO is less than or equal to 22 percent; siO 2 2 And Ge 2 O 3 The sum of the contents is less than or equal to 62 percent; in terms of molar content, na 2 O and K 2 Sum of O content and B 2 O 3 The content ratio is 0.9-1.4; na (Na) 2 O and K 2 Sum of O content, minus Al 2 O 3 Content, difference thereof and B 2 O 3 The content ratio is 0.4-0.8.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.
Preferably, the optical glass with high photosensitivity and low elastic modulus further comprises Sb in percentage by mass 2 O 3 And/or As 2 O 3 ；Sb 2 O 3 And As 2 The sum of the contents of O is less than or equal to 0.8 percent.
Preferably, the refractive index of the above-mentioned high-photosensitivity low-elastic-modulus optical glass is 1.50 to 1.55; photosensitivity 5X 10 -3 ～10×10 -3 (ii) a The elastic modulus is 60-70GPa; the average dispersion coefficient is 60-65; coefficient of linear expansion of 70X 10 -7 /℃～85×10 -7 /° c; the glass transition temperature is 600-700 ℃; the sagging temperature of the glass is 750-800 ℃; the softening point of the glass is 800-850 ℃.
Preferably, the transmittance of the high-photosensitivity low-elasticity-modulus optical glass in a spectrum of 200-300 nm is less than or equal to 20 percent; the transmittance in the spectrum of 400-1800 nm wave band is more than or equal to 95 percent; the transmittance in the spectrum of 1100-1600 nm wave band is more than or equal to 99 percent; the in-spectrum transmittance was measured according to GB/T7962.12-2010, and the test samples were 5mm and 15mm thick glass sheets.
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. The preparation method of the optical glass with high photosensitivity and low elastic modulus provided by the invention comprises the following steps:
1) Weighing the raw materials according to the formula proportion, and uniformly mixing; the raw materials comprise: 50-60% SiO 2 ，9～10％ B 2 O 3 ，0～7％ Ge 2 O 3 ，4～7％ Al 2 O 3 ，5～12％ PbO，5～10％ BaO，5～6％K 2 O，4～6％ Na 2 O; wherein, B 2 O 3 And Al 2 O 3 The sum of the contents is less than or equal to 16 percent; b is 2 O 3 The sum of the content of PbO and PbO is less than or equal to 22 percent; siO 2 2 And Ge 2 O 3 The sum of the contents is less than or equal to 62 percent; in terms of molar content, na 2 O and K 2 Sum of O content and B 2 O 3 The content ratio is 0.9-1.4; na (Na) 2 O and K 2 Sum of O content, minus Al 2 O 3 Content, difference thereof and B 2 O 3 The content ratio is 0.4-0.8;
2) And adding the mixture into a crucible, melting at 1250-1450 ℃, clarifying, and pouring to obtain the high-photosensitivity low-elastic-modulus optical glass.
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. The volume grating provided by the invention comprises the optical glass with high photosensitivity and low elastic modulus.
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. The invention provides a preparation method of a volume grating, which comprises the following steps:
1) Covering the high-photosensitivity low-elasticity-modulus optical glass by using a mask plate;
2) And irradiating the optical glass by using ultraviolet laser or femtosecond laser to ensure that the refractive index of the optical glass is changed periodically to obtain the volume grating.
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. According to the present invention, there is provided an optical fiber comprising:
a core made of the above high-photosensitivity low-elastic-modulus optical glass; and the combination of (a) and (b),
the cladding is made of quartz glass or deep ultraviolet transparent glass material; the transmittance of the cladding in the spectrum of the wave band of 200-300 nm is more than 90 percent; the in-spectrum transmittance was measured according to GB/T7962.12-2010, and the test samples were 5mm and 15mm thick glass sheets.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.
Preferably, the optical fiber has a numerical aperture of 0.3 to 0.6 and a fiber loss of 0.4 to 1.0dB/m.
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. The preparation method of the optical fiber provided by the invention comprises the following steps:
1) Preparing a core glass rod from the optical glass with high photosensitivity and low elastic modulus; preparing a cladding glass tube by using quartz glass or a deep ultraviolet transparent glass material;
2) Vertically immersing the fiber core glass rod and the cladding glass tube in absolute ethyl alcohol with the temperature of 70 ℃ and the mass concentration of 99%, and cleaning for 3 times by using 20kHz ultrasonic waves;
3) And sleeving the fiber core glass rod in the cladding glass tube, assembling an optical fiber preform, and drawing to obtain the optical fiber.
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. According to the fiber grating provided by the invention, the fiber core material is the optical glass with high photosensitivity and low elastic modulus.
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. The preparation method of the fiber grating provided by the invention comprises the following steps:
1) Covering the fiber core of the optical fiber by using a mask plate;
2) And irradiating the fiber core by using ultraviolet laser or femtosecond laser to ensure that the refractive index of the fiber core is changed periodically to obtain the fiber grating.
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. The optical glass with high photosensitivity and low elastic modulus provided by the invention is applied to the technical fields of optical fiber sensing, optical fiber laser and optical fiber communication.
By means of the technical scheme, the optical glass with high photosensitivity and low elastic modulus, and the preparation method and the application thereof provided by the invention at least have the following advantages:
the invention provides high-photosensitivity low-elasticity-modulus optical glass and a preparation method and application thereof, which lead the photosensitivity (delta n) of the optical glass to be optimized and designed by the formula of the optical glass d ) Up to (5-10) x 10 -3 The photosensitivity stability is good, and the elastic modulus (E) is as low as 60-70GPa; the optical glass or the optical fiber prepared from the optical glass has high intrinsic photosensitivity and good photosensitivity stability, can realize rapid grating writing by irradiation of ultraviolet laser or femtosecond laser, has good photosensitivity stability after irradiation of the ultraviolet laser or the femtosecond laser, cannot decline in the using process, and does not change in the photosensitivity condition after annealing at the temperature of 300 ℃ for 2 hours; and the optical fiber prepared by the method also has lower elastic modulus, can generate larger deformation, and is easy to prepare into an optical fiber sensor or a high-power optical fiber laser with high sensitivity and high precision. Meanwhile, the optical glass has excellent comprehensive performance. Furthermore, the numerical aperture of the optical fiber prepared by the method is 0.3-0.6, the application requirements of different numerical apertures can be met, the optical fiber loss is 0.4-0.8dB/m, the loss is low, and the method is suitable for the fields of short-distance optical fiber sensing, communication, laser and the like.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description will be given to the embodiments, structures, features and effects of the optical glass with high photosensitivity and low elastic modulus according to the present invention, and the preparation method and applications thereof, in conjunction with the preferred embodiments.
The invention provides high-photosensitivity low-elasticity-modulus optical glass which comprises the following components in percentage by mass: 50-60% SiO 2 ，9～10％ B 2 O 3 ，0～7％ Ge 2 O 3 ，4～7％ Al 2 O 3 ，5～12％ PbO，5～10％ BaO，5～6％ K 2 O，4～6％ Na 2 O。
In the above technical solution of the present invention, siO 2 Is the main body of the glass forming skeleton and is the main component of the glass skeleton. By mass percent, siO 2 The content is 50-60%, which is beneficial to reducing the thermal expansion coefficient of the glass and improving the thermal stability, chemical stability, softening temperature, heat resistance, hardness, mechanical strength and the like of the glass; however, when SiO 2 When the content is higher than 60%, the melting difficulty is increased. The present invention strictly defines the SiO 2 The content of (A) is 50wt% -60 wt%.
B 2 O 3 Is a glass forming oxide, is also a component for forming a glass framework, and is a cosolvent for reducing the melting viscosity of glass. In the present invention, B 2 O 3 But also plays a key role in improving the photosensitivity of the glass and reducing the dispersion and the refractive index. Boron oxygen trihedron [ BO 3 ]And boron-oxygen tetrahedron [ BO 4 ]Boron may be trihedral [ BO ] under different conditions as structural elements 3 ]Or boron-oxygen tetrahedron [ BO 4 ]In the presence of B, it is difficult to form boron-oxygen tetrahedron under high-temperature melting conditions, but B is present only in the form of trihedron under certain conditions at low temperature 3+ There is a tendency to abstract free oxygen to form tetrahedra, making the structure compact and increasing the low temperature viscosity of the glass, so that it has characteristics of decreasing the viscosity of the glass at high temperature and increasing the viscosity of the glass at low temperature. Under the action of ultraviolet laser irradiation or femtosecond laser irradiation, the boron and the oxygen in the glass have three sidesBody [ BO ] 3 ]And boron-oxygen tetrahedron [ BO 4 ]The configuration at the microscopic level is transformed, which is the main cause of the photosensitivity of the glass. According to experimental research, the invention strictly limits B in percentage by mass 2 O 3 The content of (A) is 9-10%.
Al 2 O 3 Has special function in glass when Al 3+ Located in the silicon oxygen tetrahedron (AlO) 4 ]Meso, and silicon-oxygen tetrahedron [ SiO ] 4 ]The glass fiber is formed into a network structure body, but the volume is larger, so that the structure is loose, the gap is large, the filling of alkali metal ions is facilitated, the strength of the glass material is improved, and the elastic modulus is reduced.
In the glass system, al 2 O 3 Is part of a glass network structure and plays a connecting role, and aluminum can capture free oxygen to form AlO 4 ]Into a glass network structure, B 2 O 3 Mainly comprises [ BO 3 ]And [ BO 4 ]The form exists in the glass network body, when the component contains 9 to 10 percent of B 2 O 3 And 4 to 7% of Al 2 O 3 In the glass network body [ AlO ] 4 ]、[BO 3 ]、[BO 4 ]And [ SiO ] 4 ]The glass and the optical fiber prepared from the glass form space structure balance, the skeleton structure of the glass is enhanced, and the strength of the glass and the optical fiber prepared from the glass is improved. When B is present 2 O 3 And Al 2 O 3 When the sum of the contents exceeds 16%, the composition is formed by [ AlO ] 4 ]、[BO 4 ]The volume is large, the structure of the glass network is loose, a large amount of alkali metal ions need to be filled, but the strength of the glass is reduced, and the Young modulus, the refractive index, the dispersion and other properties of the glass material are influenced.
GeO 2 And is also a network former, and Ge can replace Si to enter the glass network because Ge and Si are the same group elements and the electronic structure of the outer layer is the same. After the irradiation of ultraviolet laser or femtosecond laser, the change of local microstructure can form the refractive index change. The invention strictly limits GeO 2 The content of (A) is 0 to 7%. Furthermore, in order to guarantee the glass melting quality and process control, the invention strictly limits SiO 2 And GeO 2 In an amount ofThe sum of which does not exceed 62%.
PbO plays an important role in improving the refractive index of glass, adjusting the thermal property of the glass, reducing the melting temperature of the glass and improving the internal quality of the glass. In addition, in the present invention, pbO is also a key factor for improving photosensitivity of the glass. This is because there are only 4 electrons in the outermost electron shells of Pb atoms, which easily absorb photons to cause energy level transition. At the same time Pb 2+ And Pb 4+ The valence state conversion occurs under the irradiation of ultraviolet laser, which causes the potential distribution change in the micro-light region, and further to O 2- The attractive force of the glass is changed, so that the microstructure of the glass is changed, and photosensitivity is formed. According to experimental research, the content of PbO is 5-12% by mass percent. PbO content exceeding 12% has serious adverse effects on the refractive index and dispersion of the glass. In order to give consideration to the parameters of the glass such as refractive index, dispersion, thermal property and the like, the invention strictly limits B 2 O 3 And the sum of the PbO content does not exceed 22%.
For B, in order to reduce glass dispersion, to increase chemical and thermal stability, and to increase photosensitivity 2 O 3 The presence in the glass is critical. It is generally considered that B 2 O 3 Should be present in the glass network predominantly in the tetrahedral form and a small proportion in the trihedral form and undergo a structural change under the action of ultraviolet radiation.
K 2 O and Na 2 O is also an alkali metal oxide, and exists as a network exosome in the glass structure to form non-bridge oxygen, so that the glass structure is relaxed, and the elastic modulus is reduced. Experimental research shows that the glass contains 5-6% of K 2 O, 4-6% of Na 2 And O, which can achieve various performances in the embodiment of the invention.
The magnitude of the elastic modulus of a glass material is generally dependent on the strength of the chemical bonds between the internal particles and also on the structure. The larger the chemical bond between the particles, the smaller the deformation, the larger the elastic modulus, the firmer the glass structure, and the elastic modulusThe larger; conversely, the smaller the elastic modulus of the glass material. Wherein the elastic modulus is equal to Al 2 O 3 、B 2 O 3 、Na 2 O、K 2 O is closely related.
In order to achieve low elastic modulus properties, the invention provides strict control of alkali metal oxides and B in the glass 2 O 3 The content ratio of (a). In the present invention, na is contained in the amount of molar content 2 O and K 2 Sum of O content and B 2 O 3 The content ratio is between 0.9 and 1.4. Meanwhile, in the present invention, the following formula represents Na in terms of molar content 2 O、K 2 O、Al 2 O 3 And B 2 O 3 In relation to the content, let Al 2 O 3 、B 2 O 3 、Na 2 O、K 2 Molar ratio of O
Comprises the following steps:
when in use
When, B 3+ And Al 3+ The glass exists in a glass network body in a tetrahedral form, the structural connection is tight, and the elastic modulus is increased; when in
Of (i) is Al 2 O 3 Instead of SiO 2 Due to Na 2 O、K 2 Deficiency of O, al 3+ Into the network body in the form of tetrahedrons, B 3+ The elastic modulus decreases from trihedron to tetrahedron. However, when Na 2 O、K 2 When O is seriously insufficient, i.e.
When, B 3+ All are in [ BO ] 3 ]Trihedral coordination state, and Al 3+ In a higher coordination state [ AlO 6 ]Filling gaps outside the networkIn part, the structure of the glass is firm and the elastic modulus is increased. According to experimental study, when Al is present 2 O 3 、B 2 O 3 、Na 2 O、K 2 Molar ratio of O
0.4 to 0.8, the glass material has a low elastic modulus, which is strictly defined by the present invention
0.4 to 0.8.
BaO is mainly used for adjusting the refractive index and dispersion coefficient of glass, and has great effect on reducing dispersion. According to experimental research, the BaO content is 5-10%.
The optical glass can also contain antimony trioxide and/or arsenic trioxide with the total content not more than 0.8 percent by mass, and the antimony trioxide and/or arsenic trioxide is mainly introduced into a glass system as a clarifier, so that bubbles in the glass melting process can be discharged, the defects of bubbles, stripes and the like generated in the glass melting process can be reduced, and the internal quality of the optical glass is improved. Preferred Sb in the invention 2 O 3 0 to 0.5% and As 2 O 3 0 to 0.4 percent.
The invention also provides a preparation method of the high-photosensitivity low-elasticity-modulus optical glass, which comprises the following steps of firstly weighing raw materials according to a formula proportion; the raw material formula is the formula of the optical glass with high photosensitivity and low elastic modulus; uniformly mixing the raw materials; then adding the mixture into a crucible, stirring in an oxygen atmosphere, melting at 1250-1450 ℃, clarifying, and finally pouring to obtain the high-photosensitivity low-elastic-modulus optical glass.
The high-photosensitivity low-elasticity-modulus optical glass prepared by the method has higher photosensitivity and deformability; photosensitivity is also called as photoinduced refractive index change, and means that the refractive index of a glass material is permanently changed under the action of ultraviolet laser or femtosecond laser; the elastic modulus is used to measure the ability of a solid material to resist deformation, i.e. the smaller the elastic modulus of the solid material is, the larger the deformation amount is, also called young's modulus. The present invention evaluates various properties of optical glass according to the following methods:
testing the refractive index before and after ultraviolet laser irradiation according to GB/T7962.1-2010, and the refractive index (n) d ) Is 1.50 to 1.55.
The elastic modulus is obtained by measuring the propagation speed of an elastic wave in a glass sample according to the GB/T7962.6-2010 ultrasonic pulse echo method, and the elastic modulus (E) is 60-70 GPa.
Testing the internal transmittance of the spectrum according to GB/T7962.12-2010, wherein the sample is a thick glass sheet with the thickness of 5mm and 15 mm; namely, respectively using a spectrophotometer to test the spectral transmittance of glass sheets with the thickness of 5mm and 15mm, and calculating the ratio of the spectral transmittance of the glass sheets with the thickness of 10mm, namely the internal transmittance of glass with the thickness of 10 mm; the result is that the transmittance in the spectrum of the wave band of 200-300 nm is less than or equal to 20 percent, and the result shows that the optical glass has extremely high light absorption rate in the deep ultraviolet wave band (namely the wave band of the fiber grating engraved by the ultraviolet laser), and the refractive index of the glass can be greatly adjusted by improving the absorption of the glass to the deep ultraviolet light, namely the intrinsic photosensitivity is high; the transmittance in the spectrum of 400-1800 nm is more than or equal to 95 percent, and the transmittance in the spectrum of 1100-1600 nm is more than or equal to 99 percent; the 1260 nm-1625 nm wave band is an optical communication wave band; that is, the optical glass of the present invention has a very low absorption rate and a high transmittance in the band, so as to reduce the light attenuation and improve the compatibility of the glass optical fiber with the conventional communication optical fiber; irradiating with ultraviolet laser under the conditions of laser wavelength of 248nm, pulse width of 10ns, pulse frequency of 50Hz, pulse energy of 20mJ, spot diameter of 5mm, irradiation time of 10min, and photosensitivity of the product of not less than 5 × 10 -3 Up to 10 × 10 -3 。
Testing Abbe number (average dispersion coefficient) according to GB/T7962.1-2010, and testing the average dispersion coefficient (Abbe number upsilon) of the Abbe number d ) Is 60 to 65.
Testing expansion coefficient, transition temperature, softening temperature and softening point according to GB/T7962.16-2010, wherein the linear expansion coefficient is 70 multiplied by 10 -7 /℃～85×10 -7 /° c; the glass transition temperature (Tg) is 600-700 ℃; the glass sag temperature (Ts) is 750-800 ℃;glass softening point (viscosity 10) 7.6 The temperature corresponding to Pa.s) is 800-850 ℃.
Preferably, the optical glass comprises the following components in percentage by mass: 50-58.5% SiO 2 ，9～10％B 2 O 3 ，3～7％ Ge 2 O 3 ，4～7％ Al 2 O 3 ，7～12％ PbO，5～10％ BaO，5～6％ K 2 O，4～6％ Na 2 O; the photosensitivity of the optical glass is more than or equal to 6.5 multiplied by 10 -3 The modulus of elasticity (E) is ≦ 66GPa, as in examples 3 to 8.
Preferably, the optical glass comprises the following components in percentage by mass: 50 to 51 percent of SiO 2 ，9～10％B 2 O 3 ，6～7％ Ge 2 O 3 ，6～7％ Al 2 O 3 ，8～12％ PbO，5.9～7％ BaO，5％ K 2 O，5～5.4％Na 2 O; the photosensitivity of the optical glass is more than or equal to 9 multiplied by 10 -3 The modulus of elasticity (E) is ≦ 62.3GPa, as in example 5 and example 8.
Preferably, the optical glass comprises the following components in percentage by mass: 50% SiO 2 ，9.5％ B 2 O 3 ，6％Ge 2 O 3 ，6％Al 2 O 3 ，12％PbO，5.9％BaO，5％K 2 O，5％Na 2 O; the photosensitivity of the optical glass is 9.5 multiplied by 10 -3 The modulus of elasticity (E) was 60.1GPa as in example 8.
The invention also provides a volume grating and a preparation method thereof, which are prepared by adopting the high-photosensitivity low-elasticity-modulus optical glass and have high photosensitivity and low elasticity modulus; the preparation method of the volume grating is to use a mask plate to cover the high-photosensitivity low-elasticity-modulus optical glass; and then irradiating the optical glass by using ultraviolet laser or femtosecond laser to ensure that the refractive index of the optical glass is changed periodically to obtain the volume grating. After the optical glass with high photosensitivity and low elastic modulus is irradiated by a mask plate and ultraviolet laser or femtosecond laser, the refractive index of the optical glass is permanently increased, and the formed volume grating has good application prospect.
The invention also provides an optical fiber comprising the high-photosensitivity low-elasticity-modulus optical glass; the optical fiber consists of a fiber core and a cladding; the fiber core is made of the high-photosensitivity low-elasticity-modulus optical glass; the cladding material is quartz glass or low-refractive-index deep ultraviolet-transmitting glass material, such as silicate glass, borate glass, phosphate glass or fluoride glass, the spectral transmittance of the glass in a 200-300 nm wave band is not more than 20%, and the spectral transmittance is more than 90%; the in-spectrum transmittance was measured according to GB/T7962.12-2010, and the test samples were 5mm and 15mm thick glass sheets.
The refractive index of the fiber core glass is 1.50-1.55, so that the numerical aperture range of the optical fiber formed by the fiber core glass and the cladding material can be controlled within 0.3-0.6, and the application requirements of different numerical apertures can be met; the optical fiber loss is 0.4-0.8dB/m, has lower loss, and is suitable for the fields of short-distance optical fiber sensing, communication, laser and the like.
The fiber core of the optical fiber adopts high-photosensitivity low-elasticity-modulus optical glass, has high intrinsic photosensitivity, can realize rapid grating writing after being irradiated by ultraviolet laser or femtosecond laser, has good photosensitivity stability after being irradiated by the ultraviolet laser or the femtosecond laser, cannot fade in the using process, and is annealed for 2 hours at the temperature of 300 ℃, so that the photosensitivity condition is not changed; furthermore, the optical fiber also has a lower elastic modulus and can generate larger deformation; based on the high photosensitivity, the photosensitive stability and the low elastic modulus, the relation is easy to prepare into a high-sensitivity and high-precision optical fiber sensor or a high-power optical fiber laser.
The optical fiber may be a single mode optical fiber or a multimode optical fiber. Wherein the diameter of the fiber core of the single-mode optical fiber is 6-10 μm, and the diameter of the cladding is 125 +/-5 μm; or the single-mode fiber is a large-size fiber, the diameter of a fiber core of the single-mode fiber is 6-10 mu m, and the diameter of a cladding of the single-mode fiber is 400 +/-5 mu m. The diameter of the core of the multimode fiber is 50-62.5 mu m, and the diameter of the cladding is 125 +/-5 mu m; or the multimode fiber is a large-size fiber, the diameter of a core of the multimode fiber is 50-62.5 mu m, and the diameter of a cladding of the multimode fiber is 400 +/-5 mu m.
The optical fiber is not limited to a single-core optical fiber and a variation in size thereof, and may be a multi-core optical fiber, a hollow-core optical fiber, or the like, and is not particularly limited in the present invention.
The invention also provides a preparation method of the optical fiber, which comprises the following steps: designing physical dimensions of a core glass rod and a cladding glass tube according to optical fiber specifications (a core diameter D1 and a cladding diameter D2), wherein the diameter of the core glass rod is D1, the outer diameter of the cladding glass tube is D2, and the inner diameter of the cladding glass tube is D1+ delta D; theoretically, D1 and D2 are equal in proportion to D1 and D2, but in the actual process of drawing by using a tube rod method, a certain gap is formed between the core rod and the cladding glass tube; when the core rod is in close contact with the cladding glass tube, the proportion is equal; the invention preferably selects the delta D of 0.1-0.5 mm, thus not only ensuring the smooth combination of the core rod and the glass tube, but also minimizing the clearance between the core rod and the glass tube; preferably D2/D1= D2/D1; then preparing a core glass rod by using the optical glass with high photosensitivity and low elastic modulus; weighing the raw materials according to the formula; uniformly mixing the weighed raw materials; melting the mixture into optical glass according to the preparation method of the optical glass, processing the optical glass into a fiber core glass rod with the diameter of D1, and polishing the surface of the fiber core glass rod; preparing a cladding glass tube by using quartz glass or a deep ultraviolet transparent glass material; processing quartz glass or deep ultraviolet-transmitting glass into a cladding glass tube with the outer diameter of D2 and the inner diameter of D1+ delta D, and polishing the inner wall and the outer wall of the glass tube by using methods such as machinery, flame and the like; vertically immersing the fiber core glass rod and the cladding glass tube in 99% absolute ethyl alcohol at the temperature of 70 ℃, cleaning for 3 times by using a 20kHz ultrasonic cleaning machine, fully removing organic impurities such as polishing solution, cooling solution, oil stain and the like, and reducing the loss of a fiber core-cladding interface; sleeving a fiber core glass rod in a cladding glass tube to assemble an optical fiber preform; fixing the optical fiber preform on the position right above a heating furnace of an optical fiber drawing tower, and moving the tail end of the optical fiber preform downwards to the highest position of the furnace temperature when the temperature of the drawing furnace meets the drawing requirement; when the cladding glass is ultraviolet-transmitting oxide glass, the drawing temperature is preferably 800-1000 ℃; when the cladding glass is quartz glass, the drawing temperature is preferably 1800-2200 ℃; the tail end of the optical fiber prefabricated rod is softened and falls at high temperature, and the optical fiber is uniformly drawn under the action of traction power.
The invention also provides a fiber grating and a preparation method thereof, wherein the fiber core material is made of the optical glass with high photosensitivity and low elastic modulus, and has high photosensitivity and low elastic modulus; the preparation method of the fiber grating comprises the following steps: 1) Covering the fiber core of the optical fiber by using a mask plate; 2) And irradiating the fiber core by using ultraviolet laser or femtosecond laser to ensure that the refractive index of the fiber core is changed periodically to obtain the fiber grating. The optical fiber with high photosensitivity and low elastic modulus is used as the fiber core, the refractive index of the fiber core part irradiated by a mask plate and ultraviolet laser or femtosecond laser is permanently increased, and the refractive index of the fiber core is periodically changed to form the fiber grating, so that the fiber grating is further applied to the fields of optical fiber sensing, fiber laser, fiber communication and the like.
The invention also provides application of the high-photosensitivity low-elasticity-modulus optical glass in the technical fields of optical fiber sensing, optical fiber laser and optical fiber communication.
The present invention will be further described with reference to the following specific examples, which should not be construed as limiting the scope of the invention, but rather as providing those skilled in the art with certain insubstantial modifications and adaptations of the invention based on the teachings of the invention set forth herein.
Unless otherwise specified, the following materials, reagents and the like are commercially available products well known to those skilled in the art; unless otherwise specified, all methods are well known in the art. Unless defined otherwise, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
Examples 1 to 8
In the embodiments 1 to 8 of the present invention, an optical glass with high photosensitivity and low elastic modulus is prepared, and the formulation composition thereof is shown in the following table 1 by mass percentage.
TABLE 1
The raw materials are weighed according to the components shown in the table 1, then mixed evenly, added into a crucible, melted and clarified at 1300 ℃, then the molten glass is poured into optical glass, and then the optical glass is subjected to main performance test, and the test results are shown in the table 2.
TABLE 2
Examples 9 to 16
Optical fibers were prepared by using the high-photosensitivity low-elastic-modulus optical glasses prepared in examples 1 to 8 of the present invention as the cores of the optical fibers, respectively. The cladding material of the optical fiber and the fiber parameters and preparation process parameters are shown in table 3 below.
TABLE 3
As can be seen from the data in tables 1 to 3, the optical glass and the optical fiber prepared from the glass have the characteristics of high photosensitivity, low elastic modulus and the like, and after being irradiated by a mask plate and ultraviolet laser or femtosecond laser, the optical glass can write a grating with periodic refractive index change on the fiber core of the optical fiber, and can be further applied to the fields of optical fiber sensing, optical fiber laser, optical fiber communication and the like.
The features of the invention claimed and/or described in the specification may be combined, and are not limited to the combinations set forth in the claims by the recitations therein. The technical solutions obtained by combining the technical features in the claims and/or the specification also belong to the scope of the present invention.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.
Claims (13)
1. An optical glass with high photosensitivity and low elastic modulus is characterized by comprising the following components in percentage by mass: 50 to 60 percent of SiO 2 ，9～10％B 2 O 3 ，0～7％Ge 2 O 3 ，4～7％Al 2 O 3 ，5～12％PbO，5～10％BaO，5～6％K 2 O，4～6％Na 2 O; wherein, B 2 O 3 And Al 2 O 3 The sum of the contents is less than or equal to 16 percent; b is 2 O 3 The sum of the content of PbO and PbO is less than or equal to 22 percent; siO 2 2 And Ge 2 O 3 The sum of the contents is less than or equal to 62 percent; in terms of molar content, na 2 O and K 2 Sum of the contents of O and B 2 O 3 The content ratio is 0.9-1.4; na (Na) 2 O and K 2 Sum of O content, minus Al 2 O 3 Content, difference thereof and B 2 O 3 The content ratio is 0.4-0.8.
2. The high-photosensitivity low-elastic-modulus optical glass according to claim 1, further comprising Sb in a mass percentage 2 O 3 And/or As 2 O 3 ；Sb 2 O 3 And As 2 The sum of the contents of O is less than or equal to 0.8 percent.
3. The high-photosensitivity low-elastic-modulus optical glass according to claim 1 or 2, characterized in that its refractive index is 1.50 to 1.55; photosensitivity 5X 10 -3 ～10×10 -3 (ii) a The elastic modulus is 60-70GPa; the average dispersion coefficient is 60-65; coefficient of linear expansion of 70X 10 -7 /℃～85×10 -7 /° c; the glass transition temperature is 600-700 ℃; the sagging temperature of the glass is 750-800 ℃; the softening point of the glass is 800-850 ℃.
4. The high-photosensitivity low-elastic-modulus optical glass according to claim 1 or 2, wherein the transmittance in the 200-300 nm band spectrum is 20% or less; the transmittance in the spectrum of 400-1800 nm wave band is more than or equal to 95 percent; the transmittance in the spectrum of 1100-1600 nm wave band is more than or equal to 99 percent; the in-spectrum transmittance was measured according to GB/T7962.12-2010, and the test samples were 5mm and 15mm thick glass sheets.
5. A preparation method of optical glass with high photosensitivity and low elastic modulus is characterized by comprising the following steps:
1) Weighing the raw materials according to the formula proportion, and uniformly mixing; the raw materials comprise: 50 to 60 percent of SiO 2 ，9～10％B 2 O 3 ，0～7％Ge 2 O 3 ，4～7％Al 2 O 3 ，5～12％PbO，5～10％BaO，5～6％K 2 O，4～6％Na 2 O; wherein, B 2 O 3 And Al 2 O 3 The sum of the contents is less than or equal to 16 percent; b is 2 O 3 The sum of the content of PbO and PbO is less than or equal to 22 percent; siO 2 2 And Ge 2 O 3 The sum of the contents is less than or equal to 62 percent; in terms of molar content, na 2 O and K 2 Sum of O content and B 2 O 3 The content ratio is 0.9-1.4; na (Na) 2 O and K 2 Sum of O content, minus Al 2 O 3 Content, difference thereof and B 2 O 3 The content ratio is 0.4-0.8;
2) And adding the mixture into a crucible, melting at 1250-1450 ℃, clarifying, and pouring to obtain the high-photosensitivity low-elastic-modulus optical glass.
6. A volume grating comprising the high-photosensitivity low-elastic-modulus optical glass according to any one of claims 1 to 4.
7. A method for preparing a volume grating is characterized by comprising the following steps:
1) Covering the high-photosensitivity low-elastic-modulus optical glass according to any one of claims 1 to 4 with a mask;
2) And irradiating the optical glass by using ultraviolet laser or femtosecond laser to ensure that the refractive index of the optical glass is changed periodically to obtain the volume grating.
8. An optical fiber, comprising:
a core made of the high-photosensitivity low-elastic-modulus optical glass according to any one of claims 1 to 4; and the combination of (a) and (b),
the cladding is made of quartz glass or deep ultraviolet transparent glass material; the transmittance of the cladding in the spectrum of the wave band of 200-300 nm is more than 90 percent; the in-spectrum transmittance was measured according to GB/T7962.12-2010, and the test samples were 5mm and 15mm thick glass sheets.
9. The optical fiber of claim 8, wherein the numerical aperture is 0.3 to 0.6 and the fiber loss is 0.4 to 1.0dB/m.
10. A method of making an optical fiber, comprising the steps of:
1) Preparing a core glass rod from the high-photosensitivity low-elastic-modulus optical glass according to any one of claims 1 to 4; preparing a cladding glass tube by using quartz glass or a deep ultraviolet transparent glass material;
2) Vertically immersing the fiber core glass rod and the cladding glass tube in absolute ethyl alcohol with the temperature of 70 ℃ and the mass concentration of 99%, and cleaning for 3 times by using 20kHz ultrasonic waves;
3) And sleeving the fiber core glass rod in the cladding glass tube, assembling an optical fiber preform, and drawing to obtain the optical fiber.
11. A fiber grating, characterized in that the core material is the high-photosensitivity low-elastic-modulus optical glass according to any one of claims 1 to 4.
12. A preparation method of fiber grating is characterized by comprising the following steps:
1) Covering the core of the optical fiber according to claim 8 or 9 with a mask;
2) And irradiating the fiber core by using ultraviolet laser or femtosecond laser to ensure that the refractive index of the fiber core is changed periodically to obtain the fiber grating.
13. The application of the optical glass with high photosensitivity and low elastic modulus in the technical fields of optical fiber sensing, optical fiber laser and optical fiber communication.
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