CN103241949A - Lead oxide containing fluoroziconate glass and preparation method thereof - Google Patents
Lead oxide containing fluoroziconate glass and preparation method thereof Download PDFInfo
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- CN103241949A CN103241949A CN2013101886320A CN201310188632A CN103241949A CN 103241949 A CN103241949 A CN 103241949A CN 2013101886320 A CN2013101886320 A CN 2013101886320A CN 201310188632 A CN201310188632 A CN 201310188632A CN 103241949 A CN103241949 A CN 103241949A
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- glass
- fluorozirconate
- preparation
- plumbous oxide
- grog
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- 239000011521 glass Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 title claims description 23
- 229910000464 lead oxide Inorganic materials 0.000 title abstract 2
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000005386 fluorozirconate glass Substances 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 7
- 229910016036 BaF 2 Inorganic materials 0.000 claims abstract description 5
- 229910016569 AlF 3 Inorganic materials 0.000 claims abstract description 4
- 229910017768 LaF 3 Inorganic materials 0.000 claims abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 239000005383 fluoride glass Substances 0.000 abstract description 7
- 238000002425 crystallisation Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 230000008025 crystallization Effects 0.000 abstract description 4
- 239000013307 optical fiber Substances 0.000 abstract description 3
- 238000007496 glass forming Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000002834 transmittance Methods 0.000 abstract 1
- 230000003287 optical effect Effects 0.000 description 9
- 101150039289 PZF1 gene Proteins 0.000 description 4
- 238000004455 differential thermal analysis Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- YBJHBAHKTGYVGT-ZKWXMUAHSA-N (+)-Biotin Chemical compound N1C(=O)N[C@@H]2[C@H](CCCCC(=O)O)SC[C@@H]21 YBJHBAHKTGYVGT-ZKWXMUAHSA-N 0.000 description 1
- 108010023321 Factor VII Proteins 0.000 description 1
- 239000005371 ZBLAN Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000000146 host glass Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- -1 optical waveguides Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- FEPMHVLSLDOMQC-UHFFFAOYSA-N virginiamycin-S1 Natural products CC1OC(=O)C(C=2C=CC=CC=2)NC(=O)C2CC(=O)CCN2C(=O)C(CC=2C=CC=CC=2)N(C)C(=O)C2CCCN2C(=O)C(CC)NC(=O)C1NC(=O)C1=NC=CC=C1O FEPMHVLSLDOMQC-UHFFFAOYSA-N 0.000 description 1
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Abstract
一种含氧化铅的氟锆酸盐玻璃及其制备方法，该玻璃的摩尔百分比组成范围为：PbO：2～15，ZrF4：45～60，BaF2：25～35，LaF3+AlF3+YF3：5～11。该玻璃在近紫外到中红外波段有很高的透过率。与现有的氟化物玻璃相比，具有更好的成玻璃性能，能显著改善光纤拉制过程中的析晶，适宜于制造大尺寸的红外材料。
A fluorozirconate glass containing lead oxide and its preparation method. The composition range of molar percentage of the glass is: PbO: 2-15, ZrF 4 : 45-60, BaF 2 : 25-35, LaF 3 +AlF 3 +YF 3 : 5～11. The glass has high transmittance in the near-ultraviolet to mid-infrared band. Compared with the existing fluoride glass, it has better glass-forming performance, can significantly improve the crystallization in the drawing process of optical fiber, and is suitable for manufacturing large-scale infrared materials.
Description
Technical field
The present invention relates to Fluorozirconate glass, particularly a kind of Fluorozirconate glass that contains plumbous oxide and preparation method thereof.
Background technology
Fluoride glass has optical application prospect widely, as for the preparation of ultra-low-loss fiber, optical waveguides, fiber amplifier etc.Succeeding in developing of bulk fluoride glass makes these materials receive publicity day by day as the application of volume infrared optical device.With ZrF
4For the fluoride glass of the main moiety of glass is called Fluorozirconate glass.Compare with other fluoride glass, the not only formation ability of Fluorozirconate glass is good, and optical property is also very good, is the main fluoride glass matrix of preparation fluoride fiber.Although developed many new systems, nearly all system is easy devitrification all.Poulain has reported that typical Fluorozirconate glass comprises 56ZrF
434BaF
26LaF
34AlF
3, abbreviate ZBLA(as referring to J.Non-Cryst.Solids, 1983,56:1-14).The Fluorozirconate glass that with ZBLA is representative has good infrared property.Because the one-tenth glass properties of difference, the present large-size glass that also should form (as thickness greater than 15mm) report.Can improve into glass properties although introduce NaF on the basis of this composition, and obtained thickness greater than the glass material of 30mm (referring to Mater.Sci.For μ m, 1991,67﹠amp; 68:13-16), but because the adding of NaF, the chemical stability of glass reduces, and is not suitable for the infrared window in the atmosphere.In fluorochemical, as the most promising ultra-low-loss fiber material, ZBLAN is widely studied, however optical fiber the crystallization problem of pulling process remain the major cause that causes optical attenuation (referring to J.Non-Cryst.Solids, 1992,140:1-9).
Summary of the invention
For solving the problem that ZBLA becomes the glass properties difference, the object of the present invention is to provide a kind of Fluorozirconate glass that contains plumbous oxide and preparation method thereof, this glass has improved the one-tenth glass properties of fluozirconate, has obtained the large size infrared glass.
Technical solution of the present invention is as follows:
A kind of Fluorozirconate glass that contains plumbous oxide, each component of this glass is as follows by mole per-cent (mol%):
PbO： 2～15
ZrF
4： 45～60,
BaF
2： 25～35,
MF
3： 5～11，
Annotate: M represents trivalent ions such as La, Al, Y.
The above-mentioned preparation method who contains the Fluorozirconate glass of plumbous oxide is characterized in that this method comprises the following steps:
1. select the molar percentage of above-mentioned glass, and the corresponding raw material of weighing;
2. with described ZrF
4, BaF
2, LaF
3+ AlF
3+ YF
3The powder of pure fluorochemical composition is put into platinum crucible after fully mixing, and crucible is put into stove and be warming up to 850 ℃ to keep 30 minutes, fully takes out after the fusing, casts directly on the template, makes the fluozirconate grog;
3. again the fluozirconate grog is put into platinum crucible, with crucible put into 830 ℃ in stove with the fusing of glass grog after, add the PbO of corresponding proportioning, stir made in 30 minutes mix after, take out and be poured in the preheating template;
4. then glass was annealed 2 hours down at 350 ℃, furnace cooling can obtain containing the Fluorozirconate glass sample of plumbous oxide to room temperature then.
Be usually used in weighing the index △ T(△ T=T that component becomes the glass properties quality
x-T
g) and S, S=(Tx-Tg) (Tp-Tx)/Tg, wherein T
gBe the transition temperature of glass, T
xFor the crystallization of glass begins temperature, T
pBe the crystallization peak temperature.△ T and the more big glass that more is conducive to into of S value are fit to the appearance of crystal grain in preparation large-size glass and the minimizing glassy product preparation process.
Technique effect of the present invention is as follows:
Gained glass of the present invention shows after tested: the S value of resulting glass is compared former pure fluorochemical and is significantly improved, and has kept the good visible infrared property of former fluoride glass simultaneously substantially.
Cutoff wavelength is greater than 6 μ m, and the glass phonon energy is low, becomes glass properties good, is fit to preparation infrared laser optical fiber and is used as fiber amplifier host glass and other optical materials.
Description of drawings
Fig. 1 is respectively differential thermal curve (PZF1) and the pure fluorochemical composition 57ZrF that the present invention contains the fluozirconate embodiment 3 of plumbous oxide
434BaF
25LaF
34AlF
3The differential thermal curve of prepared glass (ZF1).
Fig. 2 consists of the hyaloid of the fluozirconate embodiment 3 that contains plumbous oxide at the test result figure of optical wavelength range 0.3～7.0 μ m transmitance among the present invention.
Embodiment
For the preparation that contains the plumbous oxide Fluorozirconate glass is described further, present embodiment is implemented according to technical solution of the present invention, provides concrete embodiment and flow process.
ZrF
4With NH
4ZrF
5Form introduce, other fluorochemicals are high-purity fluoride raw material.Concrete experimentation is formed at the molar percentage that table 1 has provided the embodiment of the invention 1,2,3,4,5 raw material, all adopts this preparation technology to carry out, and carries out in two steps:
1. prepare powder 1000 grams of pure fluorochemical composition according to certain proportioning, after fully mixing, put into platinum crucible, crucible is put into stove and be warming up to 850 ℃ of maintenances 30 minutes, fully take out after the fusing, cast directly on the template, make the grog of pure fluozirconate;
2. take by weighing grog 1000 gram, be reentered in the platinum crucible, crucible is put into 830 ℃ in stove with after the fusing of glass grog, add the PbO of corresponding proportioning, stir made in 30 minutes mix after, take out and be poured in the preheating template;
3. then glass was annealed 2 hours down at 350 ℃, 24 hours furnace cooling can obtain containing the Fluorozirconate glass sample of plumbous oxide to room temperature then.
The glass sample that obtains is carried out differential thermal (DTA) analysis, and the differential thermal curve (PZF1) and the pure Fluorozirconate glass that obtain embodiment 3 samples are formed 57ZrF
434BaF
25LaF
34AlF
3Differential thermal curve (ZF1) test result as shown in Figure 1.Wherein the ZF1 curve the △ T of corresponding glass be 80 ℃, S is 6.78; And curve PZF1 the △ T of corresponding glass be 100 ℃, S is 12.Bigger △ T(△ T=T
x-T
g) with S(S=(Tx-Tg) (Tp-Tx)/Tg) value show that the Fluorozirconate glass PZF1 that contains plumbous oxide has the better glass properties that becomes than pure Fluorozirconate glass ZF1, is fit to preparation large size infra-red material.
Be that the transmitance of 0.3～7.0 μ m is tested to the gained glass sample in optical wavelength range, thickness of sample is 6mm, and test result as shown in Figure 2.As seen from the figure, the transmitance of most of optical wavelength reaches 90%, and the Fluorozirconate glass that contains plumbous oxide of the present invention has good near ultraviolet and was popular in performance to China and foreign countries.
Table 1 the present invention contains the relevant composition proportion (molar percentage) of the Fluorozirconate glass embodiment of plumbous oxide
Table 1
Following table 2 has provided the characteristic temperature of the corresponding proportioning gained of embodiment glass in the table 1 and the size of anti-crystallization ability stable factor S.The characteristic temperature value of glass obtains by differential thermal analysis (DTA), and the temperature rise rate in the test process is 10 ℃/min.
Table 2
| Embodiment | T g（℃） | T x（℃） | T p（℃） | T m（℃） | S |
| 1 | 295 | 380 | 414 | 539 | 9.1 |
| 2 | 300 | 400 | 438 | 516 | 12.6 |
| 3 | 296 | 389 | 422 | 526 | 10.4 |
| 4 | 296 | 380 | 412 | 531 | 9 |
| 5 | 296 | 383 | 412 | 537 | 8.5 |
Table 2
The ZBLA glass S value of oxygen-free lead is 6.78, and by above-mentioned differential thermal analysis as can be known, glass is formed in the above-mentioned example bigger S value, has shown that we obtain better glass and form performance by adding PbO, is fit to preparation large size infrared glass.
Claims (2)
1. a Fluorozirconate glass that contains plumbous oxide is characterized in that, the molar percentage compositing range of this glass is as follows:
PbO： 2～15，
ZrF
4： 45～60，
BaF
2： 25～35,
LaF
3+AlF
3+YF
3： 5～11。
2. the described preparation method who contains the Fluorozirconate glass of plumbous oxide of claim 1 is characterized in that this method comprises the following steps:
1. the molar percentage of the selected described glass of claim 1, and the corresponding raw material of weighing;
2. with described ZrF
4, BaF
2, LaF
3+ AlF
3+ YF
3The powder of pure fluorochemical composition is put into platinum crucible after fully mixing, and crucible is put into stove and be warming up to 850 ℃ to keep 30 minutes, fully takes out after the fusing, casts directly on the template, makes the fluozirconate grog;
3. again the fluozirconate grog is put into platinum crucible, with crucible put into 830 ℃ in stove with the fusing of glass grog after, add the PbO of corresponding proportioning, stir made in 30 minutes mix after, take out and be poured in the preheating template;
4. then glass was annealed 2 hours down at 350 ℃, furnace cooling can obtain containing the Fluorozirconate glass sample of plumbous oxide to room temperature then.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013101886320A CN103241949A (en) | 2013-05-21 | 2013-05-21 | Lead oxide containing fluoroziconate glass and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013101886320A CN103241949A (en) | 2013-05-21 | 2013-05-21 | Lead oxide containing fluoroziconate glass and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN103241949A true CN103241949A (en) | 2013-08-14 |
Family
ID=48921860
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013101886320A Pending CN103241949A (en) | 2013-05-21 | 2013-05-21 | Lead oxide containing fluoroziconate glass and preparation method thereof |
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| Country | Link |
|---|---|
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1105002A (en) * | 1993-08-12 | 1995-07-12 | 武汉大学 | Preparing fluozirconate glass by homogeneous coprecipitation method |
| US6352949B1 (en) * | 1999-06-15 | 2002-03-05 | Peter Willems | Fluoro glass ceramic showing photostimulable properties |
| CN1673141A (en) * | 2005-03-02 | 2005-09-28 | 中国科学院上海光学精密机械研究所 | Fluorozirconate glass containing tellurium dioxide |
-
2013
- 2013-05-21 CN CN2013101886320A patent/CN103241949A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1105002A (en) * | 1993-08-12 | 1995-07-12 | 武汉大学 | Preparing fluozirconate glass by homogeneous coprecipitation method |
| US6352949B1 (en) * | 1999-06-15 | 2002-03-05 | Peter Willems | Fluoro glass ceramic showing photostimulable properties |
| CN1673141A (en) * | 2005-03-02 | 2005-09-28 | 中国科学院上海光学精密机械研究所 | Fluorozirconate glass containing tellurium dioxide |
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Application publication date: 20130814 |