CN102173584A - Phosphate glass containing 5% to 20% of aluminum oxide and 2% to 15% of yttrium oxide - Google Patents

Abstract

The invention discloses phosphate glass containing 5% to 20% of aluminum oxide and 2% to 15% of yttrium oxide and belongs to the technical field of optical functional materials. In the prior art, the phosphate glass has a large thermal expansion coefficient which is the major influencing factor on the thermal stability of phosphate glass. The phosphate glass provided by the invention contains the following components in percentage by weight: 60 to 80% of P2O5, 5 to 20 % of Al2O3, 2 to 15 % of Y2O3, 2 to 18 % of MgO, 10 to 25 % of F2, and 0.3 to 0.6% of Sb2O3. The thermal expansion coefficient (alpha) of the phosphate glass is less than 50*10-7/DEG C. One or more the following rare earth oxides are added: Pr2O3, Nd2O3, Eu2O3, Dy2O3, Ho2O3, Er2O3, Tm2O3 and Yb2O3, to prepare phosphate laser glass.

Description

The phosphate glass that contains 5～20% aluminum oxide, 2～15% yttrium oxide

Technical field

The present invention relates to a kind of phosphate glass that contains 5～20% aluminum oxide, 2～15% yttrium oxide, have the characteristics of ultra low heat expansion coefficient, high hydrolytic resistance, high thermal stability.Add rare earth oxide Pr ₂O ₃, Nd ₂O ₃, Eu ₂O ₃, Dy ₂O ₃, Ho ₂O ₃, Er ₂O ₃, Tm ₂O ₃, Yb ₂O ₃In one or several, obtain phosphate laser glass.Belong to the optical functional materials technical field.

Background technology

Mixing rare earth ion in glass is a kind of approach of preparation laserable material.

Though silicate glass has good thermostability and chemical stability, because its lower rear-earth-doped concentration and narrower gain bandwidth make it can not satisfy the needs of wide-band tuning superpower laser and amplifier.

Though fluoride glass has lower phonon energy, higher rear-earth-doped concentration, the gain bandwidth and the spectral range of broad,, its chemical stability is relatively poor, and very easily crystallization has limited its range of application.

And phosphate glass has the characteristics of high chemical stability, low-heat spectrum number, high rear-earth-doped concentration, and, glass ingredient is adjustable in a big way, prepare large size easily and have the glass devices of high homogeneity, price is relatively cheap, is suitable as very much the doping with rare-earth ions laser host material.Prepared laserable material stimulated emission cross section is big, gain factor and quantum yield height, output rating height, fluorescence lifetime are long, becomes the desirable laserable material of superpower laser and economical laser fusion laser apparatus.Mix Yb ³⁺, mix Yb altogether ³⁺/ Er ³⁺Phosphate laser glass energy storage efficiency height, fluorescence lifetime long, have and InGaAs diode pumped wavelength (900～1000nm) effective coupled advantages.

Existing phosphate glass thermal expansivity is big, and thermal expansivity is greatly the principal element that influences the phosphate glass thermostability.Phosphate laser glass LHG-7 thermal expansivity as Japanese Bao Gu is 102 * 10 ^-7/ ℃, the LHG-8 thermal expansivity is 112 * 10 ^-7/ ℃, the LHG-10 thermal expansivity is 145 * 10 ^-7/ ℃, Chinese N24 phosphate laser glass thermal expansivity is 156 * 10 ^-7/ ℃, U.S. KTCC7 phosphate laser glass thermal expansivity is 105 * 10 ^-7/ ℃, German Xiao Te LG630 phosphate laser glass thermal expansivity is 97 * 10 ^-7/ ℃.

Summary of the invention

In order to overcome the existing big deficiency of phosphate glass thermal expansivity, the invention provides a kind of phosphate glass that contains 5～20% aluminum oxide, 2～15% yttrium oxide, this phosphate glass has the ultra low heat expansion coefficient, thereby have good thermostability, more be suitable as the doping with rare-earth ions laser host material.

The component and the weight percentage of the present invention's the phosphate glass that contains 5～20% aluminum oxide, 2～15% yttrium oxide are as follows:

P ₂O ₅?60～80％；Al ₂O ₃?5～20％；Y ₂O ₃?2～15％；MgO?2～18％；F ₂?10～25％；Sb ₂O ₃?0.3～0.6％。

The selected reason of component, the qualification reason of each component concentration are as follows:

P ₂O ₅Be that glass network generates body, weight percentage at least 60%, otherwise the easy crystallization of phosphate glass are higher than 80% phosphate glass chemical stability variation.

Al ₂O ₃Effect be to improve the chemical stability of phosphate glass, reduce thermal expansivity and chromatic dispersion simultaneously, improve processability.Weight percentage is lower than 5%, and the effect that reduces thermal expansivity is not obvious, and weight percentage can make the glass metal viscosity increase greater than 20%, infusibility and difficult bubble, the striped of eliminating in the glass.

Y ₂O ₃Effect be to reduce the phosphate glass thermal expansivity, improve chemical stability.Y ₂O ₃Weight percentage can make temperature of fusion raise greater than 15%.

The effect of MgO is to reduce the temperature of fusion of phosphate glass, improves processability.

F ₂Effect be that fluorion has identical proton number with the OH group, OH group generation chemical reaction in fluorine and the glass:

MF+OH→M-O+HF↑

Help eliminating the OH group in the phosphate glass.

Sb ₂O ₃As finings, eliminate the glass metal bubble.

Described phosphate glass thermalexpansioncoefficient is less than 50 * 10 ^-7/ ℃, specific refractory power is less than 1.55, and softening temperature is greater than 590 ℃, and transition temperature is greater than 560 ℃.Add rare earth oxide Pr ₂O ₃, Nd ₂O ₃, Eu ₂O ₃, Dy ₂O ₃, Ho ₂O ₃, Er ₂O ₃, Tm ₂O ₃, Yb ₂O ₃In one or several, the preparation phosphate laser glass.

Embodiment

P ₂O ₅60～80%, preferred 65～70%;

Al ₂O ₃5～20%, preferred 10～15%;

Y ₂O ₃2～15%, preferred 6～9%, add and Y ₂O ₃Similar substance La ₂O ₃0～8% or/and Nb ₂O ₅0～8%, La ₂O ₃Preferred 0～6%, Nb ₂O ₅Preferred 0～6%, La ₂O ₃, Nb ₂O ₅Effect and Y ₂O ₃Identical;

MgO 2～18%, and interpolation and MgO similar substance BaO 0～10% are or/and K ₂O 0～12%, BaO, K ₂The effect of O is identical with MgO;

F ₂?10～25％；

Sb ₂O ₃0.3～0.6%, add and Sb ₂O ₃Similar goods and materials CeO ₂0～1%, CeO ₂With Sb ₂O ₃Identical;

Add Cr ₂O ₃0～0.5%, as sensitizing agent.

Adopt common opticglass manufacture method can make the present invention's phosphate glass.By each component raw material oxide compound of glass ingredient weight percentage weighing, nitrate, carbonate, fluorochemical, mix, put into platinum crucible, in the globars electric furnace, found, 1440～1480 ℃ of temperature, 2～6 hours time, stirring, clarification, homogenizing cool to 1400 ℃, be poured in the cast iron mould of 550～620 ℃ of preheatings, be incubated 3 hours, reduce to room temperature with 5～8 ℃/hour speed then, promptly obtain the phosphate glass finished product.

The present invention's phosphate glass specific embodiment and performance see following table for details:

Claims (6)

1. phosphate glass that contains 5～20% aluminum oxide, 2～15% yttrium oxide is characterized in that its component and weight percentage are as follows:

P ₂O ₅?60～80％；Al ₂O ₃?5～20％；Y ₂O ₃?2～15％；MgO?2～18％；F ₂?10～25％；Sb ₂O ₃?0.3～0.6％。

2. phosphate glass according to claim 1 is characterized in that P ₂O ₅Preferred 65～70%; Al ₂O ₃Preferred 10～15%; Y ₂O ₃Preferred 6～9%.

3. phosphate glass according to claim 1 is characterized in that, adds and Y ₂O ₃Similar substance La ₂O ₃0～8% or/and Nb ₂O ₅0～8%, La ₂O ₃Preferred 0～6%, Nb ₂O ₅Preferred 0～6%.

4. phosphate glass according to claim 1 is characterized in that, interpolation and MgO similar substance BaO 0～10% are or/and K ₂O 0～12%.

5. phosphate glass according to claim 1 is characterized in that, adds and Sb ₂O ₃Similar goods and materials CeO ₂0～1%.

6. phosphate glass according to claim 1 is characterized in that, adds Cr ₂O ₃0～0.5%.