CN104860534A - Phosphate-silicate laser neodymium glass with thermal shock resistance, and preparation method thereof - Google Patents

Abstract

The invention discloses phosphate-silicate laser neodymium glass with thermal shock resistance, and a preparation method thereof. The glass is composed of 40-56mol% of P2O5, 8-22mol% of SiO2, 15-20mol% of Al2O3, 10-15mol% of MgO, 10-15mol% of Li2O, 0.2-3mol% of Nd2O3, and 0-0.3mol% of Sb2O3. The phosphate-silicate laser neodymium glass has relatively low thermal expansion coefficient, relatively high fracture toughness and relatively high thermal conductivity. The glass can withstand higher thermal shock and is prevented from being damaged. The glass also has a moderate stimulated emission cross section and a relatively long fluorescence lifetime, thus is widely applied as a gain medium in a repetition-frequency large-energy laser system.

Description

Silicophosphate laser neodymium glass of a kind of heat shock resistance and preparation method thereof

Technical field

The invention belongs to laser glass preparation field, silicophosphate laser neodymium glass being specifically related to a kind of heat shock resistance and preparation method thereof, this glass has lower thermal expansivity, larger fracture toughness property and higher thermal conductivity, there is moderate stimulated emission cross section and higher fluorescence lifetime simultaneously, can be used for repetition intensity laser system.

Technical background

Phosphate laser glass has the advantages such as the moderate and spectrum property of phonon energy is good, be widely used in current macro-energy both domestic and external, high-peak power laser device, but the thermomechanical property of existing phosphate laser glass is poor, be difficult to bear stronger thermal shocking, limit its application in repetition intensity laser system, so the phosphate laser glass finding thermomechanical property superior is of crucial importance.And the quality factor of the thermomechanical property of glass is as follows:

$\mathrm{FOM}=\frac{\mathrm{SK}(1-v)}{\mathrm{\αE}}$

Wherein S is fracture toughness property, and K is thermal conductivity, and ν is Poisson's ratio, and α is thermal expansivity, and E is Young's modulus.Obviously, the phosphate laser glass of heat shock resistance, should have lower thermal expansivity, larger fracture toughness property and higher thermal conductivity.

The widely used phosphate laser neodymium glass for repetition intensity laser system has certain resistance to sudden heating both at home and abroad at present, as the APG-1 glass of German Schott AG, its thermal expansivity, fracture toughness property, thermal conductivity and stimulated emission cross section are 99.6 × 10 respectively ^-7/ K (20-300 DEG C), 0.60MPa*m ^1/2, 0.83W/mK (90 DEG C) and 3.4 × 10 ^-20cm ².But these glass still cannot meet growing repetition intensity laser system to the requirement of neodymium glass thermomechanical property, so the thermomechanical property improving neodymium glass is further very important.

The advantage of silicate glass is that its thermomechanical property is good, and chemical stability is high, but its spectral quality is poor.And phosphate glass has outstanding spectral quality, but not as silicate glass in thermomechanical property.Basic thought of the present invention adds SiO in phosphate system ₂, obtain thermomechanical property excellence and the object of the good silicophosphate laser neodymium glass of spectral quality to reach.

This patent passes through at phosphoric acid salt P ₂o ₅-Al ₂o ₃-Li ₂the SiO of proper content is introduced in O-MgO system ₂, regulate glass ingredient and improve preparation technology, provide the good and silicophosphate laser neodymium glass that spectral quality is moderate of a kind of thermomechanical property.

Summary of the invention

Silicophosphate laser neodymium glass that the invention provides a kind of heat shock resistance and preparation method thereof, this glass has good thermomechanical property, as lower thermal expansivity, larger fracture toughness property and higher thermal conductivity etc., can be used as the gain media in repetition intensity laser system.

The present invention is at phosphoric acid salt P ₂o ₅-Al ₂o ₃-Li ₂in O-MgO system, introduce the SiO of proper content ₂(8-22mol%), regulate glass ingredient and improve preparation technology, the thermal expansivity that reduce further glass, the fracture toughness property increasing glass, improve the thermal conductivity of glass, thus improve the thermal shock resistance of glass.

Concrete technical solution of the present invention is as follows:

A silicophosphate laser neodymium glass for heat shock resistance, the component of its molar percentage is:

Composition mol%

P ₂O ₅40-56

SiO ₂8-22

Al ₂O ₃15-20

MgO 10-15

Li ₂O 10-15

Nd ₂O ₃0.2-3

Sb ₂O ₃0-0.3

The preparation method of above-mentioned silicophosphate laser neodymium glass, comprises the following steps:

(1) take raw material according to the above ratio, Homogeneous phase mixing, form compound;

(2) described compound is joined in quartz crucible, crucible is placed in 1350-1500 DEG C of silicon carbide smelting furnace and founds 2-3 hour, obtain glass metal;

(3) add a cover on described quartz crucible, in glass metal, pass into oxygen, dewater 50-80 minute;

(4), after stopping ventilation, at 1300-1450 DEG C, in oxygen atmosphere, 2-3 hour is clarified to glass metal;

(5) glass metal was down to 1200-1350 DEG C in 15 minutes, mechanical stirring 8-10 hour in oxygen atmosphere;

(6) glass metal was down to 1100-1250 DEG C in 15 minutes, glass metal is poured into the upper sizing of iron plate of preheating, after sizing in the rapid retort furnace proceeded at 540-580 DEG C, is incubated after 2-3 hour, be cooled to room temperature with the speed of 10-20 DEG C/h, obtain neodymium glass.

Compared with prior art, the invention has the beneficial effects as follows:

(1) SiO in existing Nd-doped phosphate glass ₂content be less than 8mol%, the present invention is at phosphoric acid salt P ₂o ₅-Al ₂o ₃-Li ₂in O-MgO system, by adding the SiO of high level ₂improve the thermomechanical property of glass, SiO ₂content up to 8-22mol%, and Al ₂o ₃content up to 15-20mol%.

(2) thermal expansivity of the silicophosphate laser neodymium glass of heat shock resistance of the present invention is in 6.9-7.9 × 10 ^-6between/K, fracture toughness property is at 0.90-1.20MPa*m ^1/2between, thermal conductivity is between 0.8-1.1W/mK, and its thermal shock resistance reaches more than 2.1 times of APG-1, and stimulated emission cross section is moderate simultaneously, remains on 2.9-3.5 × 10 ^-20cm ²in scope, fluorescence lifetime remains within the scope of 380-450 μ s.Therefore, this glass can meet the needs to the higher repetition intensity laser system of thermal shock resistance requirement.

Accompanying drawing explanation

Fig. 1 is the fluorescence spectrum figure of silicophosphate laser neodymium glass within the scope of 850-1450nm of heat shock resistance in the embodiment of the present invention 3, thickness of sample 5mm.

Fig. 2 is the abosrption spectrogram of silicophosphate laser neodymium glass within the scope of 300-1000nm of heat shock resistance in the embodiment of the present invention 3, and thickness of sample is 3mm.

Fig. 3 is the thermal dilatometry figure of the silicophosphate laser neodymium glass of heat shock resistance in the embodiment of the present invention 3.

Fig. 4 is the fluorescence lifetime figure of the silicophosphate laser neodymium glass of heat shock resistance in the embodiment of the present invention 3, thickness of sample 5mm.

Embodiment

Below in conjunction with embodiment, the invention will be further elaborated.Table 1 lists the molar percentage composition of silicophosphate laser neodymium glass 8 embodiments of heat shock resistance of the present invention.

The composition (mol%) of the silicophosphate neodymium glass embodiment 1-8 of table 1 heat shock resistance

The preparation method of embodiment 1-8 is as follows:

(1) take raw material, Homogeneous phase mixing according to the molar percentage of embodiment 1-8 component in table 1, form compound;

(2) described compound is joined in quartz crucible, crucible is placed in 1350-1500 DEG C of silicon carbide smelting furnace and founds 2-3 hour;

(3) add a cover on described quartz crucible, in glass metal, pass into oxygen, dewater 50-80 minute;

(4), after stopping ventilation, at 1300-1450 DEG C, in oxygen atmosphere, 2-3 hour is clarified to glass metal;

(5) glass metal was down to 1200-1350 DEG C in 15 minutes, mechanical stirring 8-10 hour in oxygen atmosphere;

(6) glass metal was down to 1100-1250 DEG C in 15 minutes, glass metal is poured into the upper sizing of iron plate of preheating, after sizing in the rapid retort furnace proceeded at 540-580 DEG C, is incubated after 2-3 hour, be cooled to room temperature with the speed of 10-20 DEG C/h, obtain neodymium glass.

Test the glass of embodiment 3, its result is as follows:

Performance	Embodiment 3	APG-1
			Thermalexpansioncoefficientα (10 -7/K)(20-300℃)	76.1	99.6
Thermal conductivity K (W/mK) (90 DEG C)	0.97	0.83
			Elastic modulus E (GPa)	81	71
Fracture toughness property S (MPa*m 1/2)	1.13	0.60
			Resistance to sudden heating R s(W/m 1/2)	1.35	0.54
Hardness H (GPa)	5.09	3.09
			Fluorescence life τ (μ s)	392	361
Stimulated emission cross section σ em(10 -20cm 2)	3.1	3.4

Can find out, the thermal shock resistance of silicophosphate laser neodymium glass of the present invention is better than APG-1, can be applicable to the repetition intensity laser system higher to thermal shock resistance requirement.

In Fig. 1, fluorescence spectrum figure is obtained by the measurement of FLS920 type time resolved spectroscopy instrument, and use xenon lamp as excitaton source, excitation wavelength is 811nm.In Fig. 2, absorption spectrum is recorded by Perkin-Elmer900UV/VIS/NIR type spectrophotometer, and test wavelength scope is 300-1000nm.In Fig. 3, thermal dilatometry is recorded by the Dilatometer402PC type dilatometer of German NETZSCH company, and temperature rise rate is 5 DEG C/min.In Fig. 4, fluorescence lifetime figure is obtained by the measurement of FLS920 type time resolved spectroscopy instrument.

Claims (2)

1. a silicophosphate laser neodymium glass for heat shock resistance, is characterized in that the molar percentage of this glass is composed as follows:

2. the preparation method of the silicophosphate laser neodymium glass of heat shock resistance according to claim 1, it is characterized in that, the method comprises the following steps:

(1) take raw material in ratio according to claim 1, Homogeneous phase mixing, form compound;

(2) described compound is joined in quartz crucible, crucible is placed in 1350-1500 DEG C of silicon carbide smelting furnace and founds 2-3 hour, obtain glass metal;

(3) add a cover on described quartz crucible, in glass metal, pass into oxygen, dewater 50-80 minute;

(4), after stopping ventilation, at 1300-1450 DEG C, in oxygen atmosphere, 2-3 hour is clarified to glass metal;

(5) glass metal was down to 1200-1350 DEG C in 15 minutes, mechanical stirring 8-10 hour in oxygen atmosphere;

(6) glass metal was down to 1100-1250 DEG C in 15 minutes, glass metal is poured into the upper sizing of iron plate of preheating, after sizing in the rapid retort furnace proceeded at 540-580 DEG C, is incubated after 2-3 hour, be cooled to room temperature with the speed of 10-20 DEG C/h, obtain neodymium glass.