WO1994008373A1 - Phosphate glass useful in high energy lasers - Google Patents

Abstract

In a high energy laser system utilizing phosphate laser glass components to amplify the laser beam, the laser system requires a generated laser beam having an emission bandwidth of less than 26 nm and the laser glass components consist essentially of (on an oxide composition basis and in mole %): P2O5 50-75, Al2O3 > 0-10.

Description

PHOSPHATE GLASS USEFUL IN HIGH ENERGY LASERS

Summary of the Invention

This invention relates to a high energy laser system and a method of generating a laser beam using phosphate laser glasses, typically neodymium-doped, which possess an advantageous combination of property qualities desirable from both laser application and manufacturability points of view. The invention also relates to phosphate laser glasses suitable for use in high energy laser systems.

The term "laser" refers to the amplification of light by the stimulated emission of radiation. In a laser, an active material, for example, a glass suitably doped with an active atomic species such as neodymium, is placed in a cavity resonator formed by two reflecting, or at least partially reflecting, mirrors.

The glasses utilized in the invention offer a combination of properties which are desirable for application in high energy lasers such as high cross section for stimulated emission, low concentration quenching of the excited state lifetime, low nonlinear refractive index, small emission bandwidth, high heat capacity, and low co-efficient of thermal expansion. The latter-two properties are particularly desirable for applying glasses of this invention as a cladding material. In accordance with the invention, solid state lasers used for the generation of high levels of total energy per pulse require that the active material possess a maximum value of the following laser figure-of-merit,, FOM_laser, expressed by

where

α is the thermal expansion;

ρ is the glass density;

C_p is the glass heat capacity;

σ is the cross section for stimulated emission;

Q is a measure of lifetime concentration quenching of the excited state;

n₂ is the nonlinear refractive index;

Δλ_abs is the average absorption bandwidth; and

Δλ_em is the emission bandwidth.

It should be noted that this laser figure-of-merit has been developed in accordance with the invention to provide guidance in selecting glasses for use in high energy laser systems. It is not intended to provide an exact and precise assessment of each glass. Still, the importance of this laser figure-of-merit can be seen from the following discussion.

Laser glasses for application in high energy laser systems preferably have a higher level of cross section for stimulated emission compared to current state-of-the-art laser glasses. Although a large cross section implies a high extraction of stored energy as amplified laser light, a low cross section is known to imply better energy storage ability. The optimum cross section for any particular laser system design thus varies; however, current state-of-the-art high energy laser system designs call for a cross section greater than 3.5 × 10^-20 cm². This is considered to be a high cross section in comparison to the range of cross sections typically observed in phosphate laser glasses.

The cross section for stimulated emission, σ , is a particularly important parameter in large fusion laser systems based on Nd-doped glass since larger cross sections are associated with higher extraction efficiencies which are expected to lead to lower overall system costs.

It is desirable in high energy laser systems that the active material have a high value for the concentration quenching factor, Q, which describes the well-known phenomena of nonradiative depletion of the excited laser state by adjacent neodymium ions in the active glass. Using the concentration quenching factor, the emission lifetime quenching curve can be described by:

where T₀ is the lifetime for a sample containing nearly no neodymium, N is the neodymium doping level in the glass, and Q is a numerical factor expressed in cm^-3 which best fits experimental data collected on a number of samples of different neodymium concentration. See, e.g., "Spectroscopic Properties of Nd⁺³ Dopant Ions in Phosphate Laser Glasses," Payne et al., Lawrence Livermore National Laboratory, UCRL-JC-105473, May 1991.

The value of nonlinear refractive index, n₂, is preferably low since this factor is directly correlated to internal damage of optical components including laser glass by the self focusing of a propagating laser beam. It arises from the change in the refractive index of the glass induced at high intensity, e.g., n = n₀ + n₂ ɸ where n is the refractive index, n₀ is the refractive index in the absence of a propagating laser beam and ɸ is an indication of the intensity of the propagating laser beam. Additionally, low nonlinearity in the refractive index de- pendent on laser intensity implies reduced distortion of beam quality as the beam propagates through laser glass components being used to amplify the laser beam.

In state-of-the-art high energy laser system designs, a variant of the glass composition employed as the active laser medium but doped with an ion or ions which absorb strongly in the region of laser activity, e.g., Cu, is attached with adhesives to the edges of slabs or discs fabricated from the active laser glass. During and after excitation of the laser glass there is considerable heating of this bordering or cladding material relative to the active laser material it surrounds. This uneven heating leads to optical distortion of the complete laser glass/cladding glass element due to the uneven heating and expansion of the two glasses. Maximizing the quantity of

minimizes the amount of optical distortion which results for a given temperature increase of the cladding glass relative to the active laser glass it surrounds.

It is also desirable to maximize the absorption bandwidth for the active species in the glass in order to maximize the absorption of flashlamp light and increase the pumping efficiency into the excited state of the laser transition. Since only a fraction (e.g., about 20%) of the total light emitted from flashlamps is actually absorbed by the laser glass, materials characterized by greater average absorption bandwidth, Δλ_abs, will lead to a greater fraction of the flashlamp light being absorbed.

Furthermore, it is desirable to minimize the emission bandwidth for the excited species in the glass to maximize the extractable energy stored in the excited stage. Measurements performed at Lawrence Livermore National Laboratory suggest that Nd-doped laser glasses with smaller bandwidths, Δλ_em, are characterized by higher extraction efficiencies. As fusion laser technology advances, the need exists for Nd-doped glass that can be used in laser systems that will likely produce more than five or even ten times as much output energy as the current state-of-the-art fusion laser systems (i.e., ≥ 0.5 or 1.0 megajoules (MJ) versus 0.1 MJ at a wavelength of 355 mm from the NOVA laser at Lawrence Livermore National Laboratory).

New high energy laser systems require large quantities of active laser glass (e.g., at least about 200, 300, 500, 1000, 2000, 3000, or 4000 optical glass components each of, for example, at least about 10 l in volume) which preferably can be produced in a short time period with high manufacturing yield, thereby minimizing the cost of the material to the end user. Solid state laser materials for these high energy laser systems should also preferably offer, in combination with good laser properties as discussed above, outstanding properties from the point of view of manufacturability. Thus, the glasses utilized in the present invention, simultaneously with offering good characteristics for laser application, also preferably possess desirable characteristics related to manufacturability such as high thermal conductivity, low Poisson's ratio, small coefficient of thermal expansion, low Young's modulus, high fracture toughness, a low glass transformation point, good water resistance of the glass surface, high solubility for platinum, and high stability by being resistant to devitrification and crystallization during melting and forming.

Therefore, it is desirable that, in accordance with the invention, the glasses exhibit a maximum value of the following production figure-of-merit, FOM_prod, expressed by

where

K is thermal conductivity;

v is Poisson's Ratio;

α is thermal expansion;

E is Young's modulus;

K_1c is fracture toughness;

T_g is glass transformation point;

F_wdur is durability of the glass to water;

F_Dvit is the crystallization and devitrification tendency of the glass; and

D_Pt is a measure of the ability of the glass to dissolve platinum.

It should be noted that this production figure-of-merit has been developed in accordance with the invention to serve as a guide in the selection of laser glasses. It is not intended to suggest an exact precise assessment of each glass. This production figure-of-merit in accordance with the invention is, however, important as can be seen from the following discussion.

The production figure-of-merit, FOM_prod, described above includes a term β where

and K is thermal conductivity, v is Poisson's Ratio, α is the thermal expansion, and E is Young's modulus. This is a well known thermal-mechanical figure-of-merit which is an indication of the likelihood that glass will break while incurring thermal and mechanical stresses associated with the manufacturing steps of annealing, grinding, polishing, cutting, routine handling, etc. This term appears twice in the expression for FOM_prod, once to reflect its importance in annealing of glass, and once with K_1c, the fracture toughness of the glass, as a reflection of its importance as a thermal shock figure-of-merit in the important manufacturing steps of fabricating, e.g., polishing, cutting, handling, etc., a final block, slab, disc, rod, etc. The FOM_prod expression also includes 1/T_g to reflect the reduced time and effort needed to fully anneal large castings of glass which have a small transformation temperature.

Also included in FOM_prod are the important measures of platinum solubility, D_pt, and devitrification tendency,

D_pt is evaluated by submerging a section of platinum into a molten glass melt, e.g., at temperatures of 1300°C to 1400°C depending on the viscosity of each glass under evaluation for 4 hours with the melt under an oxygen atmosphere. Platinum dissolution into the glass melt is evidenced by a yellow coloration of the samples, corresponding to absorption of the glass in the blue part of the spectrum. The resultant ability to dissolve platinum is evaluated by measuring the absorption coefficient of glass samples at 400 nm. See, e.g., "Platinum Solubility in Phosphate Laser Glass," Hayden et al., Lawrence Livermore National Laboratory, UCRL-JC-105475, June 1991.

During the development of this invention, F_Dvit was not precisely quantitatively evaluated. Instead, glasses were accepted or rejected (that is to say, F_Dvit was set equal to 1 or 0, respectively) based on microscopic visual inspection of a platinum strip containing samples of the glass under evaluation which had been placed in a gradient furnace covering, temperatures from 600°C to 1000°C, for a time sufficient so that any tendency toward devitrification or crystallization was evident upon removal of the strip from the furnace. It is also possible to identify glasses with a severe devitrification tendency by Differential Thermal Analysis (DTA) which detects and displays exothermic or endothermic reactions within a small sample of the glass under evaluation. See, e.g., "ThermalMechanical and Physical Chemical Phosphate Laser Glasses," Elder et al., Lawrence Livermore National Laboratory, UCRL-JC-105474, July 1991. A glass which is more aggressive to platinum is easier to produce in a form free of metallic platinum particles which, upon absorption of laser radiation, become damage sites within the final glass element, potentially rendering the material useless as a high quality optical element. In a similar manner, a stable glass which is not prone to devitrification during manufacturing is easier to produce in a form free of crystals and free of phase separation, which is important for production of glasses with the high optical quality essential for laser glass used in high energy laser systems.

Also appearing in FOM_prod is a measure of glass durability toward attack by water, F_wdur. This parameter is evaluated by submerging a sample of the glass to be tested in 50°C water for 24 hours, measuring the weight loss, and normalizing the result per square centimeter of tested area. The weight loss per square centimeter of tested area is referred to as D_wdur. See, e.g., Elder et al., supra .

Potentially, a somewhat higher solubility in water is an advantage during the glass polishing; however, it is desirable that F_wdur not be so large that the glass is readily attacked by sources of water such as humidity to which surfaces might be exposed during storage or actual use. Consistent with this, glasses with values of D_wdur

> 0.3 mg/cm²/day were rejected; that is, the value of F _Wdur was set equal to 0.

It is known for some time that phosphate laser glasses have a low threshold value for the laser effect, and phosphate glass compositions have been commercially available for some time as optical components for use in laser systems.

Nevertheless, a need has remained for improved development of phosphate compositions, e.g., to simultaneously improve both the thermal-mechanical properties and the laser properties of phosphate laser glasses, thus making available glasses which combine in the same material prop erties desirable both for manuf acturability with a high production yield and for application as an active laser material.

Prior art phosphate laser glasses contain a wide variety of components including, for example, Al₂O₃, SiO₂, alkali metal oxides (Na₂O, K₂O, Li₂O, especially), alkaline earth metal oxides, etc., in addition to the base component, P₂O₅. Prior art glasses having the good laser properties desirable high energy solid state laser systems are described in U.S. Patent Nos. 4,075,120; 4,248,732; and 4,239,645. However, the glasses of these inventions are thermomechanically somewhat undesirable from the manuf acturability point of view. These glasses do not emphasize the identity or the amount of alkali and alkaline earth metal oxides.

Other phosphate laser glasses place emphasis on the use of K₂O and BaO to impart pronounced athermal character to the laser glass. See, e.g., U.S. 4,022,707; U.S. 4,076,541; and U.S. 4,108,673. While other publications require the use of Li₂O, e.g., U.S. 4,929,387, and/or MgO, e.g., U.S. 5,032,315, to obtain glasses with exceptional properties for use in high average power laser systems. Still another publication, U.S. 4,333,848, emphasizes the use of Li₂O with BaO to achieve this athermal characteristic in a laser glass.

Still other laser glass publications exist which prescribe the necessary use of SiO₂, e.g., U.S. 4,820,662, DE 34 35 133, JP 51-107312, and DE 36 09 247, and/or B₂O₃, e.g., U.S. 4,661,284, to obtain improvements in the characteristics desirable in laser glasses for high power solid state laser systems.

Many other laser phosphate publications exist which describe a wide variety of glasses such as JP 49-114615(4), JP 60-191029(3) , JP 51-107311, JP 50-3411, JP 51-30812, SU-355,916, U.S. 3,846,142. In these patents, no particular emphasis is placed on alkali metal oxides. Further patents equate all metal oxides, e.g., U.S. 4,120,814, U.S. 3,979,322, U.S. 4,225,459, U.S. 3,580,859, and U.S. 4,470,922.

JP 54-38311 indicates a preference for Li₂O, but in phosphate glasses containing components such as CuO and V₂O₅.

It has now been discovered that the requirements for high energy laser systems can be satisfied through the employment of phosphate glasses having a desirable combination of laser properties and simultaneously having a desirable combination of properties for manufacturability.

The invention thus relates to a high energy laser system using a phosphate glass possessing desirable properties such as high cross section for stimulated emission, low emission bandwidth, low concentration quenching of the excited state lifetime, low nonlinear refractive index, high heat capacity and low coefficient of thermal expansion, in combination with desirable characteristics related to manufacturability such as high thermal conductivity, low Poisson's ratio, small coefficient of thermal expansion, low Young's modulus, high fracture toughness, a low glass transformation point, good water resistance of the glass surface, high solubility for platinum and high stability as shown by being resistant to devitrification and crystallization during melting and forming.

In accordance with one aspect, the invention relates to a high energy laser system utilizing phosphate laser glass components in which the parameters of the laser system and the beam generated thereby require that the phosphate laser glass components have an emission bandwidth of less than about 26 nm, and wherein the glass consists essentially of (on an oxide composition basis):

Mole%

Especially

General Preferred Preferred

P₂O₅ 50-75 55-75 60-70 Al₂O₅ >0-10 1-9 2-6 K₂O >0-30 8-28 10-24 MgO 0-30 0-24 0-20 CaO 0-30 0-24 0-20

Li₂O 0-20 0-15 0-10

Na₂O 0-20 0-15 0-10

Rb₂O 0-20 0-15 0-10

Cs₂O 0-20 0-15 0-10

BeO 0-20 0-15 0-10

SrO 0-20 0-15 0-10

BaO 0-20 0-15 0-10

ZnO 0-20 0-15 0-10

PbO 0-20 0-15 0-10

B₂O₃ 0-10 0-8 0-5

Y₂O₃ 0-10 0-8 0-5

La₂O₃ 0-8 0-5 0-4

Ln₂O₃ 0.1-8 0.1-8 0.1-8

Sum RO >0-30 4-24 5-20 (R = Mg, Ca)

Sum R' ₂c 1 0-20 0-15 0-10 (R' = Li, Na, Rb, Cs)

Sum R"O 0-20 0-15 0-10 (R" = Be, Sr, Ba, Zn, Pb)

SSuum R"'₂O₃ 0-10 0-8 0-5

(R"' = B, Y)

Ln₂0₃ represents the sum of the oxides of active lasing lanthanides of atomic number 58-71. The preferred active lasing species is Nd₂O₃. It is also possible to use non-lanthanide active lasing species (e.g., Ti or V) in place of Ln₂O₃.

In accordance with the invention, the laser system preferably can operate at an energy level of at least about 0.1 MJ, particularly at least 0.5 MJ, 1.0 MJ, 1.5 MJ, or 2.0 MJ, and especially up to at least 3.0 MJ, 4.0 MJ or 5.0 MJ (for example, about 0.2-10 nanosecond pulse lengths at an energy level of at least 0.5 MJ and a wavelength of 355 nm). In addition, the laser system can operate at lower energy levels such as at least about 10 kilojoules or at least about 1 kilojoule. Further, the laser system preferably focuses at least about 100 beams on a target and use at least 200 laser glass components. Laser systems operating at such energy levels require laser glass exhibiting high extraction efficiencies. For this reason, it has been determined that laser glass components having a low Δλ_em, preferably < about 26 nm, e.g., ≤ 26.1 nm, are needed. A high cross section, e.g., > 3.5 × 10^-20 cm², or > 3.7 × 10^-20 cm², is also advantageous. Also, a low glass transformation point, for example, ≤ 487°C or ≤ 470°C is desirable. High average absorption bandwidth, e.g., Δλ_abs > 16 nm, is also beneficial. Other beneficial properties are thermal expansion α (20-300°C) at less than 144 × 10^-7/K; thermal conductivity K of greater than 0.52 W/mK; and nonlinear refractive index n₂ of less than 1.15.

In other preferred aspects, the glass also has the following important properties:

Damaging inclusions per liter essentially zero

Stability to devitrification high

Stability to crystallization high

K , thermal conductivity > 0.5 W/mK v , Poisson's ratio < .28

ce, thermal expansion from 20-300°C < 145 × 10^-7/K

E, Young's modulus ≤ 50 GPa

K_1c, fracture toughness > 0.40 MPa m^1/2 ρ, glass density > 2.60 g/cm³ C_p, glass heat capacity > 0.50 J/gK σ, cross section > 3.5 × 10^-20 cm²

Q, concentration quenching factor > 7 × 10²⁰ cm^-3 n₂, nonlinear refractive index < 1.2 × 10^-13 esu

Δλ_abs > 16 nm

Δλ_em < 26 nm

T_g, glass transformation point < 460°C

D_wdur, durability of the glass to water < 0.20 mg/cm² day

D_Pt, platinum solubility (@ 400 nm) > 0.03 cm^-1

It is further preferred that these properties exceed even these goals, e.g.,

K, thermal conductivity > 0.55 W/mK α, thermal expansion from 20-300°C < 140 × 10^-7/K

E, Young's modulus < 45 GPa

K_1c, fracture toughness > 0.50 MPa m^1/2 σ, cross section > 4.0 × 10^-20 cm² Q, concentration quenching factor ≥ 8 × 10²⁰ cm^-3 n₂, nonlinear refractive index < 1.1 × 10^-13 esu

Brief Description of the Drawings

Various other objects, features and attendant advantages of the present invention will be more fully appreciated as the same becomes better understood when considered in conjunction with the following discussion and the accompanying drawings wherein:

Figures 1a, 1b and 1c show the values of FOM_laser', defined below, for the glass examples of Tables 1, 2, and 3, respectively;

Figures 2a, 2b and 2c show the values of FOM_prod', defined below, for the glass examples of Tables 1, 2, and 3, respectively;

Figures 3a, 3b and 3c show the values of FOM_laser', for the glass examples of Tables 4 and 5;

Figures 4a, 4b and 4c show the values of FOM_prod', for the glass examples of Tables 4 and 5;

Figures 5a, 5b, 5c and 5d show the values of FOM_prod', for the glass examples of Tables 6 and 7;

Figures 6a, 6b, 6c and 6d show the values of FOM_laser', for the glass examples of Tables 6 and 7; and

Figure 7 shows the values of D_wdur for some glass examples of Tables 6 and 7.

Detailed Description

Special emphasis in this invention is placed on those properties which appear in the following, abbreviated FOM formulae:

and

wherein the meaning of each is discussed above.

Also emphasized are the properties of emission bandwidth, platinum solubility, and devitrification tendency. Preferably, FOM_laser' is > 25 (esu·cm)^-1, FOM_prod' is > 0.60 × 10^-6 m²/sec, bandwidth for emission is < about 26 nm, D_Pt is > 0.025 cm^-1 at 400 nm, and the glass exhibits good stability as evaluated by visual inspection for the presence of crystallization, devitrification, phase separation, etc.

These glass compositions employ P₂O₅ as the principle glass former. The level of P₂O₅ is preferably maximized. Generally, the P₂O₅ content is 50-75, preferably 55-75, especially 60-70 mole%. The P₂O₅ content can also be defined in terms of 51, 52, 53, 54, 56, 57, 58, 59, 61, 62, 63, 64, 65, 66, 67, 68, 69, 71, etc., mole%.

Al₂O₃ is also an important component. It imparts to the glass better chemical durability and better thermomechanical properties such as K and α. However, the amount of Al₂O₃ should not be so high as to induce crystallization. The level of Al₂O₃ is generally > 0 to 10%, preferably 1-9% (e.g., 2-8.8%), especially 2-8 mole%, for example, 2-6 mole% or 2-7 mole%. Other levels of Al₂O₃ are 3, 4, 5 and 7 mole%.

Figures 1a, 1b and 1c show the results of FOM_laser, evaluations for glass compositions in Tables 1, 2 and 3. As can be seen in Figure la, high levels of P₂O₅ and minimal utilization of Al₂O₃ provide a high value of FOM_laser, due to a reduction in the value of n₂, while increasing Q and σ . Figure lb shows that a reduction in modifier content, in this case, K₂O and BaO, has a detrimental impact of FOM_laser, . Figure 1c indicates that a high level of P₂0₅, over modifier content, is preferred.

Figures 2a, 2b and 2c show the results of FQM_prod, evaluations for glass compositions in Tables 1, 2 and 3. Figure 2a shows that, in addition to high levels of P₂O₅, some level of Al₂O₃ increase still offers a slight improvement in FOM_prod'. Figure 2b and Figure 2c demonstrate the preference in these glasses for high P₂O₅ in order to increase the value of FOM_prod,.

The alkali metal content and identity are particularly important. In particular, the presence of potassium is important for meeting the parameters necessary for simultaneously raising the figures of merit for both laser application and manufacturability. Generally, the amount of K₂O is > 0 to 30%, preferably 8-28%, especially 10-24 mole%. The amount of K₂O can also be 1, 2, 3, 4, 5, 6, 7, 9, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 25, etc., mole%. See, e.g., Examples 102, 105-107, and 109-112.

Small additions of sodium are generally tolerable, e.g., less than about 3 to 5 mole% Na₂O. The amount acceptable will vary somewhat as a function of base glass composition. Low amounts of lithium are also acceptable in the glasses. In general, less than about, e.g., 3 to 5 mole% Li₂O, is consistent with producing a glass with the mentioned desirable characteristics for manufacturability and application in high energy laser systems. In general, the total amount of the alkali metal oxides Li₂O, Na₂O, Rb₂O and Cs₂O will be 0-20%, preferably 0-15%, especially 0-10 mole%, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16, etc., mol%. See, e.g., Examples 124, 126, and 129.

As can be seen in Figure 3a, Figure 3b and Figure 3c, incorporation of high molecular weight alkali metals provides a high value of FOM_laser', due to reduction in the value of n₂, simultaneously with increasing and marginally impacting the value of Q. On the other hand, low molecular weight alkali metal species impart to a glass desirable thermomechanical properties which lead to a high value for FOM_prod'. See Figure 4a, Figure 4b and Figure 4c.

The alkaline earth metal content and identity are also of particular importance. In particular, the presence of CaO and/or MgO is desirable for meeting the parameters necessary for simultaneously offering a high figure-of-merit for both laser application and manufacturability. Generally, the amount of MgO is 0-30 mole%, preferably 0-24 mole%, especially 0-20 mole%, e.g., 0-7 mole%. See, e.g., Examples 123-126 and 139-142. Similarly, the amount of CaO is generally 0-30%, preferably 0-24%, especially 0-20 mole%, e.g., 7-30 mole%. See, e.g., 131-136 and 138. The combined amount of MgO and CaO, however, is preferably > 0-30%, particularly 4-24%, especially 5-20%. Other possible amounts for either MgO or CaO are 1, 2, 3, 4, 5, 6,

8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, etc., mole%.

It is possible to have MgO or CaO present without the other. For example, the glass can contain > 0-30 mole%

MgO without any CaO, or > 0-30 mole% CaO without any MgO, such as 5-20 mole% CaO or 10-15 mole% CaO.

Barium, BaO, can also be present; the amount acceptable will vary somewhat as a function of base glass composition. In general, the amount of BaO is 0-20%, preferably 0-15%, especially 0-10 mole%, for example, about 3 to 5 mole% or less BaO is consistent with producing a glass with the mentioned desirable characteristics for manufacturability and application in laser systems for producing high energy levels.

As can be seen in Figures 3a, 3b, and 3c, incorporation of high molecular weight alkaline earth metals provides only a slightly higher value of FOM_laser', due to an increase in the value of n₂, combined with minimal impact on the value of Q and an increase in the value of σ. However, as demonstrated in Figures 4a, 4b, and 4c, low molecular weight alkali metal species also impart desirable thermomechanical properties to the glass leading to a higher value for FOM_prod' .

The addition of SiO₂ and B₂O₃ while not required can improve thermomechanical properties. The impact of SiO₂ and B₂O₃ substitutions for either P₂O₅ or Al₂O₃ are similar, as shown in Figures 5a-5d and Figures 6a-6d. Substitutions of SiO₂ and B₂O₃ for Al₂O₃ are advantages for laser properties. See, e.g., Figures 6a and 6c, which shows substitutions of SiO₂. Substitution of B₂O₃ for Al₂O₃ results in an increase in FOM_laser, due to a smaller value of n₂ and larger values for Q and σ . The inclusion of SiO₂ and B₂O₃ is, however, detrimental to durability of the glass to attack by water, as seen in Figure 7. Here, the increase in glass dissolution rate, expressed as mg of material lost per square centimeter of tested surface per day of exposure, is documented for partial, e.g., 50%, and complete replacement of Al₂O₃ by B₂O₃ and SiO₂.

With respect to BeO, SrO, BaO, ZnO and PbO, the amount of these metal oxides are each generally within the range 0-20%, preferably 0-15%, especially 0-10 mole%, with their total combined amount also being generally 0-20%, preferably 0-15%, especially 0-10 mole%.

The amounts of B₂O₃ and Y₂O₃ present are each generally 0-10%, preferably 0-8%, especially 0-5 mole%. Similarly, the total combined amount of B₂O₃ and Y₂O₃ is generally 0-10%, preferably 0-8%, especially 0-5 mole%.

As mentioned above, it is desirable for the glass to have a maximal P₂O₅ content and, in turn, to possess a high amount of P₂O₅ relative to modifiers. Therefore, the value of P₂O₅/(3∑R₂O₃ + MgO), wherein R is Al, La, Ln, Y and B, is preferably at least about 1.5, particularly at least about 2.0, and especially at least about 2.3.

When used as a lasing medium, the amount of a lasing species or lasing system (e.g., a lasing species/energy transfer species combination) present in the glass is effective for lasing, e.g., often 0.01-8 mole% in total. Optionally, higher amounts can be used, e.g., up to 10% or even up to 20% or higher in total.

Nd₂O₃, the most preferred lasing species, is added to the glasses in sufficient quantity to achieve the desired lasing activity, as is true for other lasing species and systems. At excessively high concentration levels (Nd₂O₃ or other lasing species), quenching of the fluorescence emission will occur. As a result, there is a corresponding drop in fluorescence lifetime of the excited state involved in the lasing transition. Suitable upper limits in a given case can be routinely determined. For example, the glass can contain 0.01, 0.05, 0.08, 0.1, 0.3, 0.5, 0.8, 1.0, 1.3, 1.5, 1.8, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0 mole%, etc.

Any conventional glass lasing species, lanthanide or nonlanthanide, can be used, e.g., Nd, Tm, Yb, Dy, Pm, Tb, Er, Ho, Ti, V, Cr, Eu, Sm, etc. In another embodiment of the present invention, the laser compositions can contain suitable co-dopants along with primary lasing ions. These include transition metals such as chromium and vanadium or lanthanide ions such as thulium and erbium. These have broad and intense absorption bands and resultant co-dopant fluorescence bands which overlap with the primary lasing ion absorption levels. This phenomena leads to a more efficient conversion of pump radiation into the excited state population of lasing ions.

The total amount of these active ions alone or in combination is 0.01-8 mole%, typically. However, as noted above, higher amounts can be used where appropriate, e.g., 7, 8, 9, 10, 11, 12, 13, 14, 15, 17, 25 mole%, etc. See, for example, Physics of Laser Fusion, Volume IV, "The Future Development of High-Power Solid State Laser Systems," Emmett et al., Lawrence Livermore National Laboratory, UCRL-53344, November 1982.

Addition of La₂O₃ allows direct substitution of Nd₂O₃ or other lasing or energy transfer lanthanide species by another oxide which is nearly an exact structural replacement of, e.g., Nd₂O₃. This allows the manufactured glass to be produced with a broad range of neodymium or other lasing species doping levels while minimizing the change from this adjustment on the physical, optical, and thermal properties of the produced glasses. Thus, La₂O₃ amounts typically are 0-8 mole%, preferably 0-5 mole%, especially 0-4 mole%, for example, 0.1, 0.2, 0.3, 0.5, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.5, 2.8, 3.0 mole%, etc.. However, higher contents are possible, e.g., up to 10% or even 20%, as a replacement for the lanthanide lasing species.

It is further possible to add small amounts, e.g., 0.1-0.3 wt.%, of conventional refining agents such as As₂O₃ and Sb₂O₃ to the composition to aid in manufacturing while not compromising the combination of properties achieved in the present invention. It is additionally possible to add small antisolarization effective amounts, e.g., 0.1-1.5 wt.%, of conventional antisolarants such as TiO₂, CeO₂ and Nb₂O₅ (as well as others, e.g., SiO₂ and Sb₂O₂) to suppress solarization of these glasses during exposure to intense UV radiation common during application as an active lasing material.

It is also possible to omit a lasing species entirely within the glass, e.g., when it is desired to use the glass in other applications (such as in optical elements, e.g., lenses, mirrors, undoped laser fiber cladding glasses, analogous to the cladding glasses of U.S. 4,217,382, etc.), where their exceptional combination of properties is beneficial. For example, a suitable optical glass component would correspond to the phosphate laser glass composition described above except that the lasing species is omitted and is replaced by 0.01-8 mole% La₂O₃.

It is also possible to omit the lasing species entirely and to instead dope the glass with one or more metal species, e.g., Cu or Sm, which impart light-filtering characteristics to the glass, e.g., for their use in other applications, such as filters, doped laser glass claddings for large discs, slabs, or other forms (see, e.g., U.S. 4,849,036), fibers (see, e.g., U.S. 4,217,382), etc., where their exceptional combination of properties is beneficial.

A suitable doped laser glass cladding, for example, would correspond to the above phosphate laser glass composition except that the active lasing species would be omitted and replaced by a component that would not ad versely affect the heat capacity and thermal expansion coefficient (e.g., 0.01-8 moles La₂O₃) and the glass would further contain a dopant capable of absorbing the laser wavelength, for example, > 0.0-2.0 wt.% of Cu₂O, e.g., 0.1, 0.3, 0.5 or 1 wt.% or about 10-30 wt.% Sm₂O₃, e.g., 10, 15, 20, 25 or 30 wt.%. for a lasing wavelength of Nd in phosphate glasses, i.e., 1.05-1.06 microns.

The laser phosphate glass composition described above can also be used as a glass waveguide. For example, the glass could be used to provide a plate waveguide wherein a certain region of the glass plate is treated (e.g., by ion exchange) to provide regions having different refractive indexes such that light will be guided through a specific region of the glass plate.

The phosphate laser glass composition may also be used as an incident light detector by virtue of its characteristic luminescence. In a glass containing fluorophores, absorbed incident light will induce the fluorophores to luminesce thereby indicating absorption of incident light.

Of course, as is clear from the foregoing discussion, the glasses of this invention are completely compatible with current state-of-the-art manufacturing methods for phosphate laser glasses. The melting, refining, homogenizing and casting of these glasses can be accomplished using the current standard procedures employed by the glass industry. The highly thermal stress resistant glasses of this invention can be formed into slabs, rods, discs, fibers, and other shapes required by the laser community and others by conventional forming techniques well known in the glass industry. The resultant glasses are of high thermal conductivity, low thermal coefficient of expansion, low Young's modulus, high cross section for stimulated emission, low nonlinear refractive index, and exhibit reduced concentration quenching of the upper state involved in the laser transition. In addition, the resultant glasses have a high solubility rate for platinum and are stable against devitrification and crystalliza tion. Thus, these glasses are readily fabricated in large volume pieces free of metallic particles and crystalline inclusions which can become macroscopic damage sites when used in a high energy laser system.

The glasses of this invention can be fully conventionally prepared by mixing the appropriate amounts of each constituent to form a batch composition which is then charged into a fused silica crucible and melted by induction heating from, e.g., 1100°C to as much as 1500°C, depending on the chosen composition. The glass can then be refined at temperatures exceeding, e.g., 1300°C from typically 2 to 4 hours, again depending on composition and melt viscosity, with equal intervals of gas bubbling and stirring. The glass is then typically cast into steel molds and annealed at the transformation temperature plus about 20°C for about 2 hours followed by cooling at about 30°C/hour. These procedures were followed in the examples below.

As noted above, the examples of this application are melted in a fused silica crucible. Under such melting conditions, as is well known, there will be some silica added from the crucible to the final glass composition. Accordingly, whereas all compositions given in this disclosure refer to the component contents as added to the batch as is conventional (batch compositions), where a fused silica crucible is employed, the final composition will contain some silica, regardless of whether Si0₂ is added as a batch component. This conventional difference from the initial batch composition is analogous to other differences between final glass compositions and batch compositions, e.g., due to the volatilization of ingredients, etc. The additional amount of silica over and above the amount included in the batch compositions will generally be no more than about 3.5, 3, 2.5, 2, 1.5, 1, 0.5 mole%, etc., especially not more than about 3 mole% and most especially not more than about 2 mole% (all on a renormalized basis). In a preferred aspect of this inven tion, there is no silica added to the batch compositions, and the final composition contains no more than 3 mole% silica, especially not more than 2 or 1 mole% silica (on the mentioned basis) due to the effect of silica dissolution from the crucible. Of course, where a nonsilica-containing crucible is employed, this effect will not occur.

The silica contribution from the crucible will vary conventionally with melt temperature and melting time. For example, in a melt of about 2 hours at a temperature of about 1300°C, about 2 wt.% of silica will be contributed from a quartz crucible, the precise amount being determined by the precise conditions involved such as glass volume exposed, crucible surface area, glass composition, degree of agitation in the melt, etc.

Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize this invention to its fullest extent. The following preferred specific embodiments are, therefore, to be construed as merely illustrative and not limitative of the remainder of the disclosure in any way whatsoever.

In the foregoing and in the following examples, all temperatures are set forth uncorrected in degrees Celsius and unless otherwise indicated, all parts and percentages are by weight.

The entire texts of all applications, patents and publications cited above are hereby incorporated by reference.

E X A M P L E S

It will be noted that several of the examples achieve properties falling outside the ranges described above as desirable. These examples thus demonstrate the importance of certain factors discussed above in achieving the desired properties. Most importantly, such examples provide valuable guidance as to how routine experimentation may be utilized to select compositions within the general composition space defined for this invention. Fully conventional consideration will, of course, be given by skilled workers in any study of these examples to the experimental errors involved in measuring the disclosed properties, e.g., ±4% for thermal conductivity and ±1% for thermal coefficient of expansion.

TABLE 1

Oxide/Melt No. 1 2 2 4

P₂O₅ 67 63 59 55 SiO₂

Al₂O₃ 0 4 8 12

B₂O₃

Li₂O

Na₂O

K₂O 15 15 15 15 BaO 15 15 15 15

MgO

CaO

Nd₂/La₂O₃

Total 100 100 100 100 n_d (@ 587.6 nm) 1.53178 1.53513 1.54005 1.54691

Abbe No. 65.84 65.88 65.84 66.18 Tg (°C) DTA 384.3 432.8 467 487.8 density (g/cm³) 2.8987 2.9354 2.9829 3.0524 K (W/mK) (@ 90°C) .46 .53 .52 .55 Poisson's ratio (v) .27 .27 .27 .26 α (10^-7/K) (@ 20-300°C) 147.6 133.2 128.7 119.8 E (10⁶ GPa) 40.3 44.9 49.6 54.7 n² (10-¹³ esu) 1.18 1.18 1.19 1.21 C_p (J/gK) .59 .61 .59 .63 K_1c (MPa m^½) .54 .45 .39 .33

D_Pt (cm^-1) (@ 400 nm) .0452 .0306 .0284D_Wdur (mg/cm²/day) .1923 .0594 .0302 .0505 σ (10^-20 cm²) 4.45 4.04 3.61 3.26 Δλ_em (nm) 23.31 24.73 26.62 28.36 T (rad) μsec 325.7 335.9 348.6 357.5

T_o (μsec) 336.5 352.6 361.7 368.8 Q (10²⁰ cm^-3) 9.14 7.91 7.9 6.62

Devit. Coeff. (0 or 1) 1 1 1 0 Durabil. Coeff. (0 or 1) 0 1 1 1

DTA = Differential Thermal Analysis

TABLE 2

Oxide/Melt No . 5 6 3 7

P₂O₅ 51.4 55.4 59 63

SiO₂

Al₂O₃ 12

B₂O₃

Li₂O

Na₂O

K₂O 22.8 18.8 15 11

BaO 22.8 18.8 15 11

MgO

CaO

Nd₂/La₂O₃ 3 3 3 3

Total 100 100 100 100 n_d (@ 587 . 6 nm) 1.53901 1.53837 1.54005 1.5389 Abbe No . 64.38 65.27 65.84 66.33 Tg ( ºC) DTA 373.6 422.2 467 528.3 density (g/cm³) 3.0816 3.0163 2.9829 2.823 K (W/mK) (@ 90 °C) .43 .47 .52 .60 Poisson' s ratio ( v) .30 .28 .26 .25 α ( 10-⁷/K) (@ 20-300 °C ) 184.7 154 128.7 121.6 E ( 10 ⁶ GPa) 38.2 43.4 49.6 54.7n₂ (10^{- 13} 1.23 1.2 1.19 1.18 C_P (J/gK) .57 .58 .59 .62

K_1c (MPa m^½) .34 .4 .39 .58

D_Pt (cm^{- 1}) (@ 400 nm ) .0335 .0306 .0251

D_Wdur (mg/cm²/day) .74581 .1403 .0302 .0521 σ (10^-20 cm²) 3.92 3.89 3.61 3.43

Δλ_em (nm) 25.69 25.49 26.62 28.21

T (rad) μsec 334.5 337.1 348.6 345.7

T_o (μsec) 346.2 357 361.7 362.1

Q (10²⁰ cm^-3) 5.72 7.83 7.9 7.1

Devit. Coeff. (0 or 1) 1 0 1 1 Durabil. Coeff. (0 or 1) 0 0 1 1

DTA = Differential Thermal Analysis

TABLE 3

Oxide/Melt No. 8 9 3 10 11

P₂O₅ 67 63 59 55 51

SiO₂

Al₂O₃

B₂O₃

Li₂O

Na₂O

K₂O 11 13 15 17 19

BaO 11 13 15 17 19

MgO

CaO

Nd₂/La₂O₃

Total 100 100 100 100 100 n_d (@ 587.6 nm) 1.53602 1.53736 1.54005 1.544 1.54699

Abbe No. 66.23 65.4 65.84 65.59 64.97

Tg (ºC) DTA 499.2 492 467 480 443 density (g/cm³) 2.8865 2.9216 2.9829 3.0336 3.0966

K (W/mK) (@ 90ºC) .56 .54 .52 .54 .50

Poisson's ratio (v) .26 .27 .26 .28 .28 a (10^-7/K) (@ 20-300°C) 112.4 115.9 128.7 139.4 143

E (10⁶ GPa) 52.6 50.7 49.6 49.8 49.4 n₂ (10^-13 esu) 1.17 1.18 1.19 1.21 1.23

C_p (J/gκ) .62 .61 .59 .59 .61

K_1c (MPa m^½) .46 .45 .39 .32 .29

D_Pt (cm^-1) (400 nm) .0435 .0306 .0315

D_Wdur (mg/cm²/day) .0136 .0153 .0302 .0707 .0963 σ (10^-20 cm²) 3.78 3.7 3.61 3.52 3.44

Δλ_em (nm) 25.45 26.19 26.62 27.35 27.91

T (rad) μsec 346.4 345.6 348.6 344.1 344.3

T_o (μsec) 359.5 359.9 361.7 358.1 351.6

Q (10²⁰ cm^-3) 8.03 8.14 7.9 6.91 7.53

Devit. Coeff. (0 or 1) 0 1 1 1 0 Durabil. Coeff. (0 or 1) 1 1 1 1 1

DTA = Differential Thermal Analysis

TABLE 4

Oxide/Melt No. 4 12 13 3 14 15

P₂O₅ 55 55 55 59 59 59 SiO₂

Al₂O₃ 12 12 12 8 8 8

B₂O₃

Li ₂O 15 15 Na₂O

K₂O 15 15 15 15

BaO 15 15

MgO 15 15 15 15 CaO

Nd₂/La₂O₃

Total 100 100 100 100 100 100 n_d (@ 587 . 6 nm) 1.54691 1.52111 1.53833 1.54005 1.51963 1.53692

Abbe No . 66.18 67.25 66.14 65.84 67.41 66.47

Tg ( ºC) DTA 487.8 523.7 469.8 467 529 478.3 density (g/cm³) 3.0524 2.6984 2.6955 2.9829 2.6638 2.6799

K (W/mK) (@ 90°C) .55 .67 .86 .52 .64 .82 Poisson' s ratio ( v ) .26 .25 .28 .26 .24 .23 α ( 10^-7/K) (@ 20-300°C) 119.8 106.5 89.8 128.7 110.5 93.6

E ( 10⁶ GPa) 54.7 58.4 71.2 49.6 55.3 69 n₂ (10^-13 esu) 1.21 1.09 1.18 1.19 1.08 1.16

C_P (J/gK) .63 .73 .74 .59 .68 .75 K_1c (MPa m^½) .33 .47 .4 .39 .49 .57

D _Pt (cm^-1) (@ 400 nm) .0284 .0306 .0254 .0118

D_Wdur (mg/cm²/day) .0505 .123 .0378 .0302 .037 .006 σ (10^-20 cm²) 3.26 3.05 3.03 3.61 3.4 3.26

Δλ_em (nm) 28.36 29.36 29.77 26.62 27.75 29.24 T (rad) μsec 357.5 379.3 369.4 348.6 360.5 348

T_o (μsec) 368.8 393.2 386.3 361.7

Q (10²⁰ cm^-3) 6.62 5.98 5.26 7.9 7.5 7

Devit. Coeff. (0 or 1) 0 1 0 1 1 1 Durabil. Coeff. (0 or 1) 1 0 1 1 1 1

DTA = Differential Thermal Analysis

TABLE 5

Oxide/Melt No. 2 16 17 19

P₂O₅ 63 63 63 63 SiO₂

Al₂O₃ 4 4 4 4

B₂O₃

Li₂O 15 Na₂O

K₂O 15 15 15

BaO 15

MgO 15 15 CaO 15

Nd₂/La₂O₃ 3 3 3

Total 100 100 100 100 n_d (@ 587.6 nm) 1.53513 1.51947 1.5177 1.53503

Abbe No. 65.88 66.39 67.09 65.98

Tg (ºC) DTA 432.8 452 502.7 462 density (g/cm³) 2.9354 2.637 2.6502 2.6591

K (W/mK) (@ 90°C) .53 .55 .62 .80 Poisson's ratio (v) .27 .25 .25 .22 α (10^-7/K) (@ 20-300ºC) 133.2 121.8 116.5 97.6

E (10⁶ GPa) 44.9 48.2 52.2 65.3 n₂ (10^-13 esu) 1.18 1.1 1.08 1.17

C_P (J/gK) .61 .66 .7 .75 K_1c (MPa m^½) .45 .52 .6 .69

D_Pt (cm^-1) (@ 400 nm) .0452 .0202

D_Wdur (mg/cm²/day) .0594 .2 .0624 .0371 σ (10^-20 cm²) 4.04 3.93 3.66 3.55

Δλ_em (nm) 24.73 25.35 26.41 26.9 T (rad) μsec 335.9 355 349.8

T_o (μsec) 352.6 364.6 367.1

Q (10²⁰ cm^-3) 7.91 8.27 7 7.76

Devit. Coeff. (0 or 1) 1 0 1 0 Durabil. Coeff. (0 or 1) 1 0 1 1

DTA = Differential Thermal Analysis

TABLE 6

Oxide/Melt No. 3 19 20 21 22 23 24

P₂O₅ 59 55 51 59 59 53 47 SiO, 8 16 4 6 12Al₂O₃ 8 4 4 8 8

B₂O₃

Li₂O

Na₂O

K₂O 15 15 15 15 15 15 15 BaO 15 15 15 15 15 15 15

MgO

CaO

Nd₂/La₂O₃ 3 3 3 3 3 3 3

Total 100 100 100 100 100 100 100 n_d (@ 587.6 nm) 1.54005 1.53465 1.53391 1.53518 .53624 1.54072 L.54286

Abbe No. 65.84 65.81 65.23 65.88 65.76 65.74 65.44 Tg (ºC) DTA 467 452 419.6 448.5 419 482.1 483.5 density (g/cm³) 2.9829 2.9443 2.9497 2.9477 2.947 3.002 3.0195 K (W/mK) (@ 90°C) .52 .51 .49 .51 .50 .54 .55 Poisson's ratio (v) .26 .27 .27 .27 .27 .26 .26 α (10^-7/K) (@ 20-300°C) 128.7 134.4 137.7 134 139 131.6 125.2 E (10⁶ GPa) 49.6 45.1 43.6 45.3 43.4 49.3 51.5 n₂ (10^-13 esu) 1.19 1.18 1.18 1.17 1.18 1.19 1.21

C_P (J/gK) .59 .61 .62 .62 .59 .61 .58 K_1c (MPa m^½) .39 .49 .77 .42 .39 .38 .43

D_Pt (cm^-1) (@ 400 nm) .0306 .0406

D_Wdur (mg/cm²/day) .0302 .2588 14.05 .07065 .3887 .1445 .175 σ (10^-20 cm²) 3.61 3.87 3.89 3.89 4.07 3.41 3.22

Δλ_em (nm) 26.62 25.3 25.02 25.47 24.76 27.65 28.9 T (rad) μsec 348.6 341.2 345.2 337.9 332.5 352.5 357.2

T_o (μsec) 361.7 357.5 351.8 346.6 363.7 369.6

Q (10²⁰ cm^-3) 7.9 7.88 8.92 8.62 7.1 6.5

Devit. Coeff. (0 or 1) 1 1 0 1 1 1 0

Durabil. Coeff. (0 or 1) 1 0 0 1 0 0 0

DTA = Differential Thermal Analysis

TABLE 7

Oxide/Melt No. 3 25 29 27 28

P₂O₅ 59 59 59 53 47

SiO₂

Al₂O₃ 8 4 0 8 8

B₂O₃ 4 8 6 12

Li₂O

Na₂O

K₂O 15 15 15 15 15

BaO 15 15 15 15 15

MgO

CaO

Nd₂/La₂O₃

Total 100 100 100 100 100 n_d (@ 587.6 nm) 1.54005 1.53624 1.53437 1.54298 1.54892

Abbe No. 65.84 65.64 66.02 66.02 65.89

Tg CO DTA 467 449 423.5 488.3 512.2 density (g/cm³) 2.9829 2.9354 2.9091 3.0068 3.043

K (W/mK) (@ 90°C) .52 .51 .53 .54 .61

Poisson's ratio (v) .26 .27 .27 .27 .26 α (10^-7/K) (@ 20-300°C) 128.7 133.3 138.7 123.6 123.8

E (10⁶ GPa) 49.6 46.2 43.6 51.9 55.2 n₂ (10^-13 esu) 1.19 1.18 1.16 1.21 1.21

C_P (J/gK) .59 .59 .65 .62 .59

K_1c (MPa m^½) .39 .42 .42 .43 .29

D_Pt (cm^-1) (@ 400 nm) .0306 .0383 .0213

D_Wdur (mg/cm²/day) .0302 .133 .265 .1079 .075 σ (10^-20 cm²) 3.61 3.81 3.95 3.48 3.22

Δλ_em (nm) 26.62 25.78 25.22 27.36 28.66

T (rad) μsec 348.6 342 336.5 349.5 356.5

T_o (μsec) 361.7 354 351.1 375.6 371.2

Q (10²⁰ cm^-3) 7.9 8.59 8.01 5.83 6.33

Devit. Coeff. (0 or 1) 1 1 0 1 0 Durabil. Coeff. (0 or 1) 1 0 0 0 1

DTA = Differential Thermal Analysis

TABLE 8

Mole %

Oxide 29 30 16 32 ₃3 34

P₂O₅ 63 63 63 63 67 65 57.6

Al₂O₃ 4 4 4 4 4 2 8.8

Li₂O

Na₂O

K₂O 25 20 15 10 13 15 17.1

MgO

CaO 5 10 15 20 13 15

BaO 13.7

Nd₂/La₂O₃ 3.0 3.0 3.0 3.0 3.0 3.0 3.0

Sb₂O₃

As₂O₃

Nb₂O₅

Total 100 100 100 100 100 100 100.2

Property

K (@ 90°C) [W/mK] .4929 .5186 .5516 .5855 .5645 .5301 .5120

Poisson's ratio, v .268 .262 .252 .246 .249 .256 .263 α [10^-7/°C] :

(@ 20-300°C) 155.5 138.3 121.8 108.4 114.7 123.8 131.0

(@ 20-40°C)

E [10⁶ GPa] 38.8 42.8 48.2 52.2 48.8 45.1 50.0

K_1c [MPa m^½] .41 .56 .52 .55 .52 .56 .40 den [g/cm³] 2.596 2.615 2.637 2.657 2.639 2.615 2.959

Tg [°C] 399 416 449 475 448 415 452

C_p [J/gK] .690 .730 .660 .700 .710 .720 .610

Dur [mg/cm²/day] .66 .38 .20 .13 .12 .34 .04

Devit. Test (0 or 1) 1 1 1 1 1 1 1

D_Pt [cm^-1] (@ 400 nm)

σ [10^-20 cm²] 4.34 4.16 3.93 3.73 3.99 4.12 3.68

Q [10²⁰ cm³] 7.72 7.86 8.58 6.90 7.30 7.81 7.50 n₂ [10^-13 esu] 1.03 1.06 1.10 1.13 1.10 1.07 1.17

Δλ_em [nm] 24.23 24.71 25.35 26.29 24.59 24.63 25.99

T_o [μsec] 352.4 354.8 357.1 372.8 357.7 353.5 360.7

T_r [μsec] 330.8 334.7 343.5 347.6 343.2 338.4 349.0 n_d 1.50686 1.51259 1.51947 1.52667 1.52064 1.51670 1.53795

Abbe No. 67.46 67.04 66.39 66.20 66.77 67.11 66.27 TABLE 9

Mole %

Oxide 35 36 37 38 39

P₂O₅ 65 65 65 65 65

Al₂O₃ 4 4 4 4 4

Li₂O

Na₂O

K₂O 14 14 21 14

MgO 14 7 7

CaO 14 7

BaO

Nd₂/La₂O₃ 3.0 3.0 3.0 3.0 3.0

Sb₂O₃

As₂O₃ .1 .1 .1 .1 .1

Nb₂O₅ .1 .1 .1 .1 .1

Total 100.2 100.2 100.2 100.2 100.2

Property

K (90°C) [W/mK] .5630 .6187 .5440 .5993 .5514

Poisson's ratio, v .250 .259 .268 .254 .261 α [10^{- 7}/°C] :

(@ 20-300°C) 118.7 116.1 142.5 115.5 131.1

(@ 20-40°C) 95.2 107.0 100.1 120.7

E [10⁶ GPa] 48.1 51.1 42.6 50.3 45.6

K_1c [MPa m^½] .55 .48 .50 .57 .64 den [g/cm³] 2.637 2.640 2.610 2.630 2.620

Tg CO 456 463 412 460 425

C_p [J/gκ] .650 - - - - - - - -

Dur [mg/cm²/day] .17 .08 .17 .09 .13

Devit. Test (0 or l) 1 1 1 1 1

D_pt . [cm^-1] (® 400 nm) .0330 .0516 .0745 .0264 .0499 σ [10-²⁰cm²] 3.84 3.76 4.24 3.83 3.99

Q [10²⁰ cm^-3] 8.13 8.21 8.83 8.17 8.60 n₂ [10^-13 esu] 1.09 1.06 1.04 1.08 1.05

Δλ _em [nm] 25.63 25.36 24.17 25.45 24.61

T_o [μsec] 356.0 355.6 349.6 356.0 351.8

T_r [μsec] 344.9 361.1 344.7 356.5 350.0 n_d 1.51959 1.51696 1.50917 1.51838 1.51347

Abbe No. 66.87 67.71 67.62 67.17 67.56

The preceding examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples.

From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.

Claims

WHAT IS CLAIMED IS:

1. In a high energy laser system utilizing phosphate laser glass components, the improvement wherein the parameters of said laser system necessitate that said phosphate laser glass components have an emission bandwidth of less than about 26 nm, and wherein said laser glass components consist essentially of (on an oxide composition basis) :

Mole%

P₂O₅ 50-75 Al₂O₃ > 0-10 K₂O > 0-30 MgO 0-30 CaO 0-30 Li₂O 0-20 Na₂O 0-20 Rb₂O 0-20 Cs₂O 0-20 BeO 0-20 SrO 0-20 BaO 0-20 ZnO 0-20 PbO 0-20 B₂O₃ 0-10 Y₂O₃ 0-10 La₂O₃ 0-8 Ln₂O₃ 0.01-8 wherein

the sum of MgO and CaO is > 0-30;

the sum of Li₂O, Na₂O, Rb₂O, and Cs₂O is 0-20;

the sum of BeO, SrO, BaO, ZnO, and PbO is 0-20;

the sum of B₂O₃ and Y₂O₃ is 0-10; and Ln₂O₃ represents the sum of the oxides of active lasing lanthanides of atomic numbers 58-71.

2. A laser system according to claim 1, wherein said glass consists essentially of:

Mole%

P₂O₅ 55-75

Al₂O₃ 1-9

K₂O 8-28

MgO 0-24

CaO 0-24

Li₂O 0-15

Na₂O 0-15

Rb₂O 0-15

Cs₂O 0-15

BeO 0-15

SrO 0-15

BaO 0-15

ZnO 0-15

PbO 0-15

B₂O₃ 0-8

Y₂O₃ 0-8

La₂O₃ 0-5

Ln₂O₃ 0.01-8 wherein

the sum of MgO and CaO is 4-24;

the sum of Li₂O, Na₂O, Rb₂O, and Cs₂O is 0-15;

the sum of BeO, SrO, BaO, ZnO, and PbO is 0-15;

the sum of B₂O₃ and Y₂O₃ is 0-8; and

Ln₂O₃ represents the sum of the oxides of active lasing lanthanides of atomic numbers 58-71.

3. A laser system according to claim 1, wherein said glass consists essentially of:

Mole% P₂O₅ 60-70

Al₂O₃ 2-6 K₂O 10-24

MgO 0-20

CaO 0-20

Li₂O 0-10

Na₂O 0-10

Rb₂O 0-10

Cs₂O 0-10

BeO 0-10

SrO 0-10

BaO 0-10

ZnO 0-10

PbO 0-10

B₂O₃ 0-5

Y₂O₃ 0-5

La₂O₃ 0-4

Ln₂O₃ 0.01-8 wherein

the sum of MgO and CaO is 5-20;

the sum of Li₂O, Na₂O, Rb₂O, and Cs₂O is 0-10;

the sum of BeO, SrO, BaO, ZnO, and PbO is 0-10;

the sum of B₂O₃ and Y₂O₃ is 0-5; and

Ln₂O₃ represents the sum of the oxides of active lasing lanthanides of atomic number 58-71.

4. A laser system according to claim 1, wherein said laser glass components exhibit the following properties:

K , thermal conductivity > 0.5 W/mK v, Poisson's ratio < .28

α, thermal expansion from 20-300° < 145 × 10^-7/K

E, Young's modulus < 50 GPa

K_1c, fracture toughness > 0.40 MPa m^1/2 ρ, glass density > 2.60 g/cm³

C_p, glass heat capacity > 0.50 J/gK σ, cross section > 3.5 × 10^-20 cm²

Q, concentration quenching factor > 7 × 10²⁰ cm^-3 n₂, non-linear refractive index < 1.2 × 10^-13 esu Δλ_abs, absorption bandwidth > 16 nm

T_g, glass transformation point < 460°C

D_wdur, durability of the glass to water < 0.20 mg/cm² day

D_Pt, platinum solubility (@ 400 nm) > 0.03 cm^-1.

5. A laser system according to claim 4, wherein said laser glass has the following properties:

K , thermal conductivity > 0.55 W/mK α, thermal expansion from 20-300°C < 140 × 10^-7/K

E, Young's modulus < 45 GPa

K_1c, fracture toughness > 0.50 MPa m^1/2 σ, cross section > 4.0 × 10^-20 cm²

Q, concentration quenching factor > 8 × 10²⁰ cm^-3 n₂, non-linear refractive index < 1.1 × 10^-13 esu.

6. A laser system according to claim 1, wherein said laser glass containing 0.01-8 mole% Nd₂O₃.

7. A laser system according to claim 2, wherein said laser glass containing 0.01-8 mole% Nd₂O₃.

8. A laser system according to claim 3, wherein said laser glass containing 0.01-8 mole% Nd₂O₃.

9. A laser system according to claim 4, wherein said laser glass containing 0.01-8 mole% Nd₂O₃.

10. A laser system according to claim 5, wherein said laser glass containing 0.01-8 mole% Nd₂O₃.

11. A laser system according to claim 1, wherein the molar ratio of P₂O₅/ (3ΣR₂O₃ + MgO) is at least 1.5, wherein R is Al, La, Ln, Y, and B.

12. A laser system according to claim 6, wherein the value of ^ ±ι₂ for said laser glass is > 25 (esu·cm)^-1.

13. A laser system according to claim 6, wherein the value of for said laser glass is > 0.60 × 10^-6

m²/sec.

14. A laser system according to claim 1, wherein the value of D_Pt of said laser glass is > 0.025 cm^-1 at 400 nm.

15. A laser system according to claim 6, wherein said laser glass has a non-linear refractive index of < 1.2 × 10^-13 esu.

16. A laser system according to claim 6, wherein the cross section, σ, of said laser glass is > 3.5 × 10^-20 cm².

17. A laser system according to claim 6, wherein the concentration quenching factor, Q, of said laser glass is > 7 × 10²⁰ cm^-3.

18. A laser system according to claim 1, wherein said system operates at an energy level of at least 0.1 MJ.

19. A laser system according to claim 1, wherein said laser glass contains 2-8.8 mole % Al₂O₃, has a T_g value of ≤ 499.2°C, and a cross-section of ≥ 3.68 × 10^-20 cm².

20. A laser system according to claim 19, wherein said laser glass contains 2-8 mole % Al₂O₃.

21. A laser system according to claim 20, wherein said laser glass has a T_g value of ≤ about 463°C.

22. A laser system according to claim 1, wherein said laser glass has the following properties :

K , thermal conductivity ≥ 0.51 W/mK α, thermal expansion from 20-300°C < 145 × 10^-7/K

E, Young's modulus < 52.6 GPa

K_1c, fracture toughness > 0.40 MPa m^1/2 σ, cross section > 3.5 × 10^-20 cm²

Q, concentration quenching factor ≥ 8 × 10²⁰ cm^-3 n₂, non-linear refractive index ≤ 1.16 × 10^-13 esu.

23. In a high energy laser system utilizing phosphate laser glass components, the improvement wherein the parameters of said laser system necessitate that said phosphate laser glass components have an emission bandwidth of less than 26 nm, and wherein said laser glass components consist essentially of (on an oxide composition basis) :

Mole%

P₂O₅ 50-75

Al₂O₃ > 0-10

K₂O > 0-30

MgO 0-30

CaO 0-30

Li₂O 0-20

Na₂O 0-20

Rb₂O 0-20

Cs₂O 0-20

BeO 0-20

SrO 0-20

BaO 0-20

ZnO 0-20

PbO 0-20

B₂O₃ 0-10

Y₂O₃ 0-10 non-lanthanide lasing species 0.01-8 wherein

the sum of MgO and CaO is > 0-30;

the sum of Li₂O, Na₂O, Rb₂O, and Cs₂O is 0-20;

the sum of BeO, SrO, BaO, ZnO, and PbO is 0-20; and the sum of B₂O₃ and Y₂O₃ is 0-10.

24. A phosphate laser glass for use in high energy laser systems consisting essentially of (on an oxide composition basis) : Mole%

P₂O₅ 50-75

Al₂O₃ > 0-10

K₂O > 0-30

MgO 0-30

CaO 7-30

Li₂O 0-20

Na₂O 0-20

Rb₂O 0-20

Cs₂O 0-20

BeO 0-20

SrO 0-20

BaO 0-20

ZnO 0-20

PbO 0-20

B₂O₃ 0-10

Y₂O₃ 0-10

La₂O₃ 0-8

Ln₂O₃ 0.01-8 wherein

the sum of Li₂O, Na₂O, Rb₂O, and Cs₂O is 0-20;

the sum of BeO, SrO, BaO, ZnO, and PbO is 0-20;

the sum of B₂O₃ and Y₂O₃ is 0-10;

the sum of MgO and CaO is 7-30;

Ln₂O₃ represents the sum of the oxides of active lasing lanthanides of atomic numbers 58-71; and wherein said glass exhibits the following properties:

K, thermal conductivity > 0.5 W/mK

v, Poisson's ratio < .28

α, thermal expansion from 20-300° < 145 × 10^-7/K

E, Young's modulus < 50 GPa

K_1c, fracture toughness > 0.40 MPa m^1/2 ρ, glass density > 2.60 g/cm³

C_p, glass heat capacity > 0.50 J/gK σ, cross section > 3.5 × 10^-20 cm²

Q, concentration quenching factor > 7 × 10²⁰ cm^-3 n₂, non-linear refractive index < 1.2 × 10^-13 esu Δλ_abs, absorption bandwidth > 16 nm

Δλ_em, emission bandwidth < 26 nm

T_g, glass transformation point < 460 °C

D_wdur, durability of the glass to water < 0.20 mg/cm² day

D_pt, platinum solubility (@ 400 nm) > 0.03 cm^-1.

25. A glass according to claim 24, wherein said glass contains 0.01-8 mole% Nd₂0₃.

26. A phosphate laser glass for use in high energy laser systems consisting essentially of (on an oxide composition basis) :

Mole%

P₂O₅ 50-75

Al₂O₃ > 0-10

K₂O > 0-30

MgO 0-7

CaO 0-30

Li₂O 0-20

Na₂O 0-20

Rb₂O 0-20

Cs₂O 0-20

BeO 0-20

SrO 0-20

BaO 0-20

ZnO 0-20

PbO 0-20

B₂O₃ 0-10

Y₂O₃ 0-10

La₂O₃ 0-8

Ln₂O₃ 0.01-8 wherein

the sum of MgO and CaO is > 0-30;

the sum of Li₂O, Na₂O, Rb₂O, and Cs₂O is 0-20;

the sum of BeO, SrO, BaO, ZnO, and PbO is 0-20;

the sum of B₂O₃ and Y₂O₃ is 0-10; and Ln₂O₃ represents the sum of oxides of active lasing lanthanide of atomic numbers 58-71,

and wherein said glass exhibits the following properties:

K , thermal conductivity > 0 . 5 W/mK

v , Poisson's ratio < . 28

α , thermal expansion from 20-300° < 145 × 10^-7/K

E, Young's modulus < 50 GPa

K_1c, fracture toughness > 0 . 40 MPa m^1/2 ρ, glass density > 2 . 60 g/cm³

C_p, glass heat capacity > 0 . 50 J/gK σ, cross section > 3 . 5 × 10^-20 cm²

Q, concentration quenching factor > 7 × 10²⁰ cm^-3 n₂, non-linear refractive index < 1 . 2 × 10^-13 esu

Δλ_abs, absorption bandwidth > 16 nm

Δλ_em, emission bandwidth < 26 nm

T_g, glass transformation point < 460°C

D_wdur, durability of the glass to water < 0.20 mg/cm² day

D_pt, platinum solubility > 0.03 cm^-1.

27. A glass according to claim 26, wherein said glass contains 0 mole% MgO and > 0-30 moles CaO.

28. A glass according to claim 26, wherein said glass contains 0.01-8 mole% Nd₂O₃.

29. In a method of generating a high energy laser beam, the improvement wherein said laser beam is generated by a laser system according to claim 1.

30. An optical glass component consisting essentially of (on an oxide composition basis):

Mole% P₂O₅ 50-75

Al₂O₃ > 0-10

K₂O > 0-30

MgO 0-30 CaO 0-30

Li₂O 0-20

Na₂O 0-20

Rb₂O 0-20

Cs₂O 0-20

BeO 0-20

SrO 0-20

BaO 0-20

ZnO 0-20

PbO 0-20

B₂O₃ 0-10

Y₂O₃ 0-10

La₂O₃ 0.1-8 wherein

the sum of MgO and CaO is > 0-30;

the sum of Li₂O, Na₂O, Rb₂O, and Cs₂O is 0-20;

the sum of BeO, SrO, BaO, ZnO, and PbO is 0-20; and the sum of B₂O₃ and Y₂O₃ is 0-10.

31. In a method of waveguiding light using a glass waveguide, the improvement wherein said waveguide is a glass consisting essentially of (on an oxide composition basis):

Mole%

P₂O₅ 50-75

Al₂O₃ > 0-10

K₂O > 0-30

MgO 0-30

CaO 0-30

Li₂O 0-20

Na₂O 0-20

Rb₂O 0-20

Cs₂O 0-20

BeO 0-20

SrO 0-20

BaO 0-20

ZnO 0-20 PbO 0-20

B₂O₃ 0-10

Y₂O₃ 0-10

La₂O₃ 0-8

Ln₂O₃ 0.1-8 wherein

the sum of MgO and CaO is > 0-30;

the sum of Li₂O, Na₂O, Rb₂O, and Cs₂O is 0-20;

the sum of BeO, SrO, BaO, ZnO, and PbO is 0-20;

the sum of B₂O₃ and Y₂O₃ is 0-10; and

Ln₂O₃ represents the sum of the oxides of active lasing lanthanides of atomic numbers 58-71.

32. A doped laser glass cladding composition consisting essentially of (on an oxide composition basis) :

Molel P₂O₅ 50-75 Al₂O₃ > 0-10 K₂O > 0-30 MgO 0-30 CaO 0-30 Li₂O 0-20 Na₂O 0-20 Rb₂O 0-20 Cs₂O 0-20 BeO 0-20 SrO 0-20 BaO 0-20 ZnO 0-20 PbO 0-20 B₂O₃ 0-10

Y₂O₃ 0-10 La₂O₃ 0.1-8 wherein

the sum of MgO and CaO is > 0-30;

the sum of Li₂O, Na₂O, Rb₂O, and Cs₂O is 0-20;

the sum of BeO, SrO, BaO, ZnO, and PbO is 0-20; and the sum of B₂O₃ and Y₂O₃ is 0-10;

and wherein said composition further contains > 0.0-2 wt.% Cu₂O or 10-30 wt.% Sm₂O₃ as a dopant.