The Harshaw Chemical Company

Other

Harshaw/filtrol Partnership

Carl F Swinehart

Herbert Packer

William F Spicuzza

Robert H Moss

Marko Sfiligoj

David A Hammond

A crucible having an inner surface is not wetted by a melt which shrinks when it solidifies is provided with indentations in the walls of the crucible to support an ingot grown in it. Supporting the crystal provides a gap between the bottom of the ingot and the inner surface of the bottom of the crucible. The gap allows more uniform heat transfer from the bottom of the crucible than is provided when there is no gap; the gap provides a controllable temperature gradient between the interior and exterior of the crucible. To direct propagation of the growth of a macrocrystal the bottom of the crucible is provided with at least one set of multiple grooves in parallel relationship with each other. Preferably a second set of multiple grooves in parallel relationship with each other intersect the grooves of the first set at an angle chosen depending upon the lattice structure of the macrocrystal to be grown. A macrocrystal grown in a crucible with twin sets of angulated grooves produces single crystals. Grooves in the floor of a conventional graphite crucible are effective to produce an ingot with minimal multiplicities, if not an essentially single crystal, even if essentially continuous contact of the bottom of the ingot with the floor is broken.

Crucible for growing macrocrystals

A crucible having an inner surface which is not wetted by a melt which shrinks when it solidifies, is provided with indentations in its walls, the indentatons located remote from its rim. The indentations are located beneath a lateral plane through the walls of the crucible, at about two-thirds (66.6%) of the vertical height of the walls, measured from the floor of the crucible, support an ingot grown in it. Supporting the crystal provides a gap between the bottom of the ingot and the inner surface of the bottom of the crucible. The gap allows more uniform heat transfer from the bottom of the crucible than is provided when there is no gap; the gap provides a controllable temperature gradient between the interior and exterior of the crucible. To direct propagation of the growth of a macrocrystal, the bottom of the crucible is provided with at least one set of multiple grooves in parallel relationship with each other. Preferably a second set of multiple grooves in parallel relationship with each other intersect the grooves of the first set at an angle chosen depending upon the lattice structure of the macrocrystal to be grown. A macrocrystal grown in a crucible with twin sets of angulated grooves produces single crystals. Grooves in the floor of a conventional graphite crucible are effective to produce an ingot with minimal multiplicities, if not an essentially single crystal, even if essentially continuous contact of the bottom of the ingot with the floor is broken.

A crucible having an inner surface is not wetted by a melt which shrinks when it solidifies is provided with indentations in the walls of the crucible to support an ingot grown in it. Supporting the crystal provides a gap between the bottom of the ingot and the inner surface of the bottom of the crucible. The gap allows more uniform heat transfer from the bottom of the crucible than is provided when there is no gap; the gap provides a controllable temperature gradient between the interior and exterior of the crucible. To direct propagation of the growth of a macrocrystal, the bottom of the crucible is provided with at least one set of multiple grooves in parallel relationship with each other. Preferably a second set of multiple grooves in parallel relationship with each other intersect the grooves of the first set at an angle chosen depending upon the lattice structure of the macrocrystal to be grown. A macrocrystal grown in a crucible with twin sets of angulated grooves produces single crystals. Grooves in the floor of a conventional graphite crucible are effective to produce an ingot with minimal multiplicities, if not an essentially single crystal, even if essentially continuous contact of the bottom of the ingot with the floor is broken.

A crucible,having an inner surface,not wetted by a melt which shrinks when it solidifies is provided with indentations,in the walls of the crucible to support an ingot grown in it. Supporting the crystal provides a gap between the bottom of the ingot,and the inner surface of the bottom of the crucible. The gap allows more uniform heat transfer from the bottom of the crucible than is provided when there is no gap; the gap provides a controllable temperature gradient between the interior and exterior of the crucible. To direct propagation of the growth of a macrocrystal, the bottom of the crucible is provided with at least one set of multiple grooves in parallel relationship with each other. Preferably a second set of multiple grooves in parallel relationship with each other intersect the grooves of the first set at an angle chosen depending upon the lattice structure of the macrocrystal to be grown. A macrocrystal grown in a crucible with twin sets of angulated grooves produces single crystals.

The addition of a getter consisting essentially of reactive oxides of boron and silicon, to a melt of an alkali metal halide serves to overcome problems of unacceptable color, afterglow and hardness attributable to trace impurities present in the melt. These trace impurities are generally metals present in a concentration less than 1 part per million (ppm) parts of melt. An ingot melt-grown from charge stock treated with the getter provides high quality optical bodies such as light pipes, laser windows and scintillators. Specific problems characteristic of a scintillator ingot grown from a highly purified alkali metal halide 'remelt', such as is obtained by crushing and melting portions of a melt-grown ingot, are overcome by adding to the remelt a portion of fresh powder stock in which the getter has been uniformly distributed. A process is taught for the Stockbarger growth of a scintillator ingot from a charge stock treated to include a getter consisting essentially of the combined reactive oxides of boron and silicon, comprising superheating a melt of treated charge stock for a period of time sufficient to react at least some of the reactive oxides with deleterious trace impurities present in the melt, and growing a scintillator ingot free from discoloration, afterglow or undue hardness due to the presence of the impurities.

Sodium iodide, light pipe

Light pipe, laser window and charge stock therefor

Getter for melt-grown scintillator ingot

Getter for melt-grown scintillator ingot and method for growing the ingot

A hot-pressed optical body which is free from absorption bands due to carbon dioxide, water, hydroxyl ion and acid fluorides in the ultraviolet, visible and near-infrared wavelength regions. Typically, the optical body is formed from a powder of an alkaline earth metal fluoride, alkali metal fluoride, or rare earth metal fluoride. One or more absorption bands due to a single impurity may be reduced or eliminated, or bands due to plural impurities may be reduced or eliminated sequentially, or simultaneously. The optical body is made by flowing a reactive, reducing gas, optionally, in combination with hydrogen fluoride gas, directly into the die cavity containing a pressable ionic fluoride powder, and either hot-pressing or extruding the powder.

Method of making an ionic fluoride optical body with reduction of

Large ultra-pure, prism-quality essentially single crystal boules and ingots of alkali metal chlorides and alkali metal bromides are grown by the methods of Kyropoulos and Stockbarger. Optically single crystals of these alkali metal halides are clear optical bodies free of haze throughout. A typical Kyropoulos grown boule of KBr of this invention is also absorption-free, and has cleavage or crystallographic planes which deviate from parallel by 1.degree. to 3.degree. per inch. By `absorption-free` is meant freedom of absorption at 7.2 microns (.mu.) due to nitrate, at 9.5-11 .mu. due to silicate, and at between 8 and 9 .mu. due to sulfate, which are the most difficult to control but as the term implies the bodies are also free of infrared absorption for impurities such as CO.sub.3.sup.-2, PO.sub.4.sup.-3, OH.sup.-, BO.sub.2.sup.-, SH.sup.-, CNO.sup.-, HCO.sub.3.sup.-, etc., which are easily avoided by use of good commercially available growth stock. A particular process for growth for either of the foregoing methods in a silica or quartz crucible, comprises growing an ultrapure ingot of KBr from a relatively impure melt containing silicate, sulfate, nitrate and nitrite ions, and includes maintaining the sodium content of the melt during growth to less than about 20 ppm (parts per million) and the barium content less than 10 ppm, adding barium bromide to the melt if necessary, and, contacting the melt with a trace of free bromine in a covered, but not air-tight, pot.

Method for growing absorption-free alkali metal halide single crystals

Large, doped crystal ingots are grown in a Stockbarger furnace from a melt of an alkali metal or alkaline earth metal salt using very slow oscillation (1 - 2 cycles per minute) of the ingot through a small arc of 5.degree. -20.degree. to produce an ingot having a more even distribution of dopant and an absence of open boundaries between macrocrystals within the ingot.

Growth of doped crystals

A process is disclosed for converting basic magnesium carbonate into pure hot-pressable magnesium fluoride such as is used for the hot-pressing of infra-red radiation transmitting optical bodies. The process includes contacting a slurry of basic magnesium carbonate with carbon dioxide to form enough magnesium bicarbonate or hydrates of magnesium carbonate, in situ, to alter the particles in the slurry. Carbonation of the slurry increases solubility of the solids by establishing an equilibrium relationship in solution between the unstable magnesium bicarbonate and hydrates of magnesium carbonate particles. When the carbonated slurry is contacted with a slight excess of hydrofluoric acid it precipitates solid particles of fine hydrous magnesium fluoride. Neutralization of excess hydrofluoric acid is effected with ammonium hydroxide. The solid particulate precipitate is dried and calcined to yield hot-pressable magnesium fluoride powder of exceptional purity and consistent quality. A hot-pressable magnesium fluoride powder has been prepared which has a specific and uniform refractive index, n.sub.D = 1.3850 at 20.degree. C; the powder is made up of primary particles the majority of which have an average particle diameter of greater than 5 .mu. (microns). These physical properties and a characteristic ill-defined X-ray diffraction pattern suggestive of an amorphous structure, allow the powder to be hot-pressed into an optical body without grinding the powder.

Hot-pressable magnesium fluoride powder

Inorganic macrocrystals are grown free of occluded gases in a quiescent melt in a Bridgmann, Stockbarger, or similar furnace by melting down the crystal feed stock under a reduced atmosphere composed primarily of a low molecular weight gas such as hydrogen, helium or neon having the ability to diffuse through the melt at a greater rate than that of nitrogen. The gas can also include a minor amount of one or more active scavenger gases. During crystal growth, the gas atmosphere over the melt is altered by replacing the low molecular weight gas with an inert gas having a lower solubility in the melt than that of the low molecular weight gas or by increasing the pressure of the low molecular weight gas at a specified point in the growth process to significantly increase the concentration needed to form bubbles in the melt and to retard evaporation of the melt.

Crystal growth procedure

A hot-pressed optical body is disclosed which is free from absorption bands due to carbon dioxide, water, hydroxyl ion and acid fluorides in the ultraviolet, visible and near-infrared wavelength regions. Typically, the optical body is formed from a powder of an alkaline earth metal fluoride, alkali metal fluoride, or rare earth metal fluoride. One or more absorption bands due to a single impurity may be reduced or eliminated, or bands due to plural impurities may be reduced or eliminated sequentially, or simultaneously. The optical body is made by flowing a reactive, reducing gas, optionally, in combination with hydrogen fluoride gas, directly into the die cavity containing a pressable powder, and either hot-pressing or extruding the powder.

Hot-pressed ionic fluoride optical bodies free of absorption bands and

A composition of matter transparent to infrared rays and shock resistant which is a directionally grown, polycrystalline solidified melt of a eutectic composition comprising at least two components wherein the ratio of the index of refraction of one to the other is within the range of 1.2 to 1.0, the directionally oriented, polycrystalline mass is grown in a controlled manner by adding heat to the melt and removing the same from the solids during the solidification step, the amount of heat being added to the melt and conducted through the solidified melt being 10.sup.3 to 10.sup.5 times the latent heat of fusion of the eutectic mixture.

Growing community of inventors

University Heights, OH, United States of America

Carl F Swinehart