US3846082A - Production of crystalline bodies of complex geometries - Google Patents

Production of crystalline bodies of complex geometries Download PDF

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Publication number
US3846082A
US3846082A US00196449A US19644971A US3846082A US 3846082 A US3846082 A US 3846082A US 00196449 A US00196449 A US 00196449A US 19644971 A US19644971 A US 19644971A US 3846082 A US3846082 A US 3846082A
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Prior art keywords
film
growing
sectional configuration
cross
growth
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US00196449A
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H Labelle
A Mlavsky
C Cronan
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Saint Gobain Ceramics and Plastics Inc
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Tyco Laboratories Inc
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Priority to BE791024D priority Critical patent/BE791024A/xx
Application filed by Tyco Laboratories Inc filed Critical Tyco Laboratories Inc
Priority to US00196449A priority patent/US3846082A/en
Priority to GB4986172A priority patent/GB1382529A/en
Priority to FR7239404A priority patent/FR2159339B1/fr
Priority to BR7786/72A priority patent/BR7207786D0/pt
Priority to IT53863/72A priority patent/IT973428B/it
Priority to CA155,843A priority patent/CA974859A/en
Priority to DE2254616A priority patent/DE2254616C3/de
Priority to JP47111956A priority patent/JPS5215075B2/ja
Priority to CH1625772A priority patent/CH576283A5/xx
Priority to NL7215097A priority patent/NL7215097A/xx
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Publication of US3846082A publication Critical patent/US3846082A/en
Assigned to INDIAN HEAD NATIONAL BANK reassignment INDIAN HEAD NATIONAL BANK SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SAPHIKON, INC.
Assigned to SAPHIKON, INC., A CORP. OF NEW HAMPSHIRE reassignment SAPHIKON, INC., A CORP. OF NEW HAMPSHIRE ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: TYCO LABORATORIES, INC., A CORP. OF MA.
Assigned to SAPHIKON, INC., A COMPANY OF NH reassignment SAPHIKON, INC., A COMPANY OF NH RELEASED BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: INDIAN HEAD NATIONAL BANK
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C30B15/34—Edge-defined film-fed crystal-growth using dies or slits
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
    • C30B29/66—Crystals of complex geometrical shape, e.g. tubes, cylinders
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/131—Glass, ceramic, or sintered, fused, fired, or calcined metal oxide or metal carbide containing [e.g., porcelain, brick, cement, etc.]

Definitions

  • the present invention involves the so-called EFG process previously known for growing monocrystalline bodies of materials such as alumina.
  • EFG stands for edge-defined, film-fed growth and designates a process for growing crystalline bodies from a melt.
  • the essential features of the EFG process are described in US. Pat. No. 3,591,348, issued July 6, 1971 to Harold E. LaBelle, Jr. for Method of Growing Crystalline Materials.
  • the shape of the crystalline body that is produced is determined by the external or edge configuration of a horizontal end surface of a forming member which for want of a better name is called a die, although it does not function in the same manner as a die.
  • crystalline bodies with a variety of shapes can be produced commencing with the simplest of seed geometries, namely, a round small diameter seed crystal.
  • the process involves growth on a seed from a liquid film or film material sandwiched between the growing body and the end surface of the die, with the liquid in the film being continuously replenished from a suitable reservoir of melt via one or more capillaries in the die member.
  • the film By appropriately controlling the pulling speed of the growing body and the temperature of the liquid film, the film can be made to spread (under the influence of the surface tension at its periphery) across the full expanse of the end surface of the die until it reaches the perimeter or perimeters thereof formed by intersection of that surface with the side surface or surfaces of the die.
  • the angle of intersection of the aforesaid surfaces of the die is such relative to the contact angle of the liquid film that the liquids surface tension will prevent it from overrunning the edge or edges of the dies end surface.
  • the angle of intersection is a right angle which is simplest to achieve and thus most practical to have.
  • the growing body grows to the shape of the film which conforms to the edge configuration of the dies end surface.
  • a substantially monocrystalline body with any one of a variety of predetermined cross-sectional configurations, e.g. bodies with circular, square or rectangu lar cross-sections. Furthermore, since the liquid film has no way of discriminating between an outside or inside edge of the dies end surface, it is possible to grow a monocrystalline body with a continuous hole by providing in that end surface a blind hole, i.e. a cavity of the same shape as the hole desired in the growing body provided, however, that any such blind hole is made large enough so that surface tension will not cause melt film around the hole to fill in over the hole.
  • a blind hole i.e. a cavity of the same shape as the hole desired in the growing body provided, however, that any such blind hole is made large enough so that surface tension will not cause melt film around the hole to fill in over the hole.
  • edge-defined, film-fed growth denotes the essential feature of the EFG process-the shape of the growing crystalline body is defined by the edge configuration of the die and growth takes place from a film of liquid which is constantly replenished.
  • the film-supporting surface of the die functions as a. substantially iso-thermal heater (i.e. the film-supporting surface has a substantially flattemperature profile along its entire expanse), and the fact that the melt film is not affected by perturbations in the melt reservoir and can be maintained at an average temperature different than the average temperature of the melt in the reservoir.
  • the present invention is a modification of the EFG technique and has as its primary object the production directly from the melt of crystalline bodies characterized by complex shapes.
  • a further object of this invention is to provide a new method based on the EFG process of producing crystalline bodies of various complex shapes.
  • a more specific object of the invention is to produce new and unique essentially monocrystalline bodies of selected materials, including bodies having an axial twist.
  • the growing body may be rotated, for example, about an axis that is (a) coincident with the pulling axis; (b) not coincident but parallel to the pulling axis; or (c) transverse to the direction of crystal growth.
  • FIG. 1 is a vertical view, partly in section, of a furnace apparatus employed in practicing the invention
  • FIG. 2 is a vertical view, partly in section and on an enlarged scale, of a crucible, die and heat susceptor as sembly employed in the apparatus of FIG. 1 for growing a twisted hollow tube of rectangular cross-section;
  • FIG. 3 is a plan view of a portion of the apparatus of FIG. 2;
  • FIG. 4 is a fragmentary view of the apparatus of FIG. 2 illustrating the initial stage of growth of a twisted hol low tube of rectangular cross-section;
  • FIG. 5 illustrates the body grown with the apparatus of FIGS. 2 and 3;
  • FIG. 6 is a fragmentary view similar to FIG. 2 of a crucible and die assembly for growing a rod of circular cross-section with a spiral circular hole extending along its length;
  • FIG. 7 is a plan view of the die assembly of FIG. 6;
  • FIG. 8 illustrates the body grown with the apparatus of FIGS. 6 and 7;
  • FIG. 9 is a view similar to FIG. 6 of a crucible and die assembly for growing a helical hollow tube of circular cross-section;
  • FIG. illustrates the body grown with the apparatus of FIG. 9
  • FIG. 11 is a fragmentary sectional view of apparatus for growing a plate of dual axis curvature
  • FIG. 12 is a cross-sectional view taken along line 12--12 of FIG. 11;
  • FIG. 13 is a plan view of the die assembly employed to grow a plate of dual axis curvature.
  • FIG. 14 illustrates on an enlarged scale the shape of the body grown with the apparatus of FIGS. 11-13.
  • a furnace 2 comprising a housing 4 and heating means in the form of an RF coil 6 which is coupled to a controllable RF power supply (not shown).
  • the coil may be moved up or down along the length of the housing and means (not shown) are provided for supporting it in any selected elevation.
  • the housing 4 has a pair of valve-controlled lines 8 and 10 for introducing and withdrawing any gas which may be required to control the atmosphere within it.
  • the housing is fluid-tight and, although not shown, it is to be understood that the housing is so constructed as to permit access to its interior for the purpose of introducing a charge of feed material and attaching a seed to the pulling mechanism hereinafter described.
  • the charge of feed material is contained within a crucible 12 (see FIG.
  • a pulling mechanism 18 that includes a pulling rod 20 provided with a chuck 22 for supporting a seed crystal 24.
  • the pulling rod 20 passes through a suitable seal 26 so that the main portion of the pulling head can be located outside of the furnace as shown.
  • the pulling mechanism is designed to impart both rotational and reciprocaltranslational movement to the pulling rod 20.
  • Such pulling mechanisms are well known in the art of crystal growth and hence their constructions form no part of the present invention.
  • the specific form of the pulling mechanism is not critical to the invention provided it is capable of providing the desired rotational and translational movement.
  • the pulling mechanism is constructed as described and illustrated in US. Pat. No. 3,552,931, issued Jan. 5, 1971 to Paul R. Doherty et al. for Apparatus for Imparting Translational and Rotational Motion.
  • the pulling mechanism of Doherty et al. employs separately controllable drive means for achieving rotational and translational movement.
  • the heat susceptor 14 is cylindrical and has a bottom wall 28 that is aflixed to the supporting member 16.
  • the top end of the susceptor is open in order to allow insertion of crucible 12 which is supported in spaced concentric relation to the susceptor by a plurality of pins 30.
  • the crucible is made of a material that will not react with or dissolve in the melt, i.e., the molten charge of feed material.
  • Mounted within crucible 12 is a die assembly identified generally by the numeral 32 and comprising a disc 34 that is secured to the crucible by a ring 36 and a rod 38 that is secured to and supported by disc 34.
  • Disc 34 also functions as a heat shield and cover for the crucible.
  • Rod 38 is made of a material that is wetted by the molten charge of feed material.
  • Rod 38 is of rectangular cross-section and is formed with a rectangular bore 40 which is large enough in cross-sectional area so that it will not function as a capillary for the molten charge of feed material which is represented at 27.
  • the bore 40 need not extend for the full length of the rod but may terminate short of its bottom end so as to form a blind hole or cavity extending down from the upper end surface 44. The latter is fiat, extends substantially horizontally, and terminates in sharp inside and outside edges as shown.
  • Rod 38 terminates close to but short of the bottom of the crucible and is provided with a plurality of small capillaries 46 that extend lengthwise of its wall and terminate in the rods upper and lower end surfaces.
  • the capillaries are sized so that by capillary action a column of melt will rise in and fill them up to the top surface 44 so long as the bottom ends of the capillaries are submerged in the melt within the crucible. It is to be noted that the height to which a column of a molten material can rise in a capillary is determined by the equation where h is the distance in cm.
  • a column of molten alumina may be expected to rise more than about 11 cm. above the level of the melt in the crucible as a result of capillary action.
  • a substantially monocrystalline tube of a ceramic material characterized by a rectangular cross-section and an axial twist is produced using the apparatus of FIGS. 1-3.
  • a seed crystal 24 (of the same composition as the feed material) is mounted in chuck 22 with the pulling rod 20 axially aligned with rod 38 of the die assembly.
  • the RF coil 6 is energized to melt the charge.
  • the capillaries fill with melt by action of capillary rise from the pool of melt 27 in the crucible and the power input to the RF coil is adjusted so that the upper surface 44 of the die is about 1040 C. higher than the melting point of the seed crystal.
  • the column of melt in each capillary has a concave meniscus with the edge of the meniscus being substantially flush with surface 44.
  • the seed crystal may be in any suitable shape, e.g. a round or rectangular rod or tube. Preferably it has been grown previously by the EFG technique so that its cross-sectional shape corresponds to the configuration of surface 44, as shown in FIG. 4. Next the seed crystal is lowered into contact with the surface 44 and held there long enough for a portion of the seed tomelt and form a liquid film 48 that overlies surface 44 and connects with the melt in the capillaries.
  • the temperature gradient along the length of the seed and the temperature of surface 44 are factors influencing how much of the tube melts and the thickness of film 48.
  • the tube functions as a heat sink and the temperature of the tube at successively higher points thereon is affected by the height of coil 6 and susceptor 14 and also the power input to the coil. In practice these parameters are adjusted so that the initial film 48 has a thickness in the order of 0.1 mm.
  • the pulling mechanism 18 is actuated so as to pull seed 24 upwardly away from surface 44 Without any rotation.
  • the pulling speed is set so that the film adhering to the tube because of surface tension will crystallize due to a drop in temperature at the solid tube liquid-film interface which occurs as a result of the pulling (it is to be noted that this interface is substantially planar and parallel to surface 44).
  • the pulling speed also must be such that surface tension will cause the film to spread fully over the surface 44 (but only if the film initially formed covers less than all of the surface).
  • successive accretions of solid continue to produce a tubular extension; however, because of the relative rotation of the seed with respect to the surface 44 and the adherence of film to the growing body due to surface tension, successive accretions are angularly displaced about the pulling axis in accordance with the rate of rotation of the pulling rod. Growth is continued until the supply of melt is exhausted to the point where it is insuificient to maintain the film 48 or until the body has reached a desired length. In the latter case growth is terminated by increasing the pulling speed to a level at Which the crystal body pulls free of the melt film.
  • the pulling speed and the tem' perature of the film may be varied during crystal growth. However, the pulling speed should not be so great nor the temperature so high as to cause the tube to pull free of the melt film.
  • the pulling speed of the tube and the temperature of the film control the film thickness which controls the rate of film spreading. Increasing the temperature of surface 44 (and hence the temperature of the film) and increasing the pulling speed each have the effect of increasing the film thickness.
  • FIG. illustrates the shape of an essentially monocrystalline body 52 grown with the apparatus of FIGS. 2 and 3 as above described.
  • the body is a hollow tube whose cross-section is characterized by rectangular inner and outer edge configurations and corresponds in shape and size to that of the surface 44 (the openings of capillaries 46 are ignored since the film 48 extends over them).
  • the inner and outer surfaces of body 52 are smooth but are curved as shown because the body has an axial twist, i.e., has a rotational transformation, resulting from rotation of the pulling rod during the growth process.
  • the film thickness is relatively small (typically in the order of about 0.1 mm.) compared to the rate of growth of the growing crystal and the axial movement of the pulling rod.
  • a film thickness of about 0.1 mm. about volumes of film (disregarding any solid-liquid density difference) are required for the body to grow about 1 cm. Notwithstanding this turnover requirement, the film 6 thickness remains substantially constant due to continual inflow of fresh melt via the capillaries.
  • the angular velocity of the body about the pulling axis must not be so great as to produce a shearing action in the film or overcome the surface tension forces which cause the film to wet and adhere to the growing solid at the interface there with. Assuming that this requirement is met, at any given instant in the growth process growth is occurring on the crystal body from all points along the full expanse of the film and the crystal body undergoes rotational transformation with successive monomolecular accretions of solid.
  • FIGS. 6 and 7 show a crucible and die assembly which may be used to grow a rod having a longitudinally and spirally extending hole.
  • the die assembly 32 comprises a circular rod 38A having a circular cavity 54 in its top end surface 44A and a plurality of capillary sized, longitudinally-extending bores 46A.
  • the crucible and die apparatus of FIG. 6 is mounted in the furnace housing within susceptor 14 so that the axis of rod 38A is aligned with the axis of pulling rod 20.
  • FIG. 8 Essentially it is a straight rod 58 with a cylindrical outer surface characterized by a longitudinally extending bore 60 that curves in a helix coaxial with the rods center axis.
  • FIG. 9 illustrates a die apparatus which is like that of FIG. 6 except that its rod 38B has a circular cavity 62 that is centered with respect to its film-supporting surface 44B. Melt is supplied to surface 44B by a plurality of capillaries 46B.
  • This crucible and die apparatus is mounted in the furnace so that rod 38B is displaced laterally, i.e., eccentric, with respect to pulling rod 20.
  • the seed is mounted in chuck 22 so that its bottom end is aligned with rod 38B. This may be accomplished by mounting the seed in the chuck in eccentric relation to the axis of pulling rod 20. With this arrangement, crystal growth conducted in the manner described above, but with the seed 24A and growing crystal rotating around an axis (represented by the broken line 66 in FIG.
  • the body 68 of FIG. 10 is a hollow tube of elliptical crosssection arranged in the form of a helix.
  • the apparatus of FIG. 6 it is also possible with the apparatus of FIG. 6 to rotate the growing body about an axis eccentric to the axis of rod 38A. If this is done, the grown body will be a hollow helix the same as that shown in FIG. 10, except that the through bore will not be coaxial, i.e., a cross-section of the hollow helix will have essentially the same shape as the rod of FIG. 8.
  • FIGS. 1l14 relate to an extension of the discovery that compound movement of the pulling rod with respect to an EF G die can result in essentially monocrystalline bodies of unique shape.
  • the crystal growing furnace comprises a housing 70 modified to provide support for an arm 72 carrying at one end a chuck 74 for holding a seed crystal 76.
  • the support for arm 72 comprises a sleeve 78 which extends through and is mounted to the wall of the furnace housing and a shaft 80 which is rotatably mounted in sleeve 78.
  • Arm 74 is affixed to the inner end of shaft 80.
  • the opposite end of shaft 80 is connected to a reversible electric motor 82 which is rigidly supported by suitable support means (not shown).
  • Shaft 80 extends horizontally and is displaced laterally from the center axis of the susceptor-erucible-die assembly 84 which is supported on rod 86 afiixed to the base of the housing.
  • the assembly 84 comprises a die which, as seen in plan view in FIG. 13, comprises a disc 34 supporting a vertically extending rod 38C that has four longitudinal surfaces, one pair of which (see 88 and 90) are straight and parallel and the other pair of which (see 92 and 94) are also parallel, but with one concave and the other convex.
  • Rod 38C also has a plurality of capillaries 46C that open into its top end surface 44C.
  • the assembly 84 is disposed in the furnace so that the rod 38C is aligned with seed 76 when the arm 72 is lowered to a selected position as shown in FIG. 11.
  • arm 72 is raised by operation of motor 82 under thermal condition conducive to crystal growth thereon.
  • the growing crystal body will grow to a crosssection corresponding to the configuration of surface 440.
  • successive accretions of grown crystal will form an extension that is curved according to the arc of movement of the seed crystal.
  • FIG. 14 shows the shape of the resulting crystal body 98.
  • its cross-section has relatively broad concave and convex sides 100 and 102 that correspond in size and shape to the side edges 92 and 94 and extend between two straight parallel sides 104 that corre spond in size and shape to side edges 88 and 90.
  • the body is curved lengthwise.
  • the body corresponds to a section of a sphere.
  • a molybdenum crucible having an internal diameter of about 1 /2 inch, 2. wall thickness of about inch, and an internal depth of about 1% inch is positioned in the furnace in the manner shown in FIGS. 1 and 2. Disposed in the crucible is a die assembly constructed generally as shown in FIGS. 2 and 3.
  • the outside dimensions of surface 44 of rod 38 are /8 inch by 4 inch; the inside dimensions of surface 44, i.e. the cross-sectional dimensions of bore 40, are /2 inch by A; inch.
  • the length of rod 38 is such that its upper end projects about inch above the crucible.
  • the four capillaries each have a diameter of about 0.03 inch.
  • the crucible is filled with substantially pure polycrystalline alpha-alumina and a monocrystalline alpha-alumina tube 24 grown previously by the EEG technique is mounted in chuck 22.
  • Tube 24 is straight and conforms in cross-section to the shape and size of end surface 44 of rod 38.
  • Tube 24 is mounted in chuck 22 so that it is aligned axially with pulling rod and also rod 38.
  • the furnace housing 4 is evacuated and filled with argon via lines 8 and 10 to a pressure of about 1 atmosphere which is maintained during the growth period.
  • the RF coil 6 is energized and operated so that the alumina in the crucible is brought to a molten condition (alumina has a melting point in the vicinity of 2 050" C.) and the surface 44 reaches a temperature of about 2070 C.
  • alumina has a melting point in the vicinity of 2 050" C.
  • the surface 44 reaches a temperature of about 2070 C.
  • the pulling mechanism is actuated and operated so that the seed tube 24 is moved into contact with the upper surface 44 of the die assembly and allowed to rest in that position long enough for the bottom end of the tube to melt and form film 48 which fully covers surface 44 and connects with the columns of melt in the capillaries.
  • the seed 24 is withdrawn vertically at the rate of about 0.1-0.2 inch per minute.
  • crystal. growth occurs on the seed, propagating vertically throughout the entire horizontal expanse of the film, with the result that the growing crystal conforms in cross-sectional area and shape to surface 44.
  • the films surface tension causes additional melt to flow out of the capillaries to maintain the volume of the film constant.
  • the pulling mechanism is caused to commence rotation of the pulling rod and to maintain such rotation at an angular velocity of about 2 degrees/min.
  • the translational pulling speed is held constant at about 0.2 in./min.
  • the pulling speed may be varied within limits (depending upon the operating temperature) without any substantial change in the cross-section of the grown crystal.
  • the operating temperature may be varied substantially (e.g., a change of as much as 15-30 degrees with respect to the melting point of alumina) without any substantial change in the cross-section of the grown crystal.
  • An important advantage of the invention is that it is applicable to crystalline materials other than alumina. It is not limited to congruently melting materials and encompasses growth of materials that solidify in cubic, rhombohedral, hexagonal and tetragonal crystal structures, including ruby, spinel, beryllia, barium titanate, yttrium aluminum garnet, lithium niobate, lithium fluoride and calcium fluoride. With respect to such other materials, the process is essentially the same as that described for alphaalumina, except that it requires different operating temperatures because of different melting points and diiferent seed crystals selected according to the material to be grown. Additionally, certain minor changes may be required in the apparatus e.g., diflerent crucible and die materials selected according to the reactivity and melting points of the melt material.
  • Laue X-ray back reflection photographs of crystal growth produced according to the foregoing invention reveals that the crystal growth usually comprises one or two and in some cases three or four crystals growing together longitudinally separated by a low angle (usually With in 4 of the c-direction) grain boundary. Therefore, for convenience and in the interest of avoiding any suggestion that the crystal growth is polycrystalline in character, we prefer to describe it as essentially monocrystalline, it being understood this term is intended to embrace a crystalline body that is comprised of a single crystal or two or more crystals, e.g., a bicrystal or tricrystal, growing together longitudinally but separated by a relatively small angle (i.e., less than about 4) grain boundary. The same term is used to denote the crystallographic nature of the seed tube.
  • end surface is intended to cover the effective film-supporting surface of the die
  • capillary is intended to denote a passageway that can take a variety of cross-sectional forms such as rectangular bores or an annular space.
  • effective film-supporting surface denotes the end surface of the die, e.g., surface 44, as it would appear if the capillary Opening or openings, e.g., capillary 46, were omitted, since when a film fully covers the end surface it extends over the capillary openings.
  • rotational transformation is intended to encompass shapes of the type shown in FIG. 14 as well as those of the type shown in FIGS. 5, 8, and 10.
  • the significant advantage of the invention is that it makes it possible to grow essentially monocrystalline bodies in a variety of complex geometric shapes for different uses.
  • the rod 38C of FIG. 13 is modified so that its upper surface 44C has the shape of an air cross-section, it is possible with the apparatus of FIGS. 11 and 12 to grow a curved body similar to that of FIG. 14 except that its cross-section will be like that of an air foil.
  • Such a body, if made of a high temperature material, is adaptable for use as a turbine blade.
  • An elongate essentially monocrystalline body having (1) a longitudinal axis, (2) a predetermined arbitrary cross-section, and (3) a longitudinally extending inner surface characterized by a rotational transformation relative to said longitudinal axis.
  • An elongate essentially monocrystalline body having a predetermined arbitrary cross-section and a transformation of said cross-section along a selected axis.
  • a body according to claim 10 wherein said crosssection is rotationally transformed about the geometric axis of said body.
  • a body according to claim 10 wherein said crosssection is rotationally transformed about an axis that is exterior to said body.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Geometry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
US00196449A 1971-11-08 1971-11-08 Production of crystalline bodies of complex geometries Expired - Lifetime US3846082A (en)

Priority Applications (11)

Application Number Priority Date Filing Date Title
BE791024D BE791024A (fr) 1971-11-08 Procede pour developper des cristaux a partir d'un bain d'une matiere
US00196449A US3846082A (en) 1971-11-08 1971-11-08 Production of crystalline bodies of complex geometries
GB4986172A GB1382529A (en) 1971-11-08 1972-10-30 Production of crystalline bodies of complex geometries
CA155,843A CA974859A (en) 1971-11-08 1972-11-07 Production of crystalline bodies of complex geometries
BR7786/72A BR7207786D0 (pt) 1971-11-08 1972-11-07 Processo para producao de corpos essencialmente monocristalinos com superficies externas e ou internas de formas complexas
IT53863/72A IT973428B (it) 1971-11-08 1972-11-07 Procedimento per la produzione di corpi cristallini di forme geometri che controllate a partire da una massa fusa e prodotto ottenuto
FR7239404A FR2159339B1 (member.php) 1971-11-08 1972-11-07
JP47111956A JPS5215075B2 (member.php) 1971-11-08 1972-11-08
CH1625772A CH576283A5 (member.php) 1971-11-08 1972-11-08
NL7215097A NL7215097A (member.php) 1971-11-08 1972-11-08
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US4323418A (en) * 1978-11-10 1982-04-06 Hitachi, Ltd. Method for growing a pipe-shaped single crystal
US4612972A (en) * 1982-01-04 1986-09-23 Olin Corporation Method and apparatus for electro-magnetic casting of complex shapes
WO1988007598A1 (en) * 1987-03-27 1988-10-06 Mobil Solar Energy Corporation An apparatus and process for edge-defined, film-fed crystal growth
US4937053A (en) * 1987-03-27 1990-06-26 Mobil Solar Energy Corporation Crystal growing apparatus
WO1992001091A1 (en) * 1990-07-10 1992-01-23 Saphikon, Inc. Apparatus for growing hollow crystalline bodies from the melt
WO1992003204A1 (en) * 1990-08-15 1992-03-05 Mobil Solar Energy Corporation Method of growing cylindrical tubular crystalline bodies
US5114528A (en) * 1990-08-07 1992-05-19 Wisconsin Alumni Research Foundation Edge-defined contact heater apparatus and method for floating zone crystal growth
US5266151A (en) * 1992-03-04 1993-11-30 Advanced Crystal Products Corporation Inside edge defined, self-filling (IESF) die for crystal growth
US5346883A (en) * 1987-08-21 1994-09-13 The Furukawa Electric Co., Ltd. Method of manufacturing superconductive products
US5370078A (en) * 1992-12-01 1994-12-06 Wisconsin Alumni Research Foundation Method and apparatus for crystal growth with shape and segregation control
US5683949A (en) * 1994-02-14 1997-11-04 General Electric Company Conversion of doped polycrystalline material to single crystal material
US6722873B2 (en) * 2001-09-10 2004-04-20 Recot, Inc. Apparatus for producing a curly puff extrudate
US20050034581A1 (en) * 2003-08-12 2005-02-17 Eugenio Bortone Method and apparatus for cutting a curly puff extrudate
US20050066881A1 (en) * 2003-09-25 2005-03-31 Canon Kabushiki Kaisha Continuous production method for crystalline silicon and production apparatus for the same
US20050227117A1 (en) * 2004-04-08 2005-10-13 Saint-Gobain Ceramics & Plastics, Inc. Single crystals and methods for fabricating same
US20070068375A1 (en) * 2005-06-10 2007-03-29 Saint-Gobain Ceramics & Plastics, Inc Transparent ceramic composite
US20080075941A1 (en) * 2006-09-22 2008-03-27 Saint-Gobain Ceramics & Plastics, Inc. C-plane sapphire method and apparatus
US20090130415A1 (en) * 2007-11-21 2009-05-21 Saint-Gobain Ceramics & Plastics, Inc. R-Plane Sapphire Method and Apparatus
USD641538S1 (en) * 2010-04-02 2011-07-19 Last Twist, Inc. Pretzel stick
USD641536S1 (en) * 2010-04-02 2011-07-19 Last Twist, Inc. Frozen confection
USD641537S1 (en) * 2010-04-02 2011-07-19 Last Twist, Inc. Sausage
RU2451117C2 (ru) * 2010-06-09 2012-05-20 Федеральное государственное унитарное предприятие Экспериментальный завод научного приборостроения со Специальным конструкторским бюро Российской академии наук Устройство для выращивания профилированных кристаллов в виде полых тел вращения
US11047650B2 (en) 2017-09-29 2021-06-29 Saint-Gobain Ceramics & Plastics, Inc. Transparent composite having a laminated structure

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US4647437A (en) * 1983-05-19 1987-03-03 Mobil Solar Energy Corporation Apparatus for and method of making crystalline bodies
FR2712608B1 (fr) * 1993-11-16 1996-01-12 Commissariat Energie Atomique Procédé de fabrication de pièces en matériau polycristallin ou monocristallin par croissance à partir d'un bain fondu.

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US3199956A (en) * 1962-10-18 1965-08-10 Technicon Instr Cocurrent packed helical coil extractor
US3370927A (en) * 1966-02-28 1968-02-27 Westinghouse Electric Corp Method of angularly pulling continuous dendritic crystals
US3561931A (en) * 1966-08-06 1971-02-09 Siemens Ag Eccentric feed rotation in zone refining
US3591348A (en) * 1968-01-24 1971-07-06 Tyco Laboratories Inc Method of growing crystalline materials

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US3031275A (en) * 1959-02-20 1962-04-24 Shockley William Process for growing single crystals
US3033660A (en) * 1959-05-05 1962-05-08 Philips Corp Method and apparatus for drawing crystals from a melt
US3199956A (en) * 1962-10-18 1965-08-10 Technicon Instr Cocurrent packed helical coil extractor
US3370927A (en) * 1966-02-28 1968-02-27 Westinghouse Electric Corp Method of angularly pulling continuous dendritic crystals
US3561931A (en) * 1966-08-06 1971-02-09 Siemens Ag Eccentric feed rotation in zone refining
US3591348A (en) * 1968-01-24 1971-07-06 Tyco Laboratories Inc Method of growing crystalline materials

Cited By (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4323418A (en) * 1978-11-10 1982-04-06 Hitachi, Ltd. Method for growing a pipe-shaped single crystal
US4612972A (en) * 1982-01-04 1986-09-23 Olin Corporation Method and apparatus for electro-magnetic casting of complex shapes
WO1988007598A1 (en) * 1987-03-27 1988-10-06 Mobil Solar Energy Corporation An apparatus and process for edge-defined, film-fed crystal growth
GB2210287A (en) * 1987-03-27 1989-06-07 Mobil Solar Energy Corp An apparatus and process for edge-defined, film-fed crystal growth
US4937053A (en) * 1987-03-27 1990-06-26 Mobil Solar Energy Corporation Crystal growing apparatus
GB2210287B (en) * 1987-03-27 1990-07-11 Mobil Solar Energy Corp An apparatus and process for edge-defined, film-fed crystal growth
US5346883A (en) * 1987-08-21 1994-09-13 The Furukawa Electric Co., Ltd. Method of manufacturing superconductive products
US5398640A (en) * 1990-07-10 1995-03-21 Saphikon, Inc. Apparatus for growing hollow crystalline bodies from the melt
WO1992001091A1 (en) * 1990-07-10 1992-01-23 Saphikon, Inc. Apparatus for growing hollow crystalline bodies from the melt
US5114528A (en) * 1990-08-07 1992-05-19 Wisconsin Alumni Research Foundation Edge-defined contact heater apparatus and method for floating zone crystal growth
WO1992003204A1 (en) * 1990-08-15 1992-03-05 Mobil Solar Energy Corporation Method of growing cylindrical tubular crystalline bodies
US5266151A (en) * 1992-03-04 1993-11-30 Advanced Crystal Products Corporation Inside edge defined, self-filling (IESF) die for crystal growth
US5370078A (en) * 1992-12-01 1994-12-06 Wisconsin Alumni Research Foundation Method and apparatus for crystal growth with shape and segregation control
US5683949A (en) * 1994-02-14 1997-11-04 General Electric Company Conversion of doped polycrystalline material to single crystal material
US7157039B2 (en) 2001-09-10 2007-01-02 Frito-Lay North America, Inc. Method and apparatus for producing a curly puff extrudate
US6722873B2 (en) * 2001-09-10 2004-04-20 Recot, Inc. Apparatus for producing a curly puff extrudate
US20040089968A1 (en) * 2001-09-10 2004-05-13 Eugenio Bortone Method and apparatus for producing a curly puff extrudate
US20080054513A1 (en) * 2003-08-12 2008-03-06 Eugenio Bortone Method and Apparatus for Cutting a Curly Puff Extrudate
US20050034581A1 (en) * 2003-08-12 2005-02-17 Eugenio Bortone Method and apparatus for cutting a curly puff extrudate
US20050066881A1 (en) * 2003-09-25 2005-03-31 Canon Kabushiki Kaisha Continuous production method for crystalline silicon and production apparatus for the same
US20100282160A1 (en) * 2004-04-08 2010-11-11 Saint-Gobain Ceramics & Plastics, Inc. Single crystals and methods for fabricating same
US8157913B2 (en) 2004-04-08 2012-04-17 Saint-Gobain Ceramics & Plastics, Inc. Method of forming a sapphire single crystal
US8685161B2 (en) 2004-04-08 2014-04-01 Saint-Gobain Ceramics & Plastics, Inc. Method of forming a sapphire crystal using a melt fixture including thermal shields having a stepped configuration
US7348076B2 (en) 2004-04-08 2008-03-25 Saint-Gobain Ceramics & Plastics, Inc. Single crystals and methods for fabricating same
US20050227117A1 (en) * 2004-04-08 2005-10-13 Saint-Gobain Ceramics & Plastics, Inc. Single crystals and methods for fabricating same
US9963800B2 (en) 2004-04-08 2018-05-08 Saint-Gobain Ceramics & Plastics, Inc. Method of making a sapphire component including machining a sapphire single crystal
USRE43469E1 (en) 2004-04-08 2012-06-12 Saint-Gobain Ceramics & Plastics, Inc. Single crystals and methods for fabricating same
US9926645B2 (en) 2004-04-08 2018-03-27 Saint-Gobain Ceramics & Plastics, Inc. Method of forming a single crystal sheet using a die having a thermal gradient along its length
US7584689B2 (en) 2005-06-10 2009-09-08 Saint-Gobain Ceramics & Plastics, Inc. Transparent ceramic composite armor
US7793580B2 (en) 2005-06-10 2010-09-14 Saint-Gobain Ceramics & Plastics, Inc. Transparent ceramic composite
US20100288117A1 (en) * 2005-06-10 2010-11-18 Saint-Gobain Ceramics & Plastics Transparent Ceramic Composite
US20090308239A1 (en) * 2005-06-10 2009-12-17 Saint-Gobain Ceramics & Plastics Transparent Ceramic Composite
US20070068376A1 (en) * 2005-06-10 2007-03-29 Saint-Gobain Ceramics & Plastics, Inc. Transparent ceramic composite
US8297168B2 (en) 2005-06-10 2012-10-30 Saint-Gobain Ceramics & Plastics, Inc. Transparent ceramic composite
US8025004B2 (en) 2005-06-10 2011-09-27 Saint-Gobain Ceramics & Plastics, Inc. Transparent ceramic composite
US20070068375A1 (en) * 2005-06-10 2007-03-29 Saint-Gobain Ceramics & Plastics, Inc Transparent ceramic composite
US20080075941A1 (en) * 2006-09-22 2008-03-27 Saint-Gobain Ceramics & Plastics, Inc. C-plane sapphire method and apparatus
US8652658B2 (en) 2006-09-22 2014-02-18 Saint-Gobain Ceramics & Plastics, Inc. C-plane sapphire method and apparatus
US20090130415A1 (en) * 2007-11-21 2009-05-21 Saint-Gobain Ceramics & Plastics, Inc. R-Plane Sapphire Method and Apparatus
USD641537S1 (en) * 2010-04-02 2011-07-19 Last Twist, Inc. Sausage
USD641536S1 (en) * 2010-04-02 2011-07-19 Last Twist, Inc. Frozen confection
USD641538S1 (en) * 2010-04-02 2011-07-19 Last Twist, Inc. Pretzel stick
RU2451117C2 (ru) * 2010-06-09 2012-05-20 Федеральное государственное унитарное предприятие Экспериментальный завод научного приборостроения со Специальным конструкторским бюро Российской академии наук Устройство для выращивания профилированных кристаллов в виде полых тел вращения
US11047650B2 (en) 2017-09-29 2021-06-29 Saint-Gobain Ceramics & Plastics, Inc. Transparent composite having a laminated structure

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DE2254616B2 (de) 1974-11-28
CA974859A (en) 1975-09-23
BE791024A (fr) 1973-05-07
JPS4875482A (member.php) 1973-10-11
BR7207786D0 (pt) 1973-09-27
DE2254616C3 (de) 1975-07-10
JPS5215075B2 (member.php) 1977-04-26
CH576283A5 (member.php) 1976-06-15
FR2159339A1 (member.php) 1973-06-22
DE2254616A1 (de) 1973-05-10

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