US3117934A - Garnet growth from barium oxide-boron oxide flux - Google Patents

Garnet growth from barium oxide-boron oxide flux Download PDF

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Publication number
US3117934A
US3117934A US103366A US10336661A US3117934A US 3117934 A US3117934 A US 3117934A US 103366 A US103366 A US 103366A US 10336661 A US10336661 A US 10336661A US 3117934 A US3117934 A US 3117934A
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Prior art keywords
garnet
oxide
flux
range
iron
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Expired - Lifetime
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US103366A
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English (en)
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Jr Robert C Linares
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AT&T Inc
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Bell Telephone Laboratories Inc
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Priority to US103366A priority Critical patent/US3117934A/en
Priority to BE611557A priority patent/BE611557A/fr
Priority to GB1412/62A priority patent/GB993533A/en
Priority to SE428962A priority patent/SE211086C1/sv
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • 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
    • C30B9/00—Single-crystal growth from melt solutions using molten solvents
    • C30B9/04—Single-crystal growth from melt solutions using molten solvents by cooling of the solution
    • C30B9/08—Single-crystal growth from melt solutions using molten solvents by cooling of the solution using other solvents
    • C30B9/12—Salt solvents, e.g. flux growth
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/26—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on ferrites
    • C04B35/2608—Compositions containing one or more ferrites of the group comprising manganese, zinc, nickel, copper or cobalt and one or more ferrites of the group comprising rare earth metals, alkali metals, alkaline earth metals or lead
    • 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
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
    • C30B29/22—Complex oxides
    • C30B29/28—Complex oxides with formula A3Me5O12 wherein A is a rare earth metal and Me is Fe, Ga, Sc, Cr, Co or Al, e.g. garnets
    • 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
    • C30B9/00—Single-crystal growth from melt solutions using molten solvents

Definitions

  • This invention relates to a method for growing single crystals of synthetic garnet in a fiux comprising barium oxide-boron oxide.
  • the synthetic garnet materials considered here can be represented by the formulas M Me O or M Me (MeO,) where O is oxygen, Me is a trivalent metal and M is yttrium or one of the rare earth elements of atomic number between 62 and 71 or a mixture of these rare earth elements with each other or with yttrium. Me may be at least one of the elements trivalent iron, gallium, seandium, chromium or cobalt.
  • single crystals of ferrimagnetic material show enhancement of certain magnetic properties associated with the polycrystalline material.
  • the resonance lines of single crystal materials are much narrower than those found in the polycrystalline material, this property forming the basis for the types of microwave devices described in copending application Serial No. 778,352, filed December 5, 1958, now US. Patent 3,016,495, issued on January 9, 1962, to P. K. Tien, and Serial No. 774,172, filed November 17, 1958, now US. Patent 3,013,229, issued on December 12, 1961, to R. W. De Grasse.
  • a convenient prior art method for producing such single crystals consisted of combining the reactants in proper proportions with a flux consisting of lead oxide, heating the mixture to form a homogeneous liquid, and forming the single crystals from a molten bath by standard crystallization procedures. This technique is discussed in detail in US. Patent 2,957,827, issued October 25, 1960, to l. W. Nielsen.
  • the present invention embodies the same general procedures as the aforementioned crystal growing methods with the exception of the flux employed.
  • the present inventive method utilizes a flux comprising barium oxide and boron oxide.
  • the use of such a flux is advantageous in several respects, the most important being that garnet growth may occur in a nontoxic congruently saturating system.
  • the FTGURE is a graphical representation on coordinates of temperature in degrees centigrade against solubility in weight percent of yttrium iron garnet showing the solubility curves of various compositions of yttrium oxide and ferric oxide in a barium oxide-boron oxide flux ratio of 3.54:1.
  • Ann important aspect of the present invention lies in the use of specific flux ratios, that is, critical ratios of barium oxide to boron oxide.
  • specific flux ratios that is, critical ratios of barium oxide to boron oxide.
  • the weight ratio of barium oxide to boron oxide be within the range of 3.16:1 to 4.55:1. It has been found that the use of a ratio of barium oxide to boron oxide of less than about 3.16: 1 results in the formation of barium ferrite, so decreasing the yield of the desired crystal and increasing the difiiculty of separation of this material 3,ll7,934 Patented Jan. 14, 1964 from the desired garnet. Studies on the growth of garnets with this flux have extended up to ratios of 4.55:1 at which point orthoferrites begin to form. An optimum ratio has been found to be 3.54:1.
  • the general procedure for crystallization processes involving the garnet systems generally employs 1300 C. as the upper limit of temperature. This limitation is set by reason of considerations pertaining to volatility of ingredients in solution, and changing composition of flux et cetera.
  • the present inventive technique permits crystallization of the garnet structures discussed above from a congruently saturating system, that is, one in which stoichiometric amounts of nutrient are employed.
  • the barium oxide-boron oxide system is not limited to stoichiornetric concentrations when trivalent iron is present and excesses of ferric oxide up to percent may be employed.
  • Curve B repre sents the optimum for crystallization rmiges in the system discussed and indicates that a flux containing an excess of 27 percent ferric oxide has the greatest crystallization range, namely, 1255 to 990 C.
  • Curves C, D, and E represent incomplete solubility curves for solutions containing up to 90 percent excess ferric oxide. It is noted that lines LM and PQ define the precise ranges in which the process can be operated without pro ducing the unwanted barium ferrite and yttrium orthoferrite.
  • the temperature range for garnet growth may vary over the range of 1255 C. to 990 C. dependent upon the particular materials and concentrations employed as discussed above.
  • Cooling rates may vary from as low as /2 C. per hour or lower to as high as 20 C. per hour. It is generally desirable to cool as slowly as possible to secure the largest possible crystal size and consequently a cooling rate of as low as /2" C. per hour is most desirable.
  • a mixture of the starting materials was weighed into a 100 cubic centimeter platinum crucible and sealed with a platinum lid.
  • the crucible was next placed into an electrically-heated furnace, was heated to a temperature of about 1260 C. and was maintained at such temperature for four hours. Controlled cooling at the rate of l to 5 C. per hour from the maximum of 1260 C. was then commenced by controlled energization of the furnace. This program was continued until approximately 975 C. At this point, the crucible was removed from the furnace and the still liquid portion poured off. After pouring off the liquid the crystals still in the crucible were permitted to cool. This is tantamount to an air quench, cooling taking of the order of one hour to reach the ambient temperature.
  • the crucible was then immersed in a vessel containing a dilute solution of nitric acid and water of the order of 30 percent by volume.
  • the acid cleaning procedure was continued until all flux residue has been removed from the crystals.
  • acid cleaning at room temperature takes of the order of four hours, although this is variable, being dependent on' the amount of residue, size of the charge, and number of clusters.
  • M is at least one member selected from the group consisting of yttrium and rare earth elements having an atomic number within the range of 62 to 71
  • Me is at least one trivalent metal selected from the group consisting of trivalent iron, gallium, scandium, chromium and cobalt
  • O is oxygen which comprises heating a nutrient consisting essentially of the constituent components of said garnet in stoichiometric amounts additionally containing up to 90 percent excess iron by weight when the trivalent matter selected is iron to a temperature of about 1260 C.
  • a flux consisting essentially of a mixture of barium oxide and boron oxide, the weight ratio of barium oxide to boron oxide being in the range of 3.16:1 to 4.55:1, the gross nutrient to flux ratio being in' the range of 1:1.8 to 1:4.5 by weight and cooling the resultant melt whereby said garnet precipitates from the melt in crystals.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Metallurgy (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
US103366A 1961-04-17 1961-04-17 Garnet growth from barium oxide-boron oxide flux Expired - Lifetime US3117934A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US103366A US3117934A (en) 1961-04-17 1961-04-17 Garnet growth from barium oxide-boron oxide flux
BE611557A BE611557A (fr) 1961-04-17 1961-12-14 Procédé d'obtention de monocristaux du type grenat
GB1412/62A GB993533A (en) 1961-04-17 1962-04-12 Improvements in or relating to the growth of single crystals of synthetic garnet
SE428962A SE211086C1 (fr) 1961-04-17 1962-04-17

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US103366A US3117934A (en) 1961-04-17 1961-04-17 Garnet growth from barium oxide-boron oxide flux

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BE (1) BE611557A (fr)
GB (1) GB993533A (fr)
SE (1) SE211086C1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3384449A (en) * 1965-07-07 1968-05-21 Army Usa Method of growing single crystals of ba2 zn2 fe12 o22
US3386799A (en) * 1965-11-16 1968-06-04 Bell Telephone Labor Inc Growth of yttrium iron garnet
US3630667A (en) * 1969-04-01 1971-12-28 Stackpole Carbon Co Production of barium ferrite
US3671436A (en) * 1969-03-20 1972-06-20 Philips Corp Method of manufacturing a sintered oxidic ferromagnetic body
US4116752A (en) * 1974-03-01 1978-09-26 Sakai Chemical Industry Co., Ltd. Production of single crystalline ferrite particles
US4199396A (en) * 1976-06-24 1980-04-22 Union Carbide Corporation Method for producing single crystal gadolinium gallium garnet
CN114182339A (zh) * 2021-10-29 2022-03-15 中国科学院福建物质结构研究所 一种生长稀土掺杂钇铁石榴石单晶材料的方法
RU2861078C1 (ru) * 2025-11-06 2026-04-28 Общество с ограниченной ответственностью "КрОМ" Способ получения монокристаллов оксида иттрия

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2957827A (en) * 1957-04-30 1960-10-25 Bell Telephone Labor Inc Method of making single crystal garnets

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2957827A (en) * 1957-04-30 1960-10-25 Bell Telephone Labor Inc Method of making single crystal garnets

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3384449A (en) * 1965-07-07 1968-05-21 Army Usa Method of growing single crystals of ba2 zn2 fe12 o22
US3386799A (en) * 1965-11-16 1968-06-04 Bell Telephone Labor Inc Growth of yttrium iron garnet
US3671436A (en) * 1969-03-20 1972-06-20 Philips Corp Method of manufacturing a sintered oxidic ferromagnetic body
US3630667A (en) * 1969-04-01 1971-12-28 Stackpole Carbon Co Production of barium ferrite
US4116752A (en) * 1974-03-01 1978-09-26 Sakai Chemical Industry Co., Ltd. Production of single crystalline ferrite particles
US4199396A (en) * 1976-06-24 1980-04-22 Union Carbide Corporation Method for producing single crystal gadolinium gallium garnet
CN114182339A (zh) * 2021-10-29 2022-03-15 中国科学院福建物质结构研究所 一种生长稀土掺杂钇铁石榴石单晶材料的方法
RU2861078C1 (ru) * 2025-11-06 2026-04-28 Общество с ограниченной ответственностью "КрОМ" Способ получения монокристаллов оксида иттрия

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Publication number Publication date
BE611557A (fr) 1962-03-30
SE211086C1 (fr) 1967-02-21
GB993533A (en) 1965-05-26

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