US3620686A - Method for solidifying while rubbing the solid-liquid interface - Google Patents

Method for solidifying while rubbing the solid-liquid interface Download PDF

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Publication number
US3620686A
US3620686A US851656A US3620686DA US3620686A US 3620686 A US3620686 A US 3620686A US 851656 A US851656 A US 851656A US 3620686D A US3620686D A US 3620686DA US 3620686 A US3620686 A US 3620686A
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Prior art keywords
solid
rubbing
liquid
interface
phase
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Expired - Lifetime
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US851656A
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English (en)
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William G Pfann
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AT&T Corp
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Bell Telephone Laboratories Inc
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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
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • C30B11/007—Mechanisms for moving either the charge or the heater
    • 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
    • C30B21/00—Unidirectional solidification of eutectic materials
    • C30B21/02—Unidirectional solidification of eutectic materials by normal casting or gradient freezing
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S420/00—Alloys or metallic compositions
    • Y10S420/902—Superplastic
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S505/00—Superconductor technology: apparatus, material, process
    • Y10S505/80—Material per se process of making same
    • Y10S505/815—Process of making per se

Definitions

  • the rubbing should break up the diffusion layer in the liquid, which is, typically, enriched in one or more of the constituents, and the equilibrium segregation coefficient between the solid and the liquid should be realized in normal freezing.
  • F inc-grained microstructures have recently become of interest in the field of superplasticity and an important application of normal freezing of a single-phase material is in the desalination of water.
  • FIG. 1 A first figure.
  • the invention pertains to the production of a solid from a melt or solution by directional freezing.
  • microstructures can be obtained by heat treatment alone such as the Zn-Al system in which a range of alloys is single phaseat elevated temperatures and two phase at room temperature. The phase transformation upon cooling produces the desired fine microstructure. Ithas been found to be difficult to produce fine-grained microstructures in single-phase materials because it is the presence of the second phase which limits grain growth.
  • Normal freezing is an important process in material purification because of the fact that during solidification thereis, typically, a large difference betweenthe concentration-of an impurity in the liquid and in the solid. If, for instance, the solid contains a much lower concentration than the liquid, the impurities are swept ahead of the advancing liquid-solidinterface. This produces an artificially high concentration of the impurities in the diffusion layer in the liquid at the interface. This causes the inclusion in the solid of more-ofthe impurity than would be deduced from the consideration of the equilibrium distribution coefficient. It hasbeen found that this diffusion layer cannot be broken up by the agitation or stirring of the liquid alone.
  • the SUMMARY OF THE INVENTION of the boundary layer allows a much closer approach to the equilibrium distribution of any dissolved substances between the liquid andthe solid.
  • the application of the invention does not necessarily lead to a material decrease in grain size since grain growth is not-inhibited by the presence of a second phase.
  • the microstructure may be modified in that the grains, although only somewhat smaller, are still roughly equiaxial and not elongated in the growth direction by the lO-to-Al ratios which are typical of directionally solidified materials.
  • This widely applicable method for producing finegrained alloys requires very little mechanical energy 'since it operates very near the melting point of the material where the material is weak.
  • the invention is applicable to a wide range of nonmetallic inorganic and organic multiphased systems.
  • the use of the invention will lead to more effective segregation of impurities during normal freezing.
  • the purpose of this normal freezing might be the purification of the body of the solid such as in the desalination of water or the concentration of the impurities in the liquid or at the end of the solid for easier identification.
  • FIG. 1 is a perspective viewpartly in section of an exemplary solidification apparatus
  • FIG. 2 is a perspective view of a wedge rubbing body
  • FIG. 3 is a perspective view of a rotary file rubbing body.
  • the invention described in this disclosure is applicable to a wide range of materials,'systems of materials and combinations of materials.
  • multiphase metallic and nonmetallic systems and single-phase materials with or without minor constituents or impurities include, for example, eutectic systems such as Pb-Sn, Sn-Zn, AlqSi, and Ag-Cu, and noneutectic systems such as the phosphor bronzes and the Al-laase, Ni-base and Zn.-base casting alloys.
  • nonmetallic organic and inorganic multiphase systems are azobenzene-benzyl and carbon tetrabromidehexachloroethane.
  • the single-phase materials to which this invention is'applicable include all crystalline materials which can be grown from a melt or solution.
  • the metals are Pb, Sn, Bi, and Ge, and semiconducting compounds, such-as InSb.
  • the many organic compounds are 'benzoic acid and acetanilide.
  • One of the more important inorganic systems is water containing salt in solution..
  • An apparatus embodying the disclosed invention-must possess some means for producing directional solidification, a nonreacting solid rubbing body and a means for producing the rubbing motion.
  • One possible method of producing directional solidification for a suitable material system is the introductionof enough heat in one part of the apparatus to maintain the material in a molten state and the removal of that heat in another part-of the apparatus.
  • Some means must be provided to maintain the rubbing 'body in contact with the advancing solid-liquid interface. Compound structures can be obtained, if desired, by providing this rubbing action over only part of the surface of the solidifying body..
  • FIG. 1 shows an exemplary apparatus which includes a heater 15 which may provide thermal energy directly or may provide high-frequency electromagnetic energy if the solidifying liquid is a conductor of electricity or contained in a conductor.
  • a heater 15 which may provide thermal energy directly or may provide high-frequency electromagnetic energy if the solidifying liquid is a conductor of electricity or contained in a conductor.
  • the thermal energy is removed in a coolant bath 11.
  • the motion of the rubbing body 14 which is depicted as a wire brush is produced by a motion generator 16 which may be a simple rotator.
  • the containing tube 19 is lowered at a controlled rate through the heater 15 into the coolant bath 11.
  • a number of trials of this invention TABLE 1.Pb-Sn SYSTEM Grain size (micron G th Rotation -------6-t--;1
  • the average grain size produced in all of these trials varied between about 5 and 20 microns which is in the range of interest for superplasticity lAlden, Acta Met 15 (1967) 471]. There is no lamellar or dendritic substructure evident in these grains.
  • the unrubbed areas immediately adjacent to the rubbed areas showed the typical grain size between 100 and 2,000 microns when looking at a section taken transverse to the growth direction.
  • the grains, when looking at a longitudinal section, were typically greater than 2 millimeters long parallel to the direction of solidification. These grains showed the typical lamellar and dendritic substructures.
  • These trials indicated that rubbing rate and growth rate were not a dominant factor in determining grain size.
  • the trials indicate that the grain size is dependent on annealing time at temperatures near the solidification temperature so that faster growth rates and larger temperature gradients should yield smaller grain size or even amorphous materials. Superplastic elongation was demonstrated using materials so produced.
  • a method for the production of a crystalline solid selected from the group consisting of metal, semiconductor or organic compound from a liquid mass by unidirectional solidification characterized in that a nonreacting solid body is maintained in contact with and rubbed against at least a portion of the solidifying surface area of said crystalline solid during solidification at the interface between said crystalline solid and said liquid mass.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Manufacture And Refinement Of Metals (AREA)
US851656A 1969-08-20 1969-08-20 Method for solidifying while rubbing the solid-liquid interface Expired - Lifetime US3620686A (en)

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US (1) US3620686A (xx)
BE (1) BE754962A (xx)
DE (1) DE2041476A1 (xx)
FR (1) FR2058114A5 (xx)
GB (1) GB1318725A (xx)
NL (1) NL7012111A (xx)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2229453A1 (de) * 1971-06-16 1972-12-28 Massachusetts Institute of Technolo gy, Cambridge, Mass (V St A) Verfahren zum Herstellen einer metal hschen Flussig Fest Mischung fur Gießver fahren
US3709284A (en) * 1971-11-19 1973-01-09 Airco Inc Apparatus for continuous casting
US3902544A (en) * 1974-07-10 1975-09-02 Massachusetts Inst Technology Continuous process for forming an alloy containing non-dendritic primary solids
US3948650A (en) * 1972-05-31 1976-04-06 Massachusetts Institute Of Technology Composition and methods for preparing liquid-solid alloys for casting and casting methods employing the liquid-solid alloys
US3951651A (en) * 1972-08-07 1976-04-20 Massachusetts Institute Of Technology Metal composition and methods for preparing liquid-solid alloy metal compositions and for casting the metal compositions
US3954455A (en) * 1973-07-17 1976-05-04 Massachusetts Institute Of Technology Liquid-solid alloy composition
US4465545A (en) * 1982-07-30 1984-08-14 The Board Of Trustees Of The Leland Stanford Junior University Method of growing single crystal cadmium telluride
US4540550A (en) * 1982-10-29 1985-09-10 Westinghouse Electric Corp. Apparatus for growing crystals
US4610754A (en) * 1982-10-29 1986-09-09 Westinghouse Electric Corp. Method for growing crystals
US4708763A (en) * 1984-08-23 1987-11-24 U.S. Philips Corporation Method of manufacturing bismuth germanate crystals
US4922995A (en) * 1987-04-08 1990-05-08 Institut Elektrosvarki Imeni E.O. Patona An Ussr Method of producing monolithic metal blanks by freezing-on techniques
US6311760B1 (en) * 1999-08-13 2001-11-06 Asea Brown Boveri Ag Method and apparatus for casting directionally solidified article
US10046386B2 (en) 2007-04-06 2018-08-14 Ashley Stone Device for casting

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2985722B1 (fr) * 2012-01-13 2014-02-14 Commissariat Energie Atomique Procede de purification du silicium.

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1892806A (en) * 1929-08-31 1933-01-03 Ingvald O Pedersen Manufacture of drawn glass
US3208112A (en) * 1961-11-01 1965-09-28 Albert W Scribner Metal casting method and apparatus
US3321282A (en) * 1964-05-12 1967-05-23 Bayer Ag Vessel subdivided by partitions into several cells transversely to its longitudinal axis
US3470039A (en) * 1966-12-21 1969-09-30 Texas Instruments Inc Continuous junction growth
US3494139A (en) * 1967-01-23 1970-02-10 Virtis Co Inc Freeze concentrator

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1892806A (en) * 1929-08-31 1933-01-03 Ingvald O Pedersen Manufacture of drawn glass
US3208112A (en) * 1961-11-01 1965-09-28 Albert W Scribner Metal casting method and apparatus
US3321282A (en) * 1964-05-12 1967-05-23 Bayer Ag Vessel subdivided by partitions into several cells transversely to its longitudinal axis
US3470039A (en) * 1966-12-21 1969-09-30 Texas Instruments Inc Continuous junction growth
US3494139A (en) * 1967-01-23 1970-02-10 Virtis Co Inc Freeze concentrator

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2229453A1 (de) * 1971-06-16 1972-12-28 Massachusetts Institute of Technolo gy, Cambridge, Mass (V St A) Verfahren zum Herstellen einer metal hschen Flussig Fest Mischung fur Gießver fahren
US3709284A (en) * 1971-11-19 1973-01-09 Airco Inc Apparatus for continuous casting
US3948650A (en) * 1972-05-31 1976-04-06 Massachusetts Institute Of Technology Composition and methods for preparing liquid-solid alloys for casting and casting methods employing the liquid-solid alloys
US3951651A (en) * 1972-08-07 1976-04-20 Massachusetts Institute Of Technology Metal composition and methods for preparing liquid-solid alloy metal compositions and for casting the metal compositions
US3954455A (en) * 1973-07-17 1976-05-04 Massachusetts Institute Of Technology Liquid-solid alloy composition
US3902544A (en) * 1974-07-10 1975-09-02 Massachusetts Inst Technology Continuous process for forming an alloy containing non-dendritic primary solids
US4465545A (en) * 1982-07-30 1984-08-14 The Board Of Trustees Of The Leland Stanford Junior University Method of growing single crystal cadmium telluride
US4540550A (en) * 1982-10-29 1985-09-10 Westinghouse Electric Corp. Apparatus for growing crystals
US4610754A (en) * 1982-10-29 1986-09-09 Westinghouse Electric Corp. Method for growing crystals
US4708763A (en) * 1984-08-23 1987-11-24 U.S. Philips Corporation Method of manufacturing bismuth germanate crystals
US4922995A (en) * 1987-04-08 1990-05-08 Institut Elektrosvarki Imeni E.O. Patona An Ussr Method of producing monolithic metal blanks by freezing-on techniques
US6311760B1 (en) * 1999-08-13 2001-11-06 Asea Brown Boveri Ag Method and apparatus for casting directionally solidified article
US10046386B2 (en) 2007-04-06 2018-08-14 Ashley Stone Device for casting

Also Published As

Publication number Publication date
DE2041476A1 (de) 1971-03-04
FR2058114A5 (xx) 1971-05-21
NL7012111A (xx) 1971-02-23
GB1318725A (en) 1973-05-31
BE754962A (fr) 1971-02-01

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