US3883944A - Method of preparing oxidation resistant materials and structures - Google Patents
Method of preparing oxidation resistant materials and structures Download PDFInfo
- Publication number
- US3883944A US3883944A US426867A US42686773A US3883944A US 3883944 A US3883944 A US 3883944A US 426867 A US426867 A US 426867A US 42686773 A US42686773 A US 42686773A US 3883944 A US3883944 A US 3883944A
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- Prior art keywords
- chromium
- aluminum
- diffusion
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- alloys
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Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
- F28F21/08—Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
- F28F21/081—Heat exchange elements made from metals or metal alloys
- F28F21/084—Heat exchange elements made from metals or metal alloys from aluminium or aluminium alloys
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K20/00—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating
- B23K20/22—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating taking account of the properties of the materials to be welded
- B23K20/227—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating taking account of the properties of the materials to be welded with ferrous layer
- B23K20/2275—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating taking account of the properties of the materials to be welded with ferrous layer the other layer being aluminium
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
- C23C10/30—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes using a layer of powder or paste on the surface
-
- 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
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49826—Assembling or joining
- Y10T29/49888—Subsequently coating
-
- 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
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/4998—Combined manufacture including applying or shaping of fluent material
- Y10T29/49982—Coating
Definitions
- ABSTRACT Preparation of iron-base alloys, particularly in the form of regenerator cores and other similar matrices, by the codiffusion of aluminum and chromium, using aluminum-iron alloy powder and chromium, aluminum-iron alloy powder and chromium-iron powder or AlCr alloy powder as sources of the aluminum and chromium and an atmosphere of mixed I-1 and HF to accomplish in situ formation of the aluminum and chromium and their diffusion, and alloying with the iron-base alloy. Assemblies may be bonded to form an integrated structure along with the heating for diffusion of aluminum and chromium.
- This invention relates generally to materials and to matrix structures of oxidation resistant iron-base alloys.
- the term iron-base alloy is used herein to define low carbon mild steel and similar iron-base alloys.
- This invention relates to a method of diffusing aluminum and chromium into iron-base alloys and iron-base matrix assemblies and the simultaneous bonding of iron-base alloy assemblies to form integral structures.
- the invention is specifically directed to regenerator cores for turbine engines although it is applicable to similar matrix structures wherein low carbon, mild steel and iron parts form various passageways, the walls of which are to be diffusion alloyed with chromium and aluminum and the parts of which are to be bonded together.
- mild steel or low carbon steel is commonly used and is used herein to describe well-known steels, particularly commercial steels, containing less than about 0.25 percent by weight carbon, balance iron and the usual impurities.
- examples of some commercial low carbon irons are Armco Supersoft (Armco Steel Co.), Bethnamel (Bethlehem Steel Corp.) and Vitrenamel (United States Steel Corp.).
- An example of a low carbon mild steel is USS Steel Foil (United States Steel Corp).
- Chromium requires high temperatures in excess of about 1,200 F. to initiate diffusion. At such a temperature, metallic aluminum wets the work piece surface and prevents the diffusion of the chromium into it.
- the present invention uses source materials for the aluminum and chromium which in combination with a certain atmosphere form proper amounts of aluminum and chromium in situ for codiffusion thereby overcoming many of the problems typically associated with the diffusion of these elements.
- This invention makes use of a novel approach in order to codiffuse aluminum and chromium and thereby provide oxidation resistant material.
- the source of the diffusing metals (aluminum and chromium) is placed in close proximity to the substrate.
- a slurry technique has been found to be very successful in this invention as a means of distributing the source of materials, directly on a substrate, such as the surfaces of a matrix assembly in the form of a regenerator core and in producing good alloying and bonding of the parts thereof by the diffusion of the aluminum and chromium as provided herein.
- Both chromium and aluminum are formed in situ at the substrate and diffused into the substrate material during a heating cycle in the presence of hydrogen and HF gas.
- the source of the aluminum is an iron-aluminum or chromium-aluminum alloy while the source of chromium may be chromium per se, an aluminum-chromium alloy or an iron-chromium alloy.
- chromium or Cr as a source material it should be taken to include not only the metal per se but CrFe and CrAl alloys as well as mixtures of Cr and CrFe or CrAl alloys.
- iron-aluminum or chromium aluminum alloys as a source of aluminum and chromium, chromium aluminum alloys or ironchromium alloys as source materials of chromium for diffusion into low carbon iron or mild steel to provide oxidation resistant materials and structures.
- regenerator cores of a novel relatively inexpensive material It is also an object to provide regenerator cores of a novel relatively inexpensive material.
- FIG. 1 is a plan view showing a regenerator core for a turbine engine and indicating the matrix structure thereof;
- FIG. 2 is an end view of FIG. 1;
- FIG. 3 is a fragmentary enlarged plan view of a portion of the matrix illustrated in FIG. 1 showing the bonded joints thereof;
- FIG. 4 is a graph illustrating the effect of atmosphere flow rate on the method of the invention.
- FIG. 5 is a graph illustrating the effect of temperature and time on the method of the invention.
- FIG. 6 is a graph illustrating the effect of slurry composition on the method of the invention with Fe-Al Cr as the source material
- FIG. 7 is a graph illustrating the effects of the diffusion atmosphere composition on the method of the invention with FeAl Cr as the source material;
- FIG. 8 illustrates and classifies the oxidationresistance of various AlCr materials at 1,400 F. in circulating air, the results being expressed in terms of weight gain due to oxidation;
- FIG. 9 is a graph illustrating the oxidation resistance of various portions of a specific regenerator matrix sample, 93.5 percent Recovery meaning that 93.5 percent of the slurry materials diffused and alloyed;
- FIG. 10 is a graph illustrating variations in slurry retention during dipping in terms of withdrawal rate, SWG meaning slurry weight gain as a result of dip- P g;
- FIGS. 11 and 12 are graphs illustrating the variations in slurry retention with changes in viscosity for several binder compositions, P & S meaning Pierce and Stevens Co;
- FIGS. 13 and 14 illustrate slurry distribution through the cross-section of a core sample resulting from dipping and its effect on resultant composition therethrough;
- FIG. 15 is a graph illustrating oxidation resistance of the cold and hot faces of are'generator core sample according to the invention having compositional variation, the alloy distribution curves being plotted on the lower ordinate, the centered curve being an oxidation weight gain curve plotted on the upper ordinate.
- the passageways in the particular design shown are formed by alternately positioned corrugated layers of low carbon iron stock and flat layers of low carbon iron stock. Other variations and designs are known. To form an integral structure theseparts are bonded together and lastly, the rim and hub are attached. The method of the invention is preferably performed on the matrix of the core prior to the attachment of the rim and hub.
- the codiffusion of aluminum and chromium into lowcarbon iron material is most efficient at high temperatures when the metals to be diffused are in close proximity or immediate physical contact with the iron base workpiece.
- the source materials are aluminum-iron and either chromium or chromium-iron or the source materials are aluminumchromium alloys, which are placed in contact with the workpiece and heated at high temperatures in a certain Reactions CrF Al CrF AlF
- the first two reactions promote the formation of fluorides.
- the other reactions indicate the reduction of these fluorides and intermediate fluorides by either hydrogen or the metals.
- the last three reactions show the actual deposition of chromium and aluminum on the surface of the workpiece.
- FIG. 4 demonstrates that the amount of materials diffused in creases as flow rate decreases and is best when the atmosphere is static.
- the amount of diffused material is expressed in terms of the approximate percent reacted and may include minor amounts trapped in some passages but not actually reacted. This is also referred to as the percent recovered.
- Pure aluminum is an active reducing agent. If used in its elemental form, it will result timewise in the premature reduction of the chromium fluorides to metallic chromium and monoaluminum fluoride at too low a temperature for the effective diffusion of aluminum into the iron. For this reason, among others, this invention substitutes aluminum alloys for pure aluminum as a source material.
- the preferred iron-aluminum alloy, preferably l:l, for example, is much less reactive and has a much higher melting point than aluminum alone. With iron-aluminum, premature reaction at low temperature is delayed until a more favorable temperature is reached and consequently a higher aluminum and chromium alloy content is produced during heating and diffusion according to the method of this invention.
- the preferred method for contacting the source materials and the workpiece comprises dipping the workpiece into a slurry containing the suspended source materials.
- Procedure 1 Decarburizing In the case of materials and assemblies using mild steel, carbon removal is usually necessary. This may be accomplished by placing thev material or assembly into a suitable heat resistant con-.
- 20Cr-80Al and 66Cr34Al may be used also. If the 'alloy is to be prepared as a powder for use in a slurry the 15-60% Cr, balance Al should be used because it is brittle and easily powdered.
- Fe-Cr alloy of 67.2% Cr balance Fe a commercial alloy has been used.
- Low carbon, low silicon ferrochromes are desirable in whichthecarbon is less than aluminum (1:1 alloy composition, by weight) powder and chromium powder mixed in the 4:5 ratio by weight and suspended in a binder such as Pierce & Stevens.
- Binder No. 9658 which is a solution of an'acrylic resin in toluene. Additions of. aluminum palmitate may be used to control the viscosity. 3 3.
- the matrix assembly is put together andv clamped, brazed, decarburized, or the'like, for temporarily holding it together. It may be cleaned and then coated with the above slurry, preferably by dipping and preferably to obtain a weight gain of about 30 percent.
- Regenerator core samples made from 0.002 inch stock exhibiting a weight gain of about5 mg/cm of surface area were found to be acceptable for turbine engine use.
- the assembly is next sealed in a suitable container which is placed in a furnace and heated up to about 700-800 F. under a flow of argon substantially to remove the binder vehicle.
- a diffusion atmosphere of hydrogen and hydrogen fluoride (about 1 percent hydrogen fluoride by volume, balance hydrogen, is preferred although about 1-5 percent is acceptable) is introduced into the container. This can be achieved by long time purging or by evacuating the container and refilling with the H -HF atmosphere.
- a positive pressure (about 4 to 6 inches of oil on an oil manometer) is preferably maintained in the con tainer during the heating and diffusing-bonding cycle, which is, for example, preferably about hours at a holding temperature of about 2,000 F. for stock having a thickness on the order of 0.002 inches.
- the container is purged with argon until room temperature is reached.
- the assembly may be weighed upon removal from the container, after loose residue has been blown out, to determine the amount of source materials used. This was the basis for the data in the graphs of FIGS. 4, 6
- Fluoride residues may subsequently be eliminated by heating the, assembly for approximately '1 hour at temperatures above l,700 F. in a wet hydrogen atmosphere.
- Source Materials CrAl alloy of 30% Cr, balance A] has been used.
- Commercially available alloys such as l5Cr-85Al,
- the silicon is less than 2 percent and the chromium runs about64-75 percent.
- Fe-Al alloy of 50% Fe 50% Al has been used. It is a commercially available material. Use of an alloy of about 45 70% Al provides one which is rather brittle and easily powdered for use in a slurry. The 50-50 alloy typically sold for use in permanent magnets is sat isfactory.
- Oxidation resistance at l,400 F. is the principal quality criterion of workpieces treated by the method of this invention. Samples were tested at that temperature in a circulating air furnace. Their weight gain, in
- results The following results list a selection of those typically obtained under different conditions for sample regenerator cores of the type shown in FIGS. 1, 2 and 3.
- the method is applicable to other matrix structures such as those shown in Hubble US. Pat. No. 3,532,157 and Topouzian US. Pat. No. 3,391,727 and the so called sunburst core.
- the diffusion treatment of this invention is believed to result in the sintering of any unreacted metal powder to the inside of the matrix passages.
- the calculated percent reacted figures therefore, include residual source materials, which do not contribute to the oxidation resistance of the substrate.
- these figures as the weightpercent of slurry constituents retained in the regenerator after the diffusion cycle, were found to be a good indication of the efficiency of the process.
- the samples referred to herein were segments cut from 10 inch diameter cores previously diffusion bonded (without AlCr diffusion) to prevent the various layers of flat and corrugated stock from coming only partially representative of the bonding of a full- 5 apa t during sectioning and subsequent processing. size unit.
- the flat and corrugated strips Samples were approximately 1 by 1 inch in sect on and forming the mat i a e bl t d t i t i a ithe length was the full thickness of an actual regeneraform contact pressure between the successive layers.
- FIG. 5 illustrates that the depth of diffusion may be With reference to FIGS. 5, 6 and 7, it can be seen obtained in shorter time intervals at higher temperathat the variables of (1) time and temperature, (2) tures with the converse also being true.
- FIG. 6 illusslurry composition and (3) atmosphere composition trates how diffusion appears to be best at a ratio of are all interrelated and should be considered insofar as Fit-Al to Cr of about 4:5 as the relative amount of optimizing the subject invention for any particular aschromium increases, up to about 4:5, then dropping sembly or material concerned. off.
- FIG. 7 indicates that a mix of about 1% HF with H is optimum in the case of source materials of AlFe Cr.
- FIG. 8 demonstrates a preferred composition best suited to the purpose of this invention as can be seen from the parts of the graph which fall into the central square area thereof labeled best.
- the area labeled good is useful but is more expensive in that larger amounts of chrome are required without any substantial gain in oxidation resistance. Weight gain is of course an indication of the amount of oxidation.
- FIG. 9 shows the relative oxidation resistance of the top and bottom faces of a sample regenerator core 4 inches in diameter prepared by codiffusing Al and Cr at 2,000 F. for 2 hours according to the subject invention, the source of Aluminum being AlFe.
- regenerator cores different results may be obtained depending on the slurry operation.
- sample cores of the type shown in FIGS. 1 and 2, wherein one face is a hot face, the other being a cold face because of the difference in temperature to which the faces are exposed in actual use certain variables were found to provide certain results.
- the graphs thereof show that SWG increases with the viscosity of the slurry.
- other variables such as corrugation spacing, fold radius and passage uniformity in the matrix along with Al and Cr source particle size also affect SWG.
- a particle size of 325 mesh has been found to be acceptable in most cases, although this can vary a great deal.
- regenerator face containing the greater relative amounts of aluminum and chromium is used as the regenerator hot face while the other face is used as the cold face, the cold face not requiring the high temperature properties of the hot face.
- FIGS. 13, 14 and 15 and Table VII below demonstrates distribution of chromium and aluminum by incremental segmentational analysis before and after diffusion processing.
- a slurry is prepared consisting of iron-aluminum and chromium powders in a 4:5 ratio (by weight) suspended in a vehicle of acrylic binder, hexane and toluene in a ratio of 6:5:1 with the addition of 0.25 percent aluminum palmitateviscosity is adjusted to about 230 (at 78 F.) centipoises, as measured with a Brookfield Viscometer.
- a low carbon iron regenerator matrix assembly preferably pre-bonded by a simple diffusion heat treatment as described above at decarburizing is coated with the above slurry by dipping, involving a controlled withdrawal rate according to FIG. 10 of about 68 inches/minute.
- a cleaning procedure using low pressure compressed air, and blotting is used to remove the resultant drip edge. Drying with warm low pressure air follows.
- a preferred slurry weight gain of about 25 to 30 percent should be obtained. Adjustment of viscosity may be used to influence retention.
- any component, such as hub, rim, etc. to be brazed to the core is assembled using a copper flake slurry.
- the slurried core is then placed in the diffusion container on an Inconel screen coated with stop-of and supported on an Inconel grid. Control samples are located at the periphery of the core and a cover made of 316 stainless steel (0.015 inches) is welded on the container which may be Inconel also.
- the container is purged with argon while being heated to about 700 to 800 F. for a minimum of 2 hours to remove the acrylic binder from the dried slurry.
- the cooled container is then evacuated to a few millimeters of mercury.
- the preferred diffusion atmosphere consisting of hydrogen and hydrogen fluoride (1 percent by volume balance substantially H is bled in until internal pressure is back to atmospheric, preferably slightly higher, then the retort is further purged by flowing the gas mixture through it for an additional 15 minutes.
- the container gas outlet is then connected to an oil manometer to establish a static atmosphere and monitor pressure during the process.
- Final temperature of about 2,000 F. is held for 2 hours.
- the static atmosphere is maintained by manipulation of the pressure regulator on the gas mixture cylinder so as to maintain a preferred height of about 4 to 6 inches in the oil manometer.
- the furnace is turned off and the container is cooled at the highest practical rate.
- the hydrogen-hydrogen fluoride atmosphere is purged from the container with an inert gas, preferably argon.
- the processed core is cleaned of loose residue by blowing with compressed air.
- the aluminum source material being selected from the group consisting of Al--Fe alloys, AlCr alloys, and mixtures thereof
- the chromium source material being 'selected from the group consisting of Cr-Fe alloys, AlCr alloys, Cr and mixtures thereof at various surfaces of the matrix assembly
- the aluminum source being selected from the group consisting of Al--Fe alloys, AlCr alloys and mixtures thereof
- the chromium source being selected from the group consisting of Cr-Fe alloys, AlCr alloys, Cr and mixtures thereof
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Abstract
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Claims (8)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US426867A US3883944A (en) | 1972-12-27 | 1973-12-20 | Method of preparing oxidation resistant materials and structures |
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US00318785A US3807030A (en) | 1972-12-27 | 1972-12-27 | Method of preparing oxidation resistant materials |
US426867A US3883944A (en) | 1972-12-27 | 1973-12-20 | Method of preparing oxidation resistant materials and structures |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4081121A (en) * | 1974-12-13 | 1978-03-28 | C.E.R.C.A., Compagnie pour 1'Etude et la Realisation de Combustibles Atomiques | Method of high temperature assembly |
WO1999042633A1 (en) * | 1998-02-23 | 1999-08-26 | MTU MOTOREN- UND TURBINEN-UNION MüNCHEN GMBH | Method for producing a slip layer which is resistant to corrosion and oxidation |
US6110262A (en) * | 1998-08-31 | 2000-08-29 | Sermatech International, Inc. | Slurry compositions for diffusion coatings |
US6287695B1 (en) * | 1996-08-30 | 2001-09-11 | Eckart-Werke Standard Bronzepulver-Werke Carl Eckart Gmbh & Co. | Corrosion-stable aluminum pigments and process for the production thereof |
Citations (9)
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US3061462A (en) * | 1959-03-26 | 1962-10-30 | Chromalloy Corp | Metallic diffusion processes |
US3096205A (en) * | 1960-05-16 | 1963-07-02 | Chromalloy Corp | Diffusion coating of metals |
US3254405A (en) * | 1962-12-13 | 1966-06-07 | Martin Marietta Corp | Thermo-chemical joining of refractory metals |
US3342971A (en) * | 1964-06-16 | 1967-09-19 | Gen Dynamics Corp | Method for brazing super alloys and refractory metals |
US3372465A (en) * | 1965-05-03 | 1968-03-12 | Texas Instruments Inc | Method of bonding layers to an austenitic chromium steel core |
US3589927A (en) * | 1965-07-01 | 1971-06-29 | Albright & Wilson | Chromising of ferrous metal substrates |
US3623901A (en) * | 1968-11-18 | 1971-11-30 | Bethlehem Steel Corp | Formation of chromium-containing coatings on both sides of steel strip with one coated side having a bright finish |
US3624678A (en) * | 1966-09-15 | 1971-11-30 | Hughes Aircraft Co | Method for making dielectric-to-metal joints for slow-wave structure assemblies |
US3690943A (en) * | 1970-04-24 | 1972-09-12 | Rca Corp | Method of alloying two metals |
-
1973
- 1973-12-20 US US426867A patent/US3883944A/en not_active Expired - Lifetime
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
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US3061462A (en) * | 1959-03-26 | 1962-10-30 | Chromalloy Corp | Metallic diffusion processes |
US3096205A (en) * | 1960-05-16 | 1963-07-02 | Chromalloy Corp | Diffusion coating of metals |
US3254405A (en) * | 1962-12-13 | 1966-06-07 | Martin Marietta Corp | Thermo-chemical joining of refractory metals |
US3342971A (en) * | 1964-06-16 | 1967-09-19 | Gen Dynamics Corp | Method for brazing super alloys and refractory metals |
US3372465A (en) * | 1965-05-03 | 1968-03-12 | Texas Instruments Inc | Method of bonding layers to an austenitic chromium steel core |
US3589927A (en) * | 1965-07-01 | 1971-06-29 | Albright & Wilson | Chromising of ferrous metal substrates |
US3624678A (en) * | 1966-09-15 | 1971-11-30 | Hughes Aircraft Co | Method for making dielectric-to-metal joints for slow-wave structure assemblies |
US3623901A (en) * | 1968-11-18 | 1971-11-30 | Bethlehem Steel Corp | Formation of chromium-containing coatings on both sides of steel strip with one coated side having a bright finish |
US3690943A (en) * | 1970-04-24 | 1972-09-12 | Rca Corp | Method of alloying two metals |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4081121A (en) * | 1974-12-13 | 1978-03-28 | C.E.R.C.A., Compagnie pour 1'Etude et la Realisation de Combustibles Atomiques | Method of high temperature assembly |
US6287695B1 (en) * | 1996-08-30 | 2001-09-11 | Eckart-Werke Standard Bronzepulver-Werke Carl Eckart Gmbh & Co. | Corrosion-stable aluminum pigments and process for the production thereof |
WO1999042633A1 (en) * | 1998-02-23 | 1999-08-26 | MTU MOTOREN- UND TURBINEN-UNION MüNCHEN GMBH | Method for producing a slip layer which is resistant to corrosion and oxidation |
US6440499B1 (en) | 1998-02-23 | 2002-08-27 | Mtu Aero Engines Gmbh | Method for producing a slip layer which is resistant to corrosion and oxidation |
US6110262A (en) * | 1998-08-31 | 2000-08-29 | Sermatech International, Inc. | Slurry compositions for diffusion coatings |
US6444054B1 (en) | 1998-08-31 | 2002-09-03 | Sermatech International, Inc. | Slurry compositions for diffusion coatings |
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Owner name: CHRYSLER CORPORATION Free format text: PARTES REASSIGN, TRANSFER AND RELINQUISH THEIR ENTIRE INTEREST UNDER SAID PATENTS ALSO RELEASE THEIR SECURITY INTEREST.;ASSIGNOR:MANUFACTURERS NATIONAL BANK OF DETROIL (CORPORATE TRUSTEE) AND BLACK DONALD E., (INDIVIDUAL TRUSTEE);REEL/FRAME:004355/0154 Effective date: 19840905 |