WO1993005877A1 - Synthese sonochimique de metaux amorphes - Google Patents

Synthese sonochimique de metaux amorphes Download PDF

Info

Publication number
WO1993005877A1
WO1993005877A1 PCT/US1992/008133 US9208133W WO9305877A1 WO 1993005877 A1 WO1993005877 A1 WO 1993005877A1 US 9208133 W US9208133 W US 9208133W WO 9305877 A1 WO9305877 A1 WO 9305877A1
Authority
WO
WIPO (PCT)
Prior art keywords
amorphous
amorphous metal
organometallic
process according
volatile
Prior art date
Application number
PCT/US1992/008133
Other languages
English (en)
Inventor
Kenneth S. Suslick
Mark E. Grinstaff
Andrzej A. Cichowlas
Seok-Burm Choe
Original Assignee
Research Corporation Technologies, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Research Corporation Technologies, Inc. filed Critical Research Corporation Technologies, Inc.
Publication of WO1993005877A1 publication Critical patent/WO1993005877A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/002—Making metallic powder or suspensions thereof amorphous or microcrystalline
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/147—Alloys characterised by their composition
    • H01F1/153—Amorphous metallic alloys, e.g. glassy metals
    • H01F1/15341—Preparation processes therefor

Definitions

  • the present invention relates to the novel synthesis of amorphous metals, metal powders, or metallic glasses, and uses thereof in a variety of applications, with such applications being their use as a catalytic material and their use as a soft magnetic material.
  • the present invention further relates to the sonochemical synthesis of these novel amorphous metals through the application of high intensity ultrasound to volatile organometallic or inorganic compounds. More particularly, this invention is directed to the synthesis of substantially pure amorphous iron and its use as a highly active catalyst for the Fischer-Tropsch hydrogenation of carbon monoxide and for hydrogenolysis and dehydrogenation of saturated hydrocarbons.
  • Amorphous materials are those materials which lack an ordered crystalline structure. This property is characteristic of liquids, in which the molecules do not have long range order in their atomic positions. All simple liquids are amorphous.
  • a solid material characteristically exhibits a molecular or atomic lattice structure which gives it a well-defined structural order over distances long compared to atomic dimensions.
  • glass retains the amorphous nature of a liquid even though it is physically rigid.
  • Metallic glasses, or amorphous metals or metal alloys are metals or metal alloys having an amorphous atomic structure analogous to that of silica glass, thus the origin of the terms "metallic glasses” and "glassy metals". These amorphous structures, as previously explained, lack long range crystalline order.
  • Metallic glasses can be obtained by subjecting a molten metal or alloy to extremely rapid cooling or quenching. The molten material is cooled so rapidly that a crystalline structure is prevented from being formed.
  • the vitreous material which is produced is predominantly amorphous and exhibits unique combinations of properties that make it capable of various applications.
  • Some known amorphous materials have exceptionally high mechanical strength and still maintain some ductility, some are exceedingly corrosion resistant and others are excellent soft magnetic materials.
  • Amorphous metals are often soft ferromagnets and as such have the potential to be used in the recording and magnetic tape industry, and more specifically in connection with magnetic read/write recording heads. Glassy metals can exhibit permeability comparable to, or higher than Permalloy, yet they are mechanically tough and not easily deformed.
  • a related commercial development of amorphous metals is their use in power transformer cores.
  • Amorphous metals with their high permittivity could replace the current transformer materials and greatly improve the energy efficiency of such power devices.
  • Amorphous materials lack grain boundaries and are consequently often chemically robust, making their use as protective coatings and materials in corrosive chemical environments such as acid batteries, sea water, etc., very beneficial.
  • Amorphous metals also have the potential to be reactive catalysts for the petroleum and chemical industries.
  • the Fischer-Tropsch process for example, converts synthesis gas, initially produced by the gasification of coal with steam and oxygen, to largely aliphatic hydrocarbons over an iron or cobalt catalyst.
  • Other processes such as dehydrogenation and hydrogenolysis are also used heavily in this area.
  • commercially available crystalline iron powders are used as catalysts.
  • amorphous metallic alloys are produced using expensive and technically difficult methods that involve the splattering of molten metals onto cold surfaces and the rapid cooling thereof with techniques such as gun, roller, or splat quenching.
  • all prior iron- containing metallic glasses contain large amounts of other alloying elements with greater than 20% being typical. See the aforementioned references along with Takashi, S. J. Matl. Sci. Lett. 6.: 844 (1987) and Luborsky, F.E., ed. Amorphous Metallic Alloys (Butterworths, London, 1983).
  • Ultrasound can induce extraordinary local, transient heating in otherwise cool liquids, with subsequently enormous cooling rates, in excess of 10 9 K/sec.
  • Ultrasound provides a unique interaction of energy and matter. For less than a few microseconds, it can produce in liquids an intense localized heating of 5500°C, almost the temperature at. the surface of the sun.
  • high intensity ultrasound is defined as ultrasound having sufficient intensity to create cavitation in a liquid.
  • “Cavitation” meaning the formation, expansion, oscillation and compression of bubbles in a liquid, can occur in the presence of ultrasound or other turbulent flow.
  • the exposure of a liquid to ultrasound is referred to as “irradiation” and the breaking of a chemical bond or bonds by the application of ultrasonic irradiation is known as “sonolysis”. Consequently, the production or synthesis of a chemical or chemical material through the use of ultrasound is called “sonochemical synthesis”.
  • acoustic cavitation As indicated above, the chemical effects of ultrasound derive from the physical phenomenon of acoustic cavitation: the creation, growth, and implosive collapse of bubbles in liquids. If the sound field in a liquid is sufficiently intense, bubbles will form in the liquid during the expansion cycle. The oscillations of the sound field make these bubbles grow and contract. At a certain size, the bubbles can be driven into an implosive collapse. Because compression of a gas creates heat, this implosion generates an intense, but short lived, hot-spot. In essence, acoustic cavitation effectively concentrates energy by transferring the low energy density of sound into the high energy density of a collapsing bubble. Ultrasound is currently being used to enhance various chemical reactions. Such "sonochemistry" includes the creation of clean and highly reactive surfaces on metals and the initiation or enhancement of catalytic reactions.
  • the present invention is directed to novel, substantially pure amorphous materials, both amorphous metals and amorphous metallic alloys, and their use as highly active heterogeneous catalysts.
  • the present invention is further directed to the process for making these novel amorphous materials which comprises using the conditions created by high intensity ultrasound to volatile organometallic or inorganic compounds.
  • amorphous metal obtained via the process of the present invention is amorphous iron.
  • Substantially pure, i.e., at least 96%, amorphous iron was produced from the sonolysis of iron pentacarbonyl, Fe(CO) 5 . Because the present process uses volatile organometallic or inorganic compounds of broad scope, the number of pure amorphous metals and metal alloys which can be produced using the present technique can also be quite large.
  • FIG. 1 is a scanning electron micrograph of an amorphous iron powder synthesized by the process of the present invention, obtained on a Hitachi S800 electron microscope.
  • Figure 2 is a transmission electron micrograph of an amorphous iron powder synthesized by the process of the present invention, obtained on a Phillips EM400T electron microscope.
  • Figure 3 is a differential scanning calorimetry of an amorphous iron powder synthesized by the process of the present invention vs. a crystalline iron- powder, obtained at 10°C/min. on a DuPont 1090 calorimeter.
  • Figure 4a shows the x-ray diffraction patterns of the amorphous iron powder synthesized by the process of the present invention before heat treatment.
  • Figure 4b shows the x-ray diffraction patterns of the amorphous iron powder of Figure 4a after crystallization at 350°C for six hours. Both Figures 4a and 4b were obtained on a Rigaku D-max diffractometer.
  • a new synthetic route to amorphous metals for example, metal powders, has been found which yields substantially pure amorphous materials, the purity of which was not obtainable up to the present invention.
  • the novel amorphous metals of the present invention are formed. More specifically, the process of making an amorphous metal in accordance with the present invention comprises irradiating a volatile organometallic or inorganic compound with high intensity ultrasound for a time and under conditions sufficient to convert the organometallic or inorganic compound into the amorphous metal.
  • volatile organometallic compounds may be used in the present process and include metal carbonyls such as Fe(CO) 5 , Cr(CO) 6 , Mo(CO) 6 , W(CO) 6 , Mn 2 (CO) 10 , and Ni(CO) 4 and other volatile organometallic compounds such as Pd(allyl) 2 , etc.
  • metal carbonyls such as Fe(CO) 5 , Cr(CO) 6 , Mo(CO) 6 , W(CO) 6 , Mn 2 (CO) 10 , and Ni(CO) 4
  • volatile organometallic compounds such as Pd(allyl) 2 , etc.
  • volatile inorganic compounds which may be used in the present process are, for example, TiCl 4 and Zr(BH 4 ) 4 .
  • the amorphous alloys of the present invention can be prepared from the ultrasonic irradiation of solutions containing two or more volatile organometallic or inorganic compounds as well as from solutions containing volatile organometallic or inorganic compounds and volatile main group compounds, wherein said main group compounds are compounds containing boron, carbon, nitrogen, silicon, phosphorus, sulfur, arsenic, selenium, antimony, tellurium or halide.
  • a preferred process includes the following steps:
  • Vapor pressure of the reaction mixture plays an important roll in the acoustic cavitation step.
  • the vapor of the inorganic or organometallic precursor should be as large a fraction of the total reaction mixture vapor as possible to enhance the yield and rate of amorphous metal formation.
  • a variety of solvents may be used in the present process with positive results, for optimum yield of the amorphous metals, it is best to utilize a low volatility or low vapor pressure solvent, i.e. a solvent having a vapor pressure approximately below 50 Torr or 0.1 atm.
  • a low volatility or low vapor pressure solvent i.e. a solvent having a vapor pressure approximately below 50 Torr or 0.1 atm.
  • decane and pentane are very similar solvents
  • decane is preferred because it is a low vapor pressure solvent and consequently better results are obtained through the use of decane.
  • liquids are also potentially useful if these liquids are relatively non-reactive and have low vapor pressures under irradiation conditions. These include, but are not limited to, aromatic liquids, ethers and polyethers, polysiloxanes, and molten salts.
  • Alkane solvents are especially useful in this process; these include saturated aliphatic hydrocarbons such as pentane, heptane, octane, decane and dodecane. Those solvents with a low vapor pressure under the reaction conditions employed herein during ultrasonic irradiation are preferred. Alkanes or other solvents that are solids at room temperatures may also be useful if the reaction is heated above their melting points.
  • dissolved gas in the liquid reaction mixture is also important. Monatomic gases are preferred relative to diatomic which are preferred relative to polyatomic gases due to their effect on the heating process during gas compression.
  • the thermal conductivity of the dissolved gas should be as low as practical.
  • the reactivity of the dissolved gas must be considered; for example, in the presence of oxygen the formation of iron oxides will occur during ultrasonic irradiation of Fe(CO) 5 .
  • xenon is preferred relative to krypton which is preferred relative to argon. In practice, argon offers an excellent compromise of cost and desirable properties.
  • the sonochemical synthesis of metallic glasses can be accomplished with low cost ultrasonic equipment. Gram quantities are easily prepared with simple laboratory ultrasonic sources of 400 W, and scale up with commercially available modular 20 kW industrial units can be readily achieved. In order to control the system vapor pressure, it is important that the reaction volume be controlled, e.g. thermostated.
  • the products of the invention are substantially pure.
  • substantially pure as employed herein and in the appended claims means purity levels of at least about 90%, and usually above 95%.
  • amorphous iron powder produced in accordance with the present invention is of an order of purity in excess of 95%. Yields approaching the 100% purity level are contemplated.
  • High resolution transmission electron micrographs reveal the icrostructure of the amorphous iron powder (See Figure 2).
  • the large particles shown in Figure 1 are composites of very small particles (lOnm) with significant void volume. Surface areas were determined by BET gas adsorption and found to be 120 m /g, which is 150 times greater than 5 ⁇ m diameter iron powder commercially available (Aldrich Chemicals).
  • the sonochemically produced amorphous iron powder sinters at unusually low temperatures. Upon treatment at 350°C, the amorphous powder becomes metallic in color and the scanning electron micrographs show loss of porosity and growth of 50 nm crystallites. This is the case when ultrasonic irradiation is done at low vapor pressure and with a dissolved gas that has a low thermal conductivity and a large ratio of the heat capacities cp/cv.
  • the magnetic properties of the amorphous iron powder have also been examined.
  • the sonochemically produced iron glass is a soft ferromagnet. It has a very low coercivity of 10 gauss at 25°C. This is a highly desirable property for various magnetic information storage and power transformer applications.
  • the catalytic activity of the amorphous iron powder was probed with two commercially important reactions: the Fischer-Tropsch process (i.e., hydrogenation of CO) and the hydrogenolysis and dehydrogenation of saturated hydrocarbons.
  • the conversion of carbon monoxide and hydrogen to low molecular weight alkanes occurred at very low reaction temperatures (200°C).
  • the amorphous powder was roughly ten times more reactive per gram than 5 ⁇ m diameter crystalline iron powder.
  • the hydrogenolysis and dehydrogenation of cyclohexane was about 100 times more efficient at 250°C for the sonochemically produced amorphous iron compared to crystalline iron.
  • the ratio of dehydrogenation to hydrogenolysis depended on temperature, but could be made as large as 0.6. It is believed that the high surface area of the amorphous iron accounts for much of the increase in chemical reactivity. As expected, crystallization and sintering of the metallic glass powders at >300°C significantly decrease their catalytic activity.

Abstract

La présente invention concerne de nouveaux métaux amorphes pratiquement purs et la synthèse sonochimique de ceux-ci consistant à iradier des composés organométalliques volatils avec des ultrasons haute intensité. La présente invention concerne également l'emploi de métaux amorphes comme catalyseurs de réaction pour divers procédés tels que l'hydrogénation Fischer-Tropsch de monoxyde de carbone et pour l'hydrogénolyse et la déshydrogénation d'hydrocarbures saturés. Est également décrite l'utilisation de ces métaux amorphes comme matériaux ferromagnétiques doux.
PCT/US1992/008133 1991-09-25 1992-09-25 Synthese sonochimique de metaux amorphes WO1993005877A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US76564791A 1991-09-25 1991-09-25
US765,647 1991-09-25

Publications (1)

Publication Number Publication Date
WO1993005877A1 true WO1993005877A1 (fr) 1993-04-01

Family

ID=25074107

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1992/008133 WO1993005877A1 (fr) 1991-09-25 1992-09-25 Synthese sonochimique de metaux amorphes

Country Status (2)

Country Link
AU (1) AU2682492A (fr)
WO (1) WO1993005877A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5766306A (en) * 1996-06-04 1998-06-16 The Boeing Company Continuous process for making nanoscale amorphous magnetic metals
US6376063B1 (en) 1998-06-15 2002-04-23 The Boeing Company Making particulates of controlled dimensions by electroplating
US7208028B2 (en) * 2002-12-30 2007-04-24 Korean Institute Of Machinery And Materials Method of producing nanophase W powder by low-pressure vapor phase reaction
CN109317164A (zh) * 2018-09-27 2019-02-12 扬州中天利新材料股份有限公司 非晶态金属催化剂及醇铝的制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2674528A (en) * 1951-01-22 1954-04-06 Gen Aniline & Film Corp Production of metal carbonyl powders of small size
EP0147581A1 (fr) * 1983-11-09 1985-07-10 Studiengesellschaft Kohle mbH Procédé de production de Magnésium en forme très divisée et très active et son utilisation
EP0423627A1 (fr) * 1989-10-14 1991-04-24 Studiengesellschaft Kohle mbH Procédé de préparation de poudre d'un métal ou d'un alliage microcristallin à amorphe, ainsi que des métaux ou alliages dissous dans des solvants organiques sans colloide protecteur
EP0469463A1 (fr) * 1990-07-31 1992-02-05 Studiengesellschaft Kohle mbH Composés métal-magnésium, leur procédé de préparation et leur utilisation pour la préparation de poudres fines de métal et d'alliages et de composés intermétalliques

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2674528A (en) * 1951-01-22 1954-04-06 Gen Aniline & Film Corp Production of metal carbonyl powders of small size
EP0147581A1 (fr) * 1983-11-09 1985-07-10 Studiengesellschaft Kohle mbH Procédé de production de Magnésium en forme très divisée et très active et son utilisation
EP0423627A1 (fr) * 1989-10-14 1991-04-24 Studiengesellschaft Kohle mbH Procédé de préparation de poudre d'un métal ou d'un alliage microcristallin à amorphe, ainsi que des métaux ou alliages dissous dans des solvants organiques sans colloide protecteur
EP0469463A1 (fr) * 1990-07-31 1992-02-05 Studiengesellschaft Kohle mbH Composés métal-magnésium, leur procédé de préparation et leur utilisation pour la préparation de poudres fines de métal et d'alliages et de composés intermétalliques

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SCIENTIFIC AMERICAN, Vol. 260, No. 2, February 1989 Suslick K.S : "The Chemical Effects of Ultrasound ", *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5766306A (en) * 1996-06-04 1998-06-16 The Boeing Company Continuous process for making nanoscale amorphous magnetic metals
US6376063B1 (en) 1998-06-15 2002-04-23 The Boeing Company Making particulates of controlled dimensions by electroplating
US6699579B2 (en) 1998-06-15 2004-03-02 The Boeing Company Particulates of controlled dimension
US7208028B2 (en) * 2002-12-30 2007-04-24 Korean Institute Of Machinery And Materials Method of producing nanophase W powder by low-pressure vapor phase reaction
CN109317164A (zh) * 2018-09-27 2019-02-12 扬州中天利新材料股份有限公司 非晶态金属催化剂及醇铝的制备方法
CN109317164B (zh) * 2018-09-27 2021-05-04 扬州中天利新材料股份有限公司 非晶态金属催化剂及醇铝的制备方法

Also Published As

Publication number Publication date
AU2682492A (en) 1993-04-27

Similar Documents

Publication Publication Date Title
Suslick et al. Sonochemical synthesis of amorphous iron
Baiker Metallic glasses in heterogeneous catalysis
US4537624A (en) Amorphous metal alloy powders and synthesis of same by solid state decomposition reactions
Yu et al. Preparation of amorphous NiCoB alloys and the effect of cobalt on their hydrogenation activity
US4537625A (en) Amorphous metal alloy powders and synthesis of same by solid state chemical reduction reactions
Suslick Applications of ultrasound to materials chemistry
Shafi et al. Sonochemical preparation and characterization of nanosized amorphous Co–Ni alloy powders
KR100979761B1 (ko) 나노사이즈 백금-티타늄 합금을 제조하는 방법
EP0650762A1 (fr) Catalyseur et procédé de reformage de méthanol et procédé de préparation de ce catalyseur
JP2007031799A (ja) 金属ナノ粒子の製造方法
US9309119B2 (en) Producing method of metal fine particles or metal oxide fine particles, metal fine particles or metal oxide fine particles, and metal-containing paste, and metal film or metal oxide film
US5766306A (en) Continuous process for making nanoscale amorphous magnetic metals
WO1993005877A1 (fr) Synthese sonochimique de metaux amorphes
Shafi et al. Preparation and magnetic properties of nanosized amorphous ternary Fe–Ni–Co alloy powders
WO2006090151A1 (fr) Procede de formation d'un alliage metallique nanocristallin
JPS6111148A (ja) アンモニア合成用鉄基剤触媒の製造方法および該方法により取得される触媒
US4783329A (en) Hydriding solid solution alloys having a body centered cubic structure stabilized by quenching near euctectoid compositions
Kim et al. Bimodal NdNiAl and NdFeB hybrid catalytic and magnetic nanoparticles laminated on Fe foam: catalytic conversion of CO+ 3H 2 to CH 4
US4485080A (en) Process for the production of diamond powder
JP3382343B2 (ja) メタノールの水蒸気改質用触媒の製造方法
US3856581A (en) Annealing air-stable magnetic materials having superior magnetic characteristics and method
EP2590765B1 (fr) Nanoparticules métalliques
Klein et al. Synthesis of submicron aluminum particles via thermal decomposition of alkyl aluminum precursors in the presence of metal seeds and their application in the formation of ruthenium aluminides
Baiker Glassy metals in catalysis
US3732091A (en) Method for preparing mutual dispersions of carbides and metals or alloys and novel products thereof

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU CA JP KP

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL SE

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA