US3367768A - Nickel powder - Google Patents

Nickel powder Download PDF

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Publication number
US3367768A
US3367768A US481157A US48115765A US3367768A US 3367768 A US3367768 A US 3367768A US 481157 A US481157 A US 481157A US 48115765 A US48115765 A US 48115765A US 3367768 A US3367768 A US 3367768A
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US
United States
Prior art keywords
powder
nitrogen
nickel
ammonia
carbonyl
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Expired - Lifetime
Application number
US481157A
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English (en)
Inventor
West De Witt Henry
Llewelyn David Myers
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huntington Alloys Corp
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International Nickel Co Inc
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Publication date
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/20—Dry methods smelting of sulfides or formation of mattes from metal carbonyls
    • 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
    • B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
    • B22F9/305—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis of metal carbonyls
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/06—Refining
    • C22B23/065—Refining carbonyl methods
    • 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
    • Y10S75/00—Specialized metallurgical processes, compositions for use therein, consolidated metal powder compositions, and loose metal particulate mixtures
    • Y10S75/953—Producing spheres

Definitions

  • Nickel carbonyl is decomposed in the hot free space of a decomposer and small amounts of ammonia and oxygen are mixed with the nickel carbonyl to produce substantially spherical carbonyl nickel powder.
  • This invention relates to carbonyl nickel powder, that is to say powder made by the thermal decomposition of nickel carbonyl vapour in the hot free space of a decomposer.
  • carbonyl nickel powder in this Way has been carried out on an industrial scale for many years, and it is well-established that according to the conditions of temperature, the concentration of carbonyl, and the presence or absence of diluent gases, e.g. carbon monoxide, the powder produced may assume one of two forms. These are the so-called A carbonyl nickel powder, which consists of discrete particles with an irregular spiky surface, and the so-called B powder, which consists of agglomerates of interlocking filaments or chains of interconnected (aggregated) particles which again are individually irregular. Type B powder has a low bulk density and has a microscopic appearance of small spongy flakes. The size of the aggregates of particles making up the chains can vary widely.
  • Another object of the invention is to provide a novel carbonyl nickel powder having a regular particle shape and high purity.
  • a further object of the invention is to provide a process of producing carbonyl nickel powder of regular particle shape by the thermal decomposition of nickel carbonyl.
  • the present invention is based on the discovery that when the decomposition of nickel carbonyl to nickel powder is carried out in the presence of a source of active or nascent nitrogen, that is to say, nitrogen formed in situ in the decomposer, so as to introduce at least 0.01% by weight of nitrogen into the powder, a remarkable and wholly unexpected change occurs in the form of the individual particles of nickel produced, which become substantially spherical.
  • a source of active or nascent nitrogen that is to say, nitrogen formed in situ in the decomposer, so as to introduce at least 0.01% by weight of nitrogen into the powder
  • the discrete particles produced in the presence of active nitrogen are no longer irregular and spiky, but are smooth and substantially spherical.
  • a similar change in the shape of the individual nickel particles occurs when the decomposition conditions are such as to lead, in the absence of active nitrogen, to the production of normal type B powder.
  • the product still consists of interlocking chains or filaments of particles, but when examined under very high magnication, for example by means of the electron microscope, these chains have the appearance of more or less branched linear aggregates of intergrown spheres.
  • carbonyl nickel powder has not hitherto been produced in the form of spherical particles, and the invention includes as novel products both the discrete and aggregated forms of carbonyl nickel powder having substantially spherical particles.
  • FIGURE l represents, at a magnification of X4000, a cluster of separate particles of conventional type A powder
  • FIGURE 2 represents, at the same magnification, a similar cluster of nitrogen-containing particles of type A nickel powder according to the invention
  • FIGURE 3 represents, at a magnification of 4500, part of a single aggregate of conventional type B powder particles.
  • FIGURE 4 represents, at a magnification of 6000, a similar type B aggregate from nitrogen-containing powder according to the invention.
  • the powders shown in FIGURES l and 3 each contained lessl than 0.01% nitrogen.
  • the type A powder of the invention shown in FIGURE 2 contained 0.016% nitrogen and had a bulk density of 2.97 g./cc., and a Fisher value of 5.5 microns, while the type B powder of the invention shown in FIGURE 4 contained 0.08% nitrogen, had a bulk density of 0.69 g./cc. and had a Fisher value of 2.6 microns.
  • the form of the powder particles is spherical it is necessary to introduce at least 0.01% by weight of nitrogen into the powder.
  • Some modification of the normal irregular, spiky shape of the particles occurs with even lower introgen contents, and as the nitrogen content is increased the particles become progressively more rounded until at a nitrogen content of 0.01% they are substantially spherical.
  • the nitrogen content may be as high as 0.2% or 0.3% or even higher, but increasing it above 0.01% does not materially change the shape of the individual particles.
  • the nitrogen contents in this specication refer to the powders in bulk. Owing to the nature of the endothermic reaction taking place, the conditions in an externally-heated carbonyl decomposer are not uniform throughout the hot free space. Hence it will be appreciated that a nickel powder product 0f the present process which has Spherical par- 10 omy of expensive ammonia, is obtained with an ammonia: ticles and in which the nitrogen content or" the product as a whole is at least 0.01%, will generally contain individual particles or aggregates of particles having nitrogen contents higher or lower than the average. We nd in If the nitrogen is to be active it is important that it should -be formed in the decomposer.
  • gaseous molecular nitrogen into the decomposer is quite 35 gen to carbonyl at an ammoniauoxygen ratio of 4:3 by volume, using a decomposer temperature of 290 C. All the powders produced were of A type.
  • the nitrogen content of the -powders decreased as the proportion of the inelective, and it is also ineifective to introduce ammonia alone.
  • the oxygen may be introduced in any convenient form, e.g. as
  • nickel powders are obtained in a carbonyl decomposer are now well understood. In general, conditions in which the rate of nucleation is high lead to the formation of type B powder, while a low rate of nucleation leads required.
  • the ammonia concentration is at least 0.3%. Pow der having spherical particles is formed at ammonia concentrations as high as 1% or even higher, but the use of such high concentrations is wasteful.
  • the oxygen concentration is preferably at least 0.15% by volume.
  • the ratio of ammonia to oxygen may be varied within wide limits, Ibut is preferably from 3:4 to 4:1 by volume. The greatest nitriding efciency, and hence the greatest econoxygen ratio of 4:3 by volume.
  • the invention also includes the process of producing favours the carburization of the powders. For this reason the gases fed to the decomposer should not contain more than traces of water vapour if lowcarbon powder is Numerous tests have been carried out to show the effect of changes in the process variables on the properties of the powder produced, and the results of these are set out in Tables I to IV below. In these tests carbon monoxide gas containing 7% by volume of nickel carbonyl (175 the novel nickel powder in which a mixture of ammonia grams nickel per cubic metre) was fed into an externally and oxygen is employed as the source of active or nascent nitrogen during the decomposition.
  • the nitrogen content of the powder increases as the concentration of ammonia in the decomposer increases. Generally speaking at least 0.2% by volume is needed particles, and were in accordance with the invention.
  • the powders of the invention have lower contents of combined carbon than nickel powder made under the same conditions in the absence of ammonia which usually contain from 0.05 to 0.08% carbon.
  • Carbonyl nickel powder is also commonly contaminated with a very small proportion, generally less than 0.01% by weight, of particles of very high carbon content, which are highly undesirable and have to be removed, e.g. by sieving.
  • the formation of such carbonaceous particles may be avoided in the present process by carrying out the decomposition in a decomposer of which the steel internal surfaces have been nitrided, e.g. by heating them in contact with ammonia gas at 500 C.
  • the novel carbonyl powders of the invention are characterized by very high purity, in particular very low contents of sulphur and of cobalt.
  • both the type A powder ders of the invention contain less than 0.0007% sulphur and less than 0.002% cobalt.
  • the spherical powders of the invention are particularly useful for powdermetallurgical purposes, since they have improved sintering properties compared with ordinary nickel powders of the same type.
  • spherical type A powder is found to sinter more readily to give bodies which have a very narrow range of pore sizes and are of interest for making electrodesA for fuel cells and lters.
  • the resulting sintered plate had a porosity of 28%, compared with 51% for an ordinary type A powder.
  • Spherical type B powder is particularly useful for making battery electrodes and other shaped centered bodies, since it has better flow properties than ordinary type B powder.
  • Nitrogen may readily be removed from the spherical powder of the invention by heating it at a moderate temperature, eg. 250 C., and substantially nitrogenfree spherical powder of either type A or type B may be produced in this way.
  • a powder having an average nitrogen content of 0.013% and containing 0.022% carbon was made by the process of the invention using a decomposer temperature of 240 C. and an ammoniamxygen ratio of 4:3.
  • the product was divided into tine and coarse fractions by sieving on a 15G-mesh sieve, and a small proportion (less than 1%) of very coarse material that was retained on a 30-mesh sieve was discarded.
  • the fine fraction which amounted to 70% of the whole, had a bulk density of 3.42 g./cc. and contained 0.016% nitrogen and 0.022% carbon, while the coarse fraction (about 30% of the Whole) had a bulk density of 1.87 g./cc. and contained only 0.005% nitrogen and 0.022% carbon.
  • the nickel particles in both fractions Were spherical. In the course fraction, the particles were highly-aggregated into dense clusters and had very good flow properties. This material is particularly useful for powdermetallurgical purposes, since its carbon content is no higher than the average for the whole of the powder,
  • Carbonyl nickel powder having substantially spherical particles and containing at least 0.01% nitrogen.
  • Carbonyl nickel powder according to claim 1 in the form of discrete, substantially spherical particles containing at least 0.01% nitrogen.
  • Carbonyl nickel powder according to. claim 1 in the form of chains of intergrown substantially spherical particles containing at least 0.01% nitrogen.
  • a ⁇ process of producing nickel powder having substantially spherical particles by the decomposition of nickel carbonyl vapour in the hot free space of a decomposer comprising introducing nickel carbonyl into the hot free space of a decomposer and mixing the nickel carbonyl with ammonia and oxygen, said ammonia and oxygen being added in small but effective amounts to introduce at least about 0.01% nitrogen into the powder formed.
  • a process according to claim 5 wherein the concentration of ammonia in the decomposer is at least about 0.2% by volume.
  • a process for producing substantially spherical nickel .powder by the decomposition of nickel carbonyl vapor in the hot free space of a decomposer which comprises introducing nickel carbonyl into the hot free space of the decomposer and mixing the nickel carbonyl with ammonia and oxygen, said ammonia and oxygen being added in small but effective amounts to form spherical nickel carbonyl powder.
  • a process according to claim 12 wherein the ratio of ammonia to oxygen is from about 3:4 to 4:1 by volume.
  • a process according to claim 13 wherein the concentration of ammonia in the decomposer is at least about 0.2% by volume.
  • a process according to claim 13 wherein the concentration of ammonia in the decomposer is atA least about 0.3% by volume.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Catalysts (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
US481157A 1964-08-19 1965-08-16 Nickel powder Expired - Lifetime US3367768A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB33907/64A GB1061579A (en) 1964-08-19 1964-08-19 Metal powders
GB1795065 1965-04-28

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US3367768A true US3367768A (en) 1968-02-06

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US480106A Expired - Lifetime US3367767A (en) 1964-08-19 1965-08-16 Method of making nickel powder

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US (2) US3367768A (enrdf_load_stackoverflow)
AT (1) AT268699B (enrdf_load_stackoverflow)
BE (2) BE668505A (enrdf_load_stackoverflow)
CH (2) CH427302A (enrdf_load_stackoverflow)
DE (1) DE1483145A1 (enrdf_load_stackoverflow)
ES (1) ES316605A1 (enrdf_load_stackoverflow)
GB (1) GB1061579A (enrdf_load_stackoverflow)
NL (3) NL6510618A (enrdf_load_stackoverflow)
SE (2) SE329009B (enrdf_load_stackoverflow)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4018596A (en) * 1973-05-15 1977-04-19 The International Nickel Company, Inc. High shrinkage powder body
US4676967A (en) * 1978-08-23 1987-06-30 Union Carbide Corporation High purity silane and silicon production
US20060048606A1 (en) * 2004-09-03 2006-03-09 Coley Kenneth S Process for producing metal powders

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3955961A (en) * 1974-04-25 1976-05-11 Robert Kenneth Jordan Carboxylate metals process
US4853030A (en) * 1988-04-15 1989-08-01 Gaf Corporation Method and apparatus for the manufacture of metallic filaments

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2884319A (en) * 1956-11-27 1959-04-28 Budd Co Acicular metal particles from metal carbonyls and method of preparation

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1759661A (en) * 1926-07-06 1930-05-20 Ig Farbenindustrie Ag Finely-divided metals from metal carbonyls

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2884319A (en) * 1956-11-27 1959-04-28 Budd Co Acicular metal particles from metal carbonyls and method of preparation

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4018596A (en) * 1973-05-15 1977-04-19 The International Nickel Company, Inc. High shrinkage powder body
US4676967A (en) * 1978-08-23 1987-06-30 Union Carbide Corporation High purity silane and silicon production
US20060048606A1 (en) * 2004-09-03 2006-03-09 Coley Kenneth S Process for producing metal powders
US7344584B2 (en) 2004-09-03 2008-03-18 Inco Limited Process for producing metal powders

Also Published As

Publication number Publication date
SE329010B (enrdf_load_stackoverflow) 1970-09-28
US3367767A (en) 1968-02-06
CH427302A (fr) 1966-12-31
SE329009B (enrdf_load_stackoverflow) 1970-09-28
NL6510895A (enrdf_load_stackoverflow) 1966-02-21
DE1483145B2 (enrdf_load_stackoverflow) 1969-09-04
NL7108568A (enrdf_load_stackoverflow) 1971-09-27
CH442761A (fr) 1967-08-31
NL144849B (nl) 1975-02-17
AT268699B (de) 1969-02-25
BE668506A (enrdf_load_stackoverflow)
DE1483146B1 (de) 1972-09-07
ES316605A1 (es) 1965-12-16
GB1061579A (en) 1967-03-15
DE1483145A1 (enrdf_load_stackoverflow) 1969-09-04
BE668505A (enrdf_load_stackoverflow) 1966-02-21
NL6510618A (enrdf_load_stackoverflow) 1966-02-21

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