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WO2012175770A2 - Composition et procédé d'obtention de pastilles de mn - Google Patents

Composition et procédé d'obtention de pastilles de mn Download PDF

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Publication number
WO2012175770A2
WO2012175770A2 PCT/ES2012/070433 ES2012070433W WO2012175770A2 WO 2012175770 A2 WO2012175770 A2 WO 2012175770A2 ES 2012070433 W ES2012070433 W ES 2012070433W WO 2012175770 A2 WO2012175770 A2 WO 2012175770A2
Authority
WO
WIPO (PCT)
Prior art keywords
composition
organic polymer
tablets
composition according
water
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/ES2012/070433
Other languages
English (en)
Spanish (es)
Other versions
WO2012175770A3 (fr
Inventor
Ricardo FERNÁNDEZ SERRANO
Gaspar GONZÁLEZ DONCEL
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.)
Consejo Superior de Investigaciones Cientificas CSIC
Original Assignee
Consejo Superior de Investigaciones Cientificas CSIC
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 Consejo Superior de Investigaciones Cientificas CSIC filed Critical Consejo Superior de Investigaciones Cientificas CSIC
Publication of WO2012175770A2 publication Critical patent/WO2012175770A2/fr
Publication of WO2012175770A3 publication Critical patent/WO2012175770A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/0006—Adding metallic additives
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/103—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing an organic binding agent comprising a mixture of, or obtained by reaction of, two or more components other than a solvent or a lubricating agent
    • 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/14—Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24—Binding; Briquetting ; Granulating
    • C22B1/242—Binding; Briquetting ; Granulating with binders
    • 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
    • C22B47/00—Obtaining manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C22/00—Alloys based on manganese
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/02—Compacting only
    • B22F2003/023—Lubricant mixed with the metal powder
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/0056—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00 using cored wires
    • C21C2007/0062—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00 using cored wires with introduction of alloying or treating agents under a compacted form different from a wire, e.g. briquette, pellet

Definitions

  • the present invention relates to a mixture of additives in the preparation of compacted tablets of metals to add as alloys to a casting of another metal, mainly aluminum. More specifically, it refers to the use of a mixture of organic polymers that, mixed in the appropriate proportions, allows to obtain Mn powder tablets with good consistency, in terms of mechanical strength, and of easy dissolution in metal casting.
  • mother alloys with low alloying element contents typically less than 60%
  • these mother alloys commonly come from previous smelters, adding difficulty in controlling their composition.
  • This type of mother alloy has raised interest very recently (US2010313712) while alloys (in the form of splashes) with up to 93% Mn content, up to 5% in total Si and Fe, have been obtained, and The rest aluminum. Its high alloy content minimizes the melting furnace temperature drop and alloy recovery rates close to 100% are announced in periods of approximately 15 minutes.
  • the main disadvantage of these mother alloys remains their high cost.
  • the second is the significant risk of flammability as a result of the fine powders that are released from this type of tablets in a high temperature environment such as that of a foundry; f) Obtain dissolution rates fast enough to minimize casting times while achieving good homogeneity of the alloy in the casting.
  • the dissolution rates of conventional tablets (up to 85% Mn) are industrially acceptable.
  • the presence of small amounts of organic waxes used as lubricants accelerates the dissolution process of the tablets when aluminum is used as a binder (US6149710).
  • these waxes do not have the same binding power as aluminum and, in addition, should not be added in percentages greater than 5% since they increase the slag of the laundry, cause excess fumes, and introduce hydrogen and carbon into the alloy resulting;
  • the Mn being the main element
  • a concentration typically> 70% the use of a mixture of organic polymers with double function, binder and lubricant, for its manufacture is presented.
  • This mixture of polymers allows to obtain compact with a good mechanical resistance while reducing the loss of fine powders during handling.
  • the dissolution of manganese during casting is favored compared to compacts that use aluminum as a binder element and the cost is reduced, since the use of this element is minimized, even being avoided.
  • a composition for the manufacture of Mn tablets characterized in that it comprises: (a) Mn powder in a percentage between 70% and 99.5% by weight, and more preferably between 70% and 97% of the composition; (b) a first powder binder selected from at least one water insoluble organic polymer or at least one water soluble organic polymer, or a mixture of both, wherein said organic polymer is not a wax; and (c) a possible second powder binder preferably selected from aluminum, iron, or their respective alloys.
  • powder is understood as the product that remains of a solid after being reduced to very small parts, generally with a particle size between 1 and 1000 um.
  • a typical range of sizes is that indicated in Tables II and III of the detailed description of the invention.
  • the method of obtaining Mn tablets from the composition described above is object of the invention.
  • Said procedure is characterized in that it comprises compacting the different elements that they form the composition at room temperature (10 ° C-45 ° C).
  • the process may comprise a stage after compacting the heat treatment of the composition.
  • the object of the invention is the Mn tablets obtained from said process and their use in metal casting, preferably, in aluminum, iron, or their respective alloys.
  • Figure 1 shows an Mn tablet obtained from 146 g of Mn and 3.75 g of PEG 5000;
  • Figure 2 shows the evolution in time of the Mn content of the experimental casting broth according to Mn tablets with different composition, compacting the powders of the mixture at different loading levels and with subsequent heat treatment;
  • Figure 3 shows the mechanical resistance normalized by the height (mm) of the tested Mn tablets and in which the load axis was applied in the transverse direction.
  • the commercial tablet represented by squares, contains 80% Mn and 20% Al, and is 200 grams in weight. The rest of the tablets have been manufactured according to the present invention and contain 95% Mn.
  • the data represented by rhombuses correspond to a tablet with 5% PEG, weighing 80 grams, compacted at low load (25Tn) and without subsequent heat treatment.
  • the data represented by circles correspond to a tablet with 2.5% PEG and 2.5% PVA, 150 grams in weight and with a subsequent heat treatment of 100 ° C for 20 min.
  • the data represented by triangles correspond to a 5% PEG tablet, 80 grams of compacted weight at 45 tons and with a subsequent heat treatment of 65 ° C and 20 min.
  • the results obtained from the tablets of the present invention are superior to those obtained from the commercial tablet. This improvement is very significant, taking into account the percentage of Mn of the tablets (95%), higher than 80% of Mn of the commercial tablets.
  • the invention relates to the use of a mixture of organic polymers for the manufacture of tablets with a high manganese content (> 70%) by compaction at a temperature close to the environment (between 10 ° C and 45 ° C) of the mixture of organic polymers with manganese and optionally, with a metal selected from aluminum, iron, or its alloys. It is ruled out to replace one of the two polymers of the invention with a wax among which are: paraffin, microcrystalline wax, polyethylene or polypropylene waxes (which are similar to paraffin but with greater strength and flexibility), oxidized polyethylene waxes or carnauba This is because they give rise to softer tablets compared to polymer / polymer blends.
  • waxes containing phenolic or aromatic components are graphitized when the temperature is raised in a vacuum or in an inert gas atmosphere, contributing carbon to the laundry.
  • the organic polymer blend consists of a water insoluble polymer (Type A) and a water soluble polymer (Type B).
  • the Type A polymer may preferably consist of a polymer selected from a group consisting of polymers of vinyl alcohols, polyurethanes, polyamides, polyacrylates and polymethacrylates, as well as any combination thereof. More preferably, said polymer may consist of polyvinyl acetate (PVA), which has a good combination of properties and a low price compared to aluminum; polyvinylbutyral, for its clean combustion that minimizes carbon residues; or poly (oxymethylene).
  • PVA polyvinyl acetate
  • the Type A polymer may consist of Kollidon®, which comprises 8 parts (w / w) of PVA and 2 parts (w / w) of polyvinylpyrrolidone.
  • the weight percentage of said Type A polymer in the composition is between 0.05% and 5.0%.
  • the Type B polymer may preferably consist of a polymer selected from a group consisting of polyethylene glycol (PEG), polyethylene oxide, polyethylene, celluloses, copolymers of ethylene, polypropylene and propylene oxide, as well as any combination thereof.
  • PEG polyethylene glycol
  • polyethylene glycol is proposed for its good combination of properties and its low price compared to aluminum, as well as polyethylene for its low price.
  • Polyethylene oxide although it has good compatibility with Type A and Type B polymers and has good thermal decomposition properties, is much more expensive than polyethylene glycol.
  • the weight percentage of Type B polymer in the composition is preferably between 0.05% and 5.0%.
  • the molecular weight of the constituent polymers of the mixture is high.
  • the molecular weight of the polymers used in the composition is preferably greater than 1000 g / mol, and more preferably, greater than 3000 g / mol.
  • the Type B polymer is PEG
  • the hydroxyl value decreases inversely proportional to the molecular weight .
  • the price of polyethylene glycol depends on the molecular weight.
  • PEG 5000-7000 has the best combination of hydroxyl value and price, so it is especially preferred in the present invention.
  • polyethylene glycol has a high oxidation index, so it decomposes into components of lower molecular weight without leaving residues around 200 ° C.
  • polyethylene glycol (PEG) of molecular weight greater than 4000 g / mol is especially preferred.
  • the described composition is constituted by the elements shown in Table I, where the preferred percentage by weight of each of said elements is also collected, so that the total sum of all of them in The composition is 100%.
  • said polymers may be present independently or in combination:
  • the main advantage of the invention is that the use of aluminum (or iron) as a binder can be completely eliminated and that the total amount of binders added to obtain the tablets can be reduced. For both reasons the cost of manufacturing tablets is reduced. In addition, the mechanical strength of the tablets improves several orders of magnitude and in parallel the dissolution times of the tablets in the broth are improved.
  • Example 1 Mix of 5% by weight of PEG in powder form, 10% by weight of aluminum in powder form and 85% by weight of electrolytic Mn from milling;
  • Example 2 Mix of 5% by weight of PEG with 95% of electrolytic Mn from milling;
  • Example 3 Mixture of 2.5% by weight of PVA + PEG with 97.5% by weight of electrolytic Mn from milling; Example 4. Measurement of the mechanical strength of the tablets obtained in examples 1 to 3.
  • Example 1. Mix of 5% by weight of PEG in powder form and 10% by weight of aluminum in powder form and 85% by weight of electrolytic Mn from milling. The powders described in Table IV were mixed in a turbot for 15 minutes at a rate of approximately 1 revolution per second to optimize the powder mixing process.
  • the granulometry of the Mn used in the procedure was that corresponding to Table II (b).
  • the granulometry of PEG powders was the one shown in Table III (b).
  • the aluminum used in the mixture was atomized aluminum powder with particle size between 100 ⁇ and 800 ⁇ .
  • the resulting mixture is poured minimizing the segregation of both components in the compaction tooling, with its inner surface lubricated with zinc stearate.
  • the powder mixture according to Tables II and III was compacted in a cold press at a temperature between 10 ° C and 45 ° C.
  • the tablet obtained was extracted by applying about 700 kg of pressure.
  • the resulting tablet had a diameter of 40 mm and a height of approximately 22 mm with a final weight of 75 grams.
  • the apparent density resulting from the process of Compaction was 2.7g / cm 3 .
  • Figure 2 shows the concentration of Mn measured by optical emission spectroscopy by spark, at different sample extraction times.
  • the recovery rate of Mn is 98%, obtaining this value in a time 2.4 times less than using only Al as the binding element.
  • Example 2 Mix of 5% by weight of PEG with 95% of electrolytic Mn from milling.
  • the powders described in Table V were mixed in a turbot for 15 minutes at a rate of approximately 1 revolution per second to optimize the powder mixing process.
  • Table V shows the intervals by weight of the different elements present in the composition: Table V. Intervals in percentage by weight of the elements comprising the composition
  • Figure 2 shows the concentration of Mn measured by optical emission spectroscopy by spark at different sample extraction times.
  • the recovery rate of Mn is 98%, obtaining this value in a time 2.4 times less than using only Al as the binding element.
  • Example 3 Mix of 2.5% by weight of PVA and PEG with 97.5% by weight of electrolytic Mn from milling.
  • the powders described in Table V were mixed in a turbot for 15 minutes at a rate of approximately 1 revolution per second to optimize the powder mixing process.
  • Figure 2 shows the concentration of Mn measured by optical emission spectroscopy by spark at different sample extraction times.
  • the recovery rate of Mn is 98%, obtaining this value in a time 2.4 times less than using only Al as the binding element.
  • Example 4. Measurement of the mechanical strength of the tablets obtained in examples 1 to 3.
  • the mechanical strength of the obtained tablets was studied by means of the so-called drop test in which the tablets were dropped in free fall from 740 mm high against a hard and rigid ground and the amount of throws needed is quantified so that the tablet loses a certain amount of material and breaks in an obvious way.
  • the results of this test are shown in Table VII.
  • Table VII shows the number of falls that each tablet has withstood in the drop test from 740 mm, together with the compaction conditions and subsequent heat treatment performed on each tablet. All tablets were compacted at 25 ° C and approximately 94 Tn. The result of number of falls in If it is less than 2, it is the average of performing the test on at least three tablets.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Powder Metallurgy (AREA)
  • Medicinal Preparation (AREA)

Abstract

L'invention concerne une composition et un procédé d'obtention de pastilles de Mn. La présente invention concerne une composition pour la fabrication de pastilles de Mn caractérisée en ce qu'elle comprend: (a) une poudre de Mn selon un pourcentage compris entre 70% et 99% en poids de la composition; (b) un premier agglomérant en poudre sélectionné parmi au moins un polymère organique insoluble dans l'eau et au moins un polymère organique soluble dans l'eau, ou un mélange des deux, ledit premier agglomérant n'étant pas une cire. L'invention concerne également un procédé pour l'obtention de ladite composition et son utilisation comme pastilles de Mn dans la coulée de métaux.
PCT/ES2012/070433 2011-06-20 2012-06-08 Composition et procédé d'obtention de pastilles de mn Ceased WO2012175770A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ES201131030A ES2395550B1 (es) 2011-06-20 2011-06-20 COMPOSICIÓN Y PROCEDIMIENTO DE OBTENCIÓN DE TABLETAS DE Mn
ESP201131030 2011-06-20

Publications (2)

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WO2012175770A2 true WO2012175770A2 (fr) 2012-12-27
WO2012175770A3 WO2012175770A3 (fr) 2013-04-11

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Country Status (2)

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ES (1) ES2395550B1 (fr)
WO (1) WO2012175770A2 (fr)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2361925A (en) * 1942-07-04 1944-11-07 Minerals And Metals Corp Preparation of manganese products
JPS4884011A (fr) * 1972-02-02 1973-11-08
US4362559A (en) * 1981-03-09 1982-12-07 American Cyanamid Company Method of introducing addition agents into a metallurgical operation
US5951737A (en) * 1998-06-16 1999-09-14 National Research Council Of Canada Lubricated aluminum powder compositions
ATE286990T1 (de) * 1999-04-15 2005-01-15 Bostlan Sa Zusatzmittel zur zuführung von metallen in aluminiumlegierungen

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Publication number Publication date
ES2395550A1 (es) 2013-02-13
ES2395550B1 (es) 2013-12-19
WO2012175770A3 (fr) 2013-04-11

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