WO2001019929A1 - Oberflächenmodifiziertes mangansulfid, verfahren zu dessen herstellung sowie dessen verwendung - Google Patents
Oberflächenmodifiziertes mangansulfid, verfahren zu dessen herstellung sowie dessen verwendung Download PDFInfo
- Publication number
- WO2001019929A1 WO2001019929A1 PCT/EP2000/008626 EP0008626W WO0119929A1 WO 2001019929 A1 WO2001019929 A1 WO 2001019929A1 EP 0008626 W EP0008626 W EP 0008626W WO 0119929 A1 WO0119929 A1 WO 0119929A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- manganese sulfide
- weight
- coating agent
- ester
- manganese
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0009—Pigments for ceramics
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
Definitions
- the invention relates to surface-modified manganese sulfide, a process for its production and the use of the surface-modified manganese sulfide as a pressing aid and as an additive in the sintering of moldings.
- the present invention relates to a sintered powder containing a content of the surface-modified manganese sulfide, a process for producing a molded article
- Manganese sulfide has proven to be a particularly suitable additive for sintering because, because of its thermal stability, it can participate in the sintering process without thermal decomposition.
- the manganese sulfide must be introduced into the sinter powder in the finest possible form.
- US Pat. No. 3,705,020 mentions a particle size of manganese sulfide of 10 to 100 ⁇ m, preferably 30 to 40 ⁇ m, and according to European patent application EP 0 183 666 the particle size is 10 ⁇ m or less.
- a small particle size enables a more homogeneous mixing of the sulfide and the production of mechanically stable molded parts. In particular, the formation of cracks is reduced.
- the small particle size and the associated large surface area of the manganese sulfide favors its reaction, in particular, moist air to MnO, Mn0 2 and MnS0 4 and thus also the clumping to larger particles or agglomerates.
- This behavior not only causes problems during storage, but when the manganese sulfide is used as a sintering additive, the clumping then leads to weakening of the structure in the finished molded parts. Especially with mechanical and thermal stress then follows the formation of cracks and the destruction of the molded part.
- the object of the present invention is therefore to provide such a manganese sulfide that does not have the features known in the prior art.
- such a manganese sulfide can be obtained by providing powdered manganese sulfide, a coating agent selected from a wax, an ester of an inorganic or organic acid or a polymer with a low melting point, or mixtures thereof an amount of 0.01 to 10% by weight. based on the weight of the manganese sulfide used, is added and the mixture is mixed over a period of time which is sufficiently large to ensure a homogeneous mixture.
- the inventors' investigations have shown that the protection against oxidation and the reduction of Moisture absorption of the otherwise hygroscopic material and the resulting agglomeration can surprisingly be prevented even by small amounts of the coating agent.
- the amount of coating agent used in the production of the coated manganese sulfide is from 0.01% by weight to 10% by weight, preferably from 0.01 to 5.0% by weight, particularly preferably from 1.0 to 3 , 0 wt .-%, based on the weight of the manganese sulfide.
- the coating is generally carried out at a temperature of 20 ° C. to 150 ° C.
- a temperature around freezing point O'C
- the mixing is usually carried out for a period of 1 minute to 60 minutes, preferably for 5 minutes to 20 minutes.
- the manganese sulfide obtained in this way is ready for immediate use, i.e. it need not be subjected to further treatment steps such as drying, neither for storage nor for its use.
- the surface-modified manganese sulfide according to the invention proves to be a lubricating pressing aid and can therefore generally be used as an additive to improve the pressing properties.
- Another advantageous property of the manganese sulfide according to the invention which has proven to be favorable precisely in connection with its storage and use, is its freedom from dust.
- the manganese sulfide can be coated in any manner known to the person skilled in the art.
- the coating agent can be added as a whole or at intervals to the manganese sulfide in a conventional mixing device such as a ploughshare mixer or tumble mixer.
- any commercially available manganese sulfide can be used, regardless of purity or particle size. If, for example, necessary for use as a sintering additive, the manganese sulfide is added before
- preferred coating materials are compounds which are either liquid at room temperature or have a relatively low melting point below 150 ° C. As indicated above, this makes it possible to work in the production of the manganese sulfide according to the invention without or with only weak heating of the mixer.
- the coating compositions according to the invention should furthermore have an evaporation point at normal pressure below 500'C, preferably in the range of approximately 200 to 300 'C, and decompose or evaporate without residue during the warming-up of the sintering mixture, since this causes the formation possible impurities in the sintered molded body is reduced.
- Coating materials used according to the invention which have the physical properties mentioned above, are preferably low-melting polymers, oils including paraffinic oils and silicone oils, waxes, a mono- to polyhydric aliphatic alcohol with 2 to 12 carbon atoms, organic and inorganic esters, in the latter case especially phosphoric acid esters.
- waxing is understood, on the one hand, to mean the esters of higher straight-chain fatty acids such as palmitic acid, hexaeicosanoic acid with higher straight-chain, monohydric alcohols such as palmityl alcohol, stearyl alcohol or octadec-9-en-l-ol.
- waxes within the meaning of the invention are also understood to mean those substances which are mostly of natural origin and which partially or predominantly contain the abovementioned fatty acid esters and which, above about 30 ° C. to 40 ° C., do not decompose into a molten, low-viscosity state Examples of such waxes are Japanese wax, lanolin or beeswax.
- waxes also includes synthetic polymers with a wax-like character, such as the so-called polyolefin waxes.
- synthetic polymers which are used in the present invention are low molecular weight polyethylene glycols and polypropylene glycols.
- oils are understood to mean, on the one hand, aliphatic oils based on mineral oils, such as the paraffinic oils.
- the aliphatic oils preferably have a chain length of 6 to 20 carbon atoms.
- the term oil also includes synthetic oils such as silicone oils, as the generic term u.a. are known for clear, colorless, hydrophobic liquids with pour points of approximately -80 to -40 ° C. of linear polydimethylsiloxanes and polymethylphenylsiloxanes.
- a low-melting polymer is understood here to mean those compounds which consist of macromolecules consist and a melting point of less than 150 have "C and an evaporation temperature of below 500 'C at atmospheric pressure.
- Preferred members of this class of compounds are polyesters, polyamides and poly-aliphatic compounds.
- esters of inorganic or organic acids can also be used as coating agents.
- Preferred inorganic acids are phosphoric acid and sulfuric acid, but other acids such as sulphurous acid, carbonic acid, ... can also be used according to the invention.
- the preferred organic acids are formic acid and lower carboxylic acids with 2 to 6 carbon atoms, e.g. Acetic acid.
- Both aliphatic and aromatic alcohols are used as ester alcohols.
- the aliphatic alcohols preferably have a chain length of 1 to 20 carbon atoms.
- Preferred aromatic alcohols are the phenols. These can have several hydroxyl groups or several aliphatic substituents with a chain length of preferably one to six carbon atoms.
- a monohydric to polyhydric aliphatic alcohol having 2 to 12 carbon atoms is understood to be an alcohol which, owing to its evaporation and flammability properties, is suitable for use in the process according to the invention.
- Aromatic compounds such as biphenyl, etc. are also suitable as further coating agents, as long as these compounds, like the other coating agents which can be used according to the invention, are characterized by low-soot and residue-free evaporation.
- a preferred class of coating materials used according to the invention are (low-viscosity) esters of phosphoric acid, in particular those with longer-chain aliphatic alcohols with chain lengths between 3 and 15 carbon atoms, preferably 6 to 13 carbon atoms, and with phenols or other aromatic alcohols with side chains of 1 to 12 carbon atoms, preferably 1 to 3 carbon atoms, such as cresols.
- These compounds are also known to the person skilled in the art as plasticizers. Examples of such compounds are tris (2-ethylhexyl) phosphate, tris (2-butoxyethyl) phosphate, triphenyl phosphate or diphenyl cresyl phosphate.
- Diphenyl cresyl phosphate is a particularly suitable representative of this class of compounds, since it is non-toxic, liquid at room temperature and low viscosity, evaporates at about 230 ° C. and also burns without soot. Another advantage of diphenyl cresyl phosphate is its relatively temperature-independent viscosity.
- a surface-modified manganese sulfide of this type is mechanical, in particular machining
- Processing of sintered moldings improves when it is in a sinter powder in the amount of 0.1 wt .-% to 1.0 wt .-%, preferably from 0.2 to 0.6 wt .-%, based on the weight of the Sinter powder is introduced.
- a further embodiment of the present invention is also directed to a sinter powder which is characterized by a content of the manganese sulfide according to the invention
- the manganese sulfide is preferably treated with the coating compositions according to the invention in the manner described above before being added to the selected metal powder.
- a further embodiment of the present invention therefore also relates to a method for producing a molding using the one according to the invention Sinter powder, the method comprising the following steps: a) compacting the sinter powder in a sinter mold which has an internal shape corresponding to the end contour of the finished molded part; b) heating the green compacts to a temperature above the evaporation temperature of the coating agent used to produce the manganese sulfide, and, if necessary, keeping the green compacts at this temperature for a period of time sufficient to ensure complete evaporation of the coating composition; c) sintering the green compacts from step b); d) removing the cooled molded parts from the sintered mold.
- a further embodiment thus comprises a molded part which can be obtained by the production / sintering method according to the invention explained above.
- the present invention is to be illustrated in more detail using a non-restrictive example.
- liquid diphenyl cresyl phosphate 20 g were added to 2000 g of manganese sulfide, which had a grain diameter of 4.96 ⁇ m (D50), in a Lödige mixer. The mixture was then mixed at 25 ° C. for 20 min.
- the manganese sulfide obtained in Example 1 and treated with 1% diphenyl cresyl phosphate was combined with uncoated manganese sulfide of the same grain diameter, ie according to EP 0 183 666 (Example 2) and a manganese sulfide composition according to US 5,768,678 (Example 3) in an atmosphere of 75% air humidity at room temperature stored for 6 days.
- the manganese sulfide coated according to the invention absorbs significantly less moisture than the uncoated material or the manganese sulfide composition of US Pat. No. 5,768,678. Consistent with this, the material according to the invention is still a fine, free-flowing powder without agglomerates after 10 weeks, while the uncoated manganese sulfide has changed to a coarse-grained, dark product during this time due to the absorption of moisture and the formation of manganese dioxide.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Powder Metallurgy (AREA)
- Luminescent Compositions (AREA)
- Catalysts (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Steroid Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
Description
Claims
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT00965916T ATE256716T1 (de) | 1999-09-10 | 2000-09-04 | Oberflächenmodifiziertes mangansulfid, verfahren zu dessen herstellung sowie dessen verwendung |
JP2001523702A JP2003509325A (ja) | 1999-09-10 | 2000-09-04 | 表面改質硫化マンガン、その製造方法及びその使用 |
DK00965916T DK1137718T3 (da) | 1999-09-10 | 2000-09-04 | Overflademodificeret mangansulfid, fremgangsmåde til fremstilling heraf samt dets anvendelse |
CA002347824A CA2347824A1 (en) | 1999-09-10 | 2000-09-04 | Surface-modified manganese sulfide, method for producing the same and use thereof |
KR1020017005899A KR20010082294A (ko) | 1999-09-10 | 2000-09-04 | 표면개량된 황화망간, 그 제조 및 이용방법 |
EP00965916A EP1137718B1 (de) | 1999-09-10 | 2000-09-04 | Oberflächenmodifiziertes mangansulfid, verfahren zu dessen herstellung sowie dessen verwendung |
DE50004789T DE50004789D1 (de) | 1999-09-10 | 2000-09-04 | Oberflächenmodifiziertes mangansulfid, verfahren zu dessen herstellung sowie dessen verwendung |
BR0007095-5A BR0007095A (pt) | 1999-09-10 | 2000-09-04 | Sulfeto de manganês com superfìcie revestida, processo para a preparação e uso do mesmo, pó de sinterização, artigo moldado, e, processo para a preparação do mesmo |
PL00347575A PL347575A1 (en) | 1999-09-10 | 2000-09-04 | Surface−modified manganese sulfide, method for producing the same and use thereof |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19943510A DE19943510C1 (de) | 1999-09-10 | 1999-09-10 | Oberflächenmodifiziertes Mangansulfid, Verfahren zu dessen Herstellung sowie dessen Verwendung |
DE19943510.3 | 1999-09-10 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2001019929A1 true WO2001019929A1 (de) | 2001-03-22 |
Family
ID=7921630
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2000/008626 WO2001019929A1 (de) | 1999-09-10 | 2000-09-04 | Oberflächenmodifiziertes mangansulfid, verfahren zu dessen herstellung sowie dessen verwendung |
Country Status (13)
Country | Link |
---|---|
EP (1) | EP1137718B1 (de) |
JP (1) | JP2003509325A (de) |
KR (1) | KR20010082294A (de) |
AT (1) | ATE256716T1 (de) |
BR (1) | BR0007095A (de) |
CA (1) | CA2347824A1 (de) |
DE (2) | DE19943510C1 (de) |
DK (1) | DK1137718T3 (de) |
ES (1) | ES2209999T3 (de) |
PL (1) | PL347575A1 (de) |
PT (1) | PT1137718E (de) |
TR (1) | TR200101158T1 (de) |
WO (1) | WO2001019929A1 (de) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6445555B1 (en) | 1999-11-24 | 2002-09-03 | American Superconductor Corporation | Method and apparatus for discharging a superconducting magnet |
KR100437643B1 (ko) * | 2001-11-30 | 2004-06-30 | 가야에이엠에이 주식회사 | 소결제품 제조시 첨가되는 복합 황화망간의 조성물 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102312281B1 (ko) * | 2021-04-26 | 2021-10-12 | 대영소결금속 주식회사 | 소결제품 제조시 첨가되는 복합 황화망간 조성물 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3705020A (en) | 1971-02-02 | 1972-12-05 | Lasalle Steel Co | Metals having improved machinability and method |
US4483905A (en) * | 1980-03-06 | 1984-11-20 | Hoganas Ag | Homogeneous iron based powder mixtures free of segregation |
EP0183666A1 (de) | 1984-11-30 | 1986-06-04 | Höganäs AB | Mangansulfid enthaltendes Eisenpulver und Verfahren zu dessen Herstellung |
EP0264287A2 (de) * | 1986-10-15 | 1988-04-20 | Hoeganaes Corporation | Pulvermischungen auf Eisenbasis |
US5698005A (en) * | 1994-09-26 | 1997-12-16 | Cfpi Industries | Composition which is simultaneously anticlumping and water-repellant for salts, simple and complex fertilizers and process for the use thereof |
US5768678A (en) | 1996-05-08 | 1998-06-16 | Pyron Corporation | Manganese sulfide composition and its method of production |
EP0900856A1 (de) * | 1997-09-02 | 1999-03-10 | T&N TECHNOLOGY LIMITED | Rostfreie gesinterte Stahllegierung mit mangan sulfid für hochtemperaturbeanspruchte Lager |
-
1999
- 1999-09-10 DE DE19943510A patent/DE19943510C1/de not_active Expired - Fee Related
-
2000
- 2000-09-04 JP JP2001523702A patent/JP2003509325A/ja active Pending
- 2000-09-04 WO PCT/EP2000/008626 patent/WO2001019929A1/de not_active Application Discontinuation
- 2000-09-04 DE DE50004789T patent/DE50004789D1/de not_active Expired - Fee Related
- 2000-09-04 BR BR0007095-5A patent/BR0007095A/pt not_active Application Discontinuation
- 2000-09-04 PL PL00347575A patent/PL347575A1/xx unknown
- 2000-09-04 TR TR2001/01158T patent/TR200101158T1/xx unknown
- 2000-09-04 AT AT00965916T patent/ATE256716T1/de not_active IP Right Cessation
- 2000-09-04 DK DK00965916T patent/DK1137718T3/da active
- 2000-09-04 KR KR1020017005899A patent/KR20010082294A/ko not_active Application Discontinuation
- 2000-09-04 ES ES00965916T patent/ES2209999T3/es not_active Expired - Lifetime
- 2000-09-04 PT PT00965916T patent/PT1137718E/pt unknown
- 2000-09-04 CA CA002347824A patent/CA2347824A1/en not_active Abandoned
- 2000-09-04 EP EP00965916A patent/EP1137718B1/de not_active Expired - Lifetime
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3705020A (en) | 1971-02-02 | 1972-12-05 | Lasalle Steel Co | Metals having improved machinability and method |
US4483905A (en) * | 1980-03-06 | 1984-11-20 | Hoganas Ag | Homogeneous iron based powder mixtures free of segregation |
US4483905B1 (en) * | 1980-03-06 | 1997-02-04 | Hoeganaes Ab | Homogeneous iron based powder mixtures free of segregation |
EP0183666A1 (de) | 1984-11-30 | 1986-06-04 | Höganäs AB | Mangansulfid enthaltendes Eisenpulver und Verfahren zu dessen Herstellung |
EP0264287A2 (de) * | 1986-10-15 | 1988-04-20 | Hoeganaes Corporation | Pulvermischungen auf Eisenbasis |
US5698005A (en) * | 1994-09-26 | 1997-12-16 | Cfpi Industries | Composition which is simultaneously anticlumping and water-repellant for salts, simple and complex fertilizers and process for the use thereof |
US5768678A (en) | 1996-05-08 | 1998-06-16 | Pyron Corporation | Manganese sulfide composition and its method of production |
EP0900856A1 (de) * | 1997-09-02 | 1999-03-10 | T&N TECHNOLOGY LIMITED | Rostfreie gesinterte Stahllegierung mit mangan sulfid für hochtemperaturbeanspruchte Lager |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6445555B1 (en) | 1999-11-24 | 2002-09-03 | American Superconductor Corporation | Method and apparatus for discharging a superconducting magnet |
KR100437643B1 (ko) * | 2001-11-30 | 2004-06-30 | 가야에이엠에이 주식회사 | 소결제품 제조시 첨가되는 복합 황화망간의 조성물 |
Also Published As
Publication number | Publication date |
---|---|
KR20010082294A (ko) | 2001-08-29 |
JP2003509325A (ja) | 2003-03-11 |
DE19943510C1 (de) | 2001-01-25 |
PT1137718E (pt) | 2004-05-31 |
EP1137718B1 (de) | 2003-12-17 |
DK1137718T3 (da) | 2004-04-13 |
ES2209999T3 (es) | 2004-07-01 |
PL347575A1 (en) | 2002-04-08 |
TR200101158T1 (tr) | 2001-08-21 |
BR0007095A (pt) | 2001-07-31 |
ATE256716T1 (de) | 2004-01-15 |
EP1137718A1 (de) | 2001-10-04 |
DE50004789D1 (de) | 2004-01-29 |
CA2347824A1 (en) | 2001-03-22 |
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