DE4421454A1 - Prodn. of finely-divided polyamide powder for e.g. coatings - Google Patents
Prodn. of finely-divided polyamide powder for e.g. coatingsInfo
- Publication number
- DE4421454A1 DE4421454A1 DE19944421454 DE4421454A DE4421454A1 DE 4421454 A1 DE4421454 A1 DE 4421454A1 DE 19944421454 DE19944421454 DE 19944421454 DE 4421454 A DE4421454 A DE 4421454A DE 4421454 A1 DE4421454 A1 DE 4421454A1
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- Germany
- Prior art keywords
- powder
- polyamide
- precipitation
- dried
- grain fraction
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/14—Powdering or granulating by precipitation from solutions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/46—Post-polymerisation treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
Abstract
Description
Gegenstand der Erfindung ist ein Verfahren zur Herstellung sehr feiner Polyamid-Pulver durch Umfällen eines Homopolyamids oder eines einheitlich zusammengesetzten Copolyamids aus alkoholischer Lösung und anschließender Vermahlung des getrockneten Fällpulvers.The invention relates to a method for producing very fine Polyamide powder by reprecipitating a homopolyamide or one composite copolyamide from alcoholic solution and subsequent Grinding the dried powder.
Beschichtungspulver auf Polyamid-Basis zeichnen sich durch ihre hohe Che mikalienbeständigkeit sowie sehr gute mechanische Eigenschaften aus. Da bei sind Pulver, die durch Umfällen aus ethanolischer Lösung erhalten werden, z. B. nach der DE-OS 29 06 647, hinsichtlich ihres Verarbeitungs verhaltens solchen Produkten überlegen, die aus einem Mahlprozeß, z. B. nach der DE-OS 15 70 392, erhalten werden, da die Fällung zu runderen und damit besser fluidisierbaren Partikeln führt. Außerdem besitzen Mahlpul ver, wie man sie z. B. nach der DE-PS 28 55 920 erhält, eine breite Korn größenverteilung, die einen hohen Klassieraufwand bedingt.Coating powders based on polyamide are characterized by their high Che resistance to chemicals and very good mechanical properties. There at are powders obtained by reprecipitation from ethanolic solution be, e.g. B. according to DE-OS 29 06 647, with regard to their processing behave such products that from a grinding process, for. B. according to DE-OS 15 70 392, can be obtained because the precipitation is more rounded and thus leads to more fluidizable particles. Also have grinding pulp ver how to z. B. receives according to DE-PS 28 55 920, a wide grain size distribution that requires a lot of classification.
Das Fällverfahren stößt an seine technischen Grenzen, wenn danach Pulver mit einem hohen Feinanteil hergestellt werden sollen, wie sie für elek trostatisch aufgebrachte Beschichtungen oder als Lackadditiv für Coil- Coating-Lacke o.ä. benötigt werden. Hierfür werden Pulver mit einer Kornobergrenze von 63 µm, z. T. auch von < 40 µm, benötigt, die in einem oder mehreren Klassierschritten aus dem gefällten und getrockneten Roh pulver abgetrennt werden müssen. Der im Rohpulver vorhandene Feinanteil ist naturgemäß begrenzt, was die Ausbeute an Nutzkorn vermindert. Zwar ist es nach der DE-OS 35 10 689 möglich, durch Anwendung niedriger Löse temperaturen zu feinen Pulvern mit recht einheitlicher Korngröße zu ge langen, diese Produkte sind normalerweise durch niedrige Schüttdichten und hohe BET-Oberflächen gekennzeichnet und deshalb als Lackadditive nur bedingt einsetzbar. In diesen Fällen kann das Zumischen von niedrig schmelzenden Copolyamiden vorteilhaft sein, derartige Mischpräzipitate sind jedoch hinsichtlich ihrer chemischen Zusammensetzung schlecht repro duzierbar. Es ist nach dem Stand der Technik nicht möglich, Feinstpulver aus Homopolyamiden mit den gewünschten hohen Schüttdichten durch Fällung oder Mahlung herzustellen. The precipitation process reaches its technical limits when powder afterwards should be produced with a high proportion of fines, as they are for elec trostatically applied coatings or as a coating additive for coil Coating varnishes or similar are needed. For this, powder with a Grain upper limit of 63 µm, e.g. T. also of <40 µm, needed in one or several classification steps from the precipitated and dried raw powder must be separated. The fine fraction present in the raw powder is naturally limited, which reduces the yield of useful grain. Though it is possible according to DE-OS 35 10 689, by using low solutions temperatures to fine powders with a fairly uniform grain size long, these products are usually due to low bulk densities and high BET surface areas and therefore only as paint additives limited use. In these cases, the admixture can be low melting copolyamides may be advantageous, such mixed precipitates are however poorly reproduced in terms of their chemical composition inducible. According to the state of the art it is not possible to use very fine powder from homopolyamides with the desired high bulk densities by precipitation or to produce grinding.
Die Schüttdichte bei vergleichbarer Korngröße ist dabei ein Maß für die Morphologie des Pulverkorns. Überwiegend glatte Primärteilchen werden durch eine hohe Schüttdichte, überwiegend stark zerklüftete Primärteil chen durch eine niedrige Schüttdichte angezeigt.The bulk density with a comparable grain size is a measure of that Morphology of the powder grain. Predominantly smooth primary particles due to a high bulk density, predominantly strongly jagged primary part Chen indicated by a low bulk density.
Überraschenderweise wurde nun gefunden, daß sich Polyamid-Feinstpulver durch Umfällen eines Homopolyamids oder eine einheitlich zusammengesetz ten Copolyamids aus alkoholischer Lösung und anschließender Vermahlung des getrockneten Fällpulvers herstellen lassen.Surprisingly, it has now been found that fine polyamide powder by reprecipitation of a homopolyamide or a uniform compound ten copolyamide from alcoholic solution and subsequent grinding of the dried powdered powder.
Die Homo- oder Copolyamide werden dabei unter Wärme in einem Alkohol mit 1 bis 3 C-Atomen gelöst, danach die Temperatur bis zur Übersättigung er niedrigt, anschließend wird die Suspension getrocknet und das getrocknete Pulver einem Mahlprozeß unterworfen.The homo- or copolyamides are heated in an alcohol 1 to 3 carbon atoms dissolved, then the temperature to supersaturation low, then the suspension is dried and the dried Powder subjected to a grinding process.
Es war dabei nicht zu erwarten, daß die erfindungsgemäß hergestellten Produkte eine hohe Schüttdichte aufweisen würden, da Mahlprozesse im all gemeinen zu zerklüfteten Primärteilchen führen.It was not to be expected that those produced according to the invention Products would have a high bulk density, since grinding processes in all mean lead to jagged primary particles.
Als Lösemittel für das Fällungsverfahren gemäß der Erfindung werden Alko hole mit 1 bis 3 C-Atomen, vorzugsweise Ethanol, verwendet. Als Ethanol kann hierbei neben wasserfreiem Ethanol der übliche Alkohol eingesetzt werden, der bis zu 10 Gewichtsprozent Wasser und die üblichen Vergäl lungsmittel, wie z. B. Methylethylketon, Petrolether, Pyridin, enthalten kann. Das Ethanol wird mindestens in der doppelten Gewichtsmenge des Polyamids eingesetzt. Vorteilhaft beträgt sie bei Wirbelsinterpulvern das Vier- bis Fünffache und bei Elektrostatikpulvern das Vier- bis Sieben fache, insbesondere etwa das Vier- bzw. 5,6-fache. Mit anderen Worten be trägt die Konzentration des Polyamids in der Lösung 35 Gewichtsprozent, vorteilhaft 25 bis 15, insbesondere etwa 20 bzw. 15 Gewichtsprozent. In diesen Konzentrationsbereichen erhält man ab der Fällung gut rührbare Suspensionen und außerdem eine gute Wärmeabführung.Alko are used as solvents for the precipitation process according to the invention Get with 1 to 3 carbon atoms, preferably ethanol, used. As ethanol In addition to anhydrous ethanol, the usual alcohol can be used be up to 10 weight percent water and the usual denatures agents such. B. methyl ethyl ketone, petroleum ether, pyridine can. The ethanol is at least twice the amount by weight Polyamides used. It is advantageous for whirl sinter powders Four to five times, and four to seven for electrostatic powders times, in particular approximately four or 5.6 times. In other words, be the concentration of the polyamide in the solution is 35 percent by weight, advantageously 25 to 15, in particular about 20 or 15 percent by weight. In These concentration ranges are readily stirrable from the precipitation Suspensions and also good heat dissipation.
In Anlehnung an die DE-OS 35 10 690 wendet man für die Fällung Lösetempe raturen von 135 bis 165°C, vorzugsweise von 140 bis 155°C, Abkühlraten von 10 bis 40 K/h, vorzugsweise 25 bis 35 K/h, sowie Fälltemperaturen von 100 bis 130°C, vorzugsweise von 105 bis 125°C, an. Im Hinblick auf die angestrebte Feinheit sind gemäß der DE-OS 35 10 691 hohe Rührerdrehzahlen vorteilhaft. Der Fällprozeß als solcher ist dem Fachmann bekannt, die für das jeweils umzufällende Polyamid am besten geeigneten Verfahrensbedin gungen können durch Vorversuche leicht ermittelt werden.In accordance with DE-OS 35 10 690 is used for the precipitation solution temperature temperatures from 135 to 165 ° C, preferably from 140 to 155 ° C, cooling rates from 10 to 40 K / h, preferably 25 to 35 K / h, and falling temperatures of 100 to 130 ° C, preferably from 105 to 125 ° C. In terms of the desired fineness are high stirrer speeds according to DE-OS 35 10 691 advantageous. The precipitation process as such is known to the person skilled in the art the most suitable process conditions for the polyamide to be reprecipitated conditions can easily be determined by preliminary tests.
Die Suspension wird bis zu der bei 20% Ethanolfeuchte einsetzenden Rie selfähigkeit des Produkts unter vermindertem Druck, Wandtemperaturen un terhalb 100°C sowie schonender mechanischer Bewegung, z. B. in langsam laufenden Schaufel- oder Taumeltrocknern getrocknet, um Grobgutbildung durch Agglomeration zu vermeiden. Nach Erreichen der Rieselfähigkeit kann die mechanische Bewegung intensiver werden und die Temperatur im Trockner auf über 100 bis zu 150°C angehoben werden.The suspension is up to the Rie starting at 20% ethanol moisture ability of the product under reduced pressure, wall temperatures and below 100 ° C and gentle mechanical movement, e.g. B. in slow running paddle or tumble dryers dried to form coarse material to avoid by agglomeration. After free flowing can the mechanical movement become more intense and the temperature in the dryer can be raised to over 100 up to 150 ° C.
Geeignete Polyamide sind z. B. die Polymerisate von Lactamen mit einer C- Atomzahl 10 bzw. die Polykondensate der entsprechenden ω-Aminocarbon säuren sowie die Polykondensate aus aliphatischen Diaminen und Dicarbon säuren mit jeweils < 10 C-Atomen und Copolyamide aus den vorgenannten Monomeren. Bevorzugt wird hydrolytisch polymerisiertes PA 12 eingesetzt. Ungeregelte Polyamide eignen sich ebenso wie geregelte Polyamide; ihre relative Lösungsviskosität, gemessen in 0,5-%iger m-Kresollösung nach DIN 53 727 beträgt 1,4 bis 2,0, bevorzugt 1,5 bis 1,8.Suitable polyamides are e.g. B. the polymers of lactams with a C- Number of atoms 10 or the polycondensates of the corresponding ω-aminocarbon acids and the polycondensates from aliphatic diamines and dicarbon acids each with <10 C atoms and copolyamides from the aforementioned Monomers. Hydrolytically polymerized PA 12 is preferably used. Unregulated polyamides are just as suitable as regulated polyamides; your relative solution viscosity, measured in 0.5% m-cresol solution according to DIN 53,727 is 1.4 to 2.0, preferably 1.5 to 1.8.
Die Fällung kann auch in Gegenwart von Pigmenten, wie Titandioxid, Ruß, BaSO₄, ZnS, Cadmiumrot, Eisenoxid, oder Stabilisatoren, wie 4-Hydroxy- 3,5-di-tert.-butyl-phenylpropionsäure, 4-Hydroxy-3,5-di-tert.-butyl-phe nyl-propionsäure-hexamethylendiamin-bisamid, -propionsäureester mit einem aliphatischen Alkohol mit 1 bis 18 C-Atomen, Tris-alkylphenyl-, Tris alkyl-, Tris-aryl- oder gemischten Estern der phosphorigen Säure, deren Alkylrest 1 bis 16 C-Atome enthält und geradkettig oder verzweigt ist, oder in Gegenwart von Tensiden vorgenommen werden.The precipitation can also take place in the presence of pigments, such as titanium dioxide, carbon black, BaSO₄, ZnS, cadmium red, iron oxide, or stabilizers, such as 4-hydroxy 3,5-di-tert-butyl-phenylpropionic acid, 4-hydroxy-3,5-di-tert-butyl-phe nyl-propionic acid-hexamethylenediamine-bisamide, -propionic acid ester with one aliphatic alcohol with 1 to 18 carbon atoms, tris-alkylphenyl, tris alkyl, tris-aryl or mixed esters of phosphorous acid, the Alkyl radical contains 1 to 16 carbon atoms and is straight-chain or branched, or in the presence of surfactants.
Nach der Fällung werden die Produkte mit sogenannten Sichtermühlen und Gegenstrahlmühlen gemahlen. Die Bandbreite des Kornspektrums ist dabei nicht entscheidend. Das Mahlgut sollte jedoch, um einen erhöhten Ener gieaufwand im Mahlschritt zu vermeiden, keine Korngrößen über 250 µm auf weisen.After the precipitation, the products are so-called sifter mills and Counter jet mills ground. The range of the grain spectrum is included not critical. The regrind should, however, to increase the energy to avoid gi expenditure in the grinding step, no grain sizes above 250 microns point.
Bei der Sichtermühle wird zweistufig bei Temperaturen von < 50°C gear beitet. Der bevorzugte Drehzahlbereich liegt zwischen 1200 bis 2400 Umdrehungen/Minute.The classifier mill has two stages at temperatures of <50 ° C works. The preferred speed range is between 1200 to 2400 Revolutions / minute.
Bei der Gegenstrahlmühle ist die Temperatur eine Prozeßvariable. Es wird bei Temperaturen von 10 bis -80°C gearbeitet. Die optimalen Temperaturen liegen zwischen 10 und -20°C. Die Temperaturen und Drehzahlbereiche bei der Gegenstrahlmühle sind prozeßvariabel. Die optimale Drehzahl liegt zwischen 1200 und 3000 U/Minute.In the counter jet mill, the temperature is a process variable. It will worked at temperatures from 10 to -80 ° C. The optimal temperatures are between 10 and -20 ° C. The temperatures and speed ranges at the counter jet mill are process variable. The optimal speed is between 1200 and 3000 rpm.
Nach dem Mahlverfahren können Produkte in einem Kaltmahlschritt bei Tem peraturen unter 10°C mit einem Kornanteil von mindestens 98 Gewichtspro zent < 63 µm, vorzugsweise < 40 µm erhalten werden. Es ist auch möglich, Produkte mit einem Kornanteil von mindestens 98 Gewichtsprozent < 32 µm nach dem erfindungsgemäßen Verfahren herzustellen. Bei Raumtemperatur kann das Fällpulver auf einen Kornanteil von mindestens 98 Gewichtspro zent feiner als 40 µm vermahlen werden.After the grinding process, products can be cold-tempered at tem temperatures below 10 ° C with a grain fraction of at least 98 per weight zent <63 microns, preferably <40 microns can be obtained. It is also possible, Products with a grain content of at least 98% by weight <32 µm to produce by the method according to the invention. At room temperature the precipitated powder can have a grain content of at least 98% by weight be ground finer than 40 µm.
Die Schüttdichten der erfindungsgemäßen Produkte betragen < 230 g/l, vor zugsweise < 250 g/l.The bulk densities of the products according to the invention are <230 g / l preferably <250 g / l.
Das erfindungsgemäße Pulver kann als Zusatz zu Coil-Coating-Lacken und zur Metallbeschichtung nach dem elektrostatischen Sprühverfahren ver wendet werden.The powder according to the invention can be used as an additive to coil coating lacquers and for metal coating using the electrostatic spray method be applied.
400 kg ungeregeltes, durch hydrolytische Polymerisation hergestelltes PA 12 mit einer relativen Lösungsviskosität von 1,62 und einem Endgruppenge halt von 75 mmol/kg COOH bzw. 69 mmol (kg NH₂ werden mit 1500 l Ethanol, vergällt mit 2-Butanon und 1% Wassergehalt, innerhalb von 5 Stunden in einem 3 m³-Rührkessel (⌀ = 160 cm) auf 145°C gebracht und unter Rühren (Blattrührer, ⌀ = 80 cm, Drehzahl = 85 Upm) 1 Stunde bei dieser Tempera tur belassen. Anschließend wird die Manteltemperatur auf 124°C reduziert und unter kontinuierlichem Abdestillieren des Ethanols mit einer Kühlrate von 25 K/h bei derselben Rührerdrehzahl die Innentemperatur auf 125°C gebracht. Von jetzt an wird bei gleicher Kühlrate die Manteltemperatur 2 bis 3 K unter der Innentemperatur gehalten, bis bei 109°C die Fällung, erkennbar an der Wärmeentwicklung, einsetzt. Die Destillationsgeschwin digkeit wird soweit erhöht, daß die Innentemperatur nicht über 109,3°C ansteigt. Nach 20 Minuten fällt die Innentemperatur ab, was das Ende der Fällung anzeigt. Durch weiteres Abdestillieren und Kühlung über den Man tel wird die Temperatur der Suspension auf 45°C gebracht und die Suspen sion danach in einen Schaufeltrockner überführt. Das Ethanol wird bei 70°C/400 mbar abdestilliert und der Rückstand anschließend bei 20 mbar/85°C 3 Stunden nachgetrocknet.400 kg of unregulated PA produced by hydrolytic polymerization 12 with a relative solution viscosity of 1.62 and an end group density content of 75 mmol / kg COOH or 69 mmol (kg NH₂ are mixed with 1500 l ethanol, denatures with 2-butanone and 1% water content, within 5 hours a 3 m³ stirred kettle (⌀ = 160 cm) brought to 145 ° C and with stirring (Blade stirrer, ⌀ = 80 cm, speed = 85 rpm) 1 hour at this tempera leave the door. The jacket temperature is then reduced to 124 ° C and while continuously distilling off the ethanol at a cooling rate of 25 K / h at the same stirrer speed the internal temperature to 125 ° C brought. From now on, the jacket temperature becomes 2 with the same cooling rate kept up to 3 K below the internal temperature until the precipitation at 109 ° C, recognizable by the heat development. The distillation rate is increased to such an extent that the internal temperature does not exceed 109.3 ° C increases. After 20 minutes, the inside temperature drops, which is the end of the Precipitation indicates. By further distilling and cooling over the man The temperature of the suspension is brought to 45 ° C. and the suspensions sion then transferred to a paddle dryer. The ethanol is at 70 ° C / 400 mbar distilled off and then the residue 20 mbar / 85 ° C for 3 hours.
Das so erhaltene getrocknete Aufgabegut wird über eine Dosierschnecke der Sichtermühle zugeführt. In der Sichtermühle wird bei 1650 U/Minute und bei Umgebungstemperatur das Aufgabegut gemahlen. Der eingesetzte Stick stoffvolumenstrom beträgt 1200 m³/h die Pressung 80 mbar.The dried feed thus obtained is the via a dosing screw Classifier mill fed. In the classifier mill is at 1650 rpm and the feed is ground at ambient temperature. The stick used material volume flow is 1200 m³ / h, the pressure 80 mbar.
Die Abscheidung des Feinstpulvers erfolgt über einen der Mühle nachge schalteten Zyklon.The fine powder is separated out via one of the mills switched cyclone.
Die Siebanalyse des Feinpulvers ergab (nach DIN 53 734):The sieve analysis of the fine powder showed (according to DIN 53 734):
< 32 µm: 98,8%,
< 40 µm: 99,2%,
< 50 µm: 100%,
Schüttdichte (nach DIN 53 466): 330 g/l.<32 µm: 98.8%,
<40 µm: 99.2%,
<50 µm: 100%,
Bulk density (according to DIN 53 466): 330 g / l.
Man wiederholt Beispiel 1 mit einem PA 12-Granulat, das durch hydroly tische LL-Polymerisation in Gegenwart von 1 Teil Dodecandisäure/100 Teile LL erhalten worden ist: ηrel = 1,60, [COOH] = 132 mmol/kg, [NH₂] = 5 mmol/kg.Example 1 is repeated with a PA 12 granulate which is hydrolyzed by table LL polymerization in the presence of 1 part of dodecanedioic acid / 100 parts LL has been obtained: ηrel = 1.60, [COOH] = 132 mmol / kg, [NH₂] = 5 mmol / kg.
Mit Ausnahme der Rührerdrehzahl (100 Upm) entsprechen die Löse-, Fäll- und Trocknungsbedingungen dem Beispiel 1.With the exception of the stirrer speed (100 rpm), the dissolving, and drying conditions in Example 1.
Das Aufgabegut wird über eine Zellenradschleuse einer Gegenstrahlmühle zugeführt. Bei einem Gasdurchsatz von 710 m³/h, 0°C Mühlentemperatur und 3000 U/Minute wird das Pulver gemahlen. Über das Sichterrad erfolgt die Trennung in Grob- und Feingut, so daß über ein abschließendes Filter die Mahlgutabscheidung durchgeführt wird.The feed material is fed through a rotary valve of a counter jet mill fed. With a gas throughput of 710 m³ / h, 0 ° C mill temperature and The powder is ground at 3000 rpm. This is done via the classifier wheel Separation into coarse and fine material, so that the final filter Grist removal is carried out.
Die Siebanalyse liefert folgendes Bild:The sieve analysis provides the following picture:
Claims (10)
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WO2023174990A1 (en) | 2022-03-15 | 2023-09-21 | Evonik Operations Gmbh | Powder for use in a layerwise process with lasers in the visible and near-infrared range |
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DE2906647C2 (en) * | 1979-02-21 | 1980-12-11 | Chemische Werke Huels Ag, 4370 Marl | Process for the production of powdery coating agents !! based on polyamides with at least 10 aliphatically bonded carbon atoms per carbonamide group |
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DE2906647C2 (en) * | 1979-02-21 | 1980-12-11 | Chemische Werke Huels Ag, 4370 Marl | Process for the production of powdery coating agents !! based on polyamides with at least 10 aliphatically bonded carbon atoms per carbonamide group |
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