DE102004009887A1 - Production of microfine fibres or powder for use e.g. in non-wovens or coating powders, involves electrostatic spinning or spraying from a thermoplastic polymer melt, e.g. polybutylene terephthalate - Google Patents
Production of microfine fibres or powder for use e.g. in non-wovens or coating powders, involves electrostatic spinning or spraying from a thermoplastic polymer melt, e.g. polybutylene terephthalate Download PDFInfo
- Publication number
- DE102004009887A1 DE102004009887A1 DE102004009887A DE102004009887A DE102004009887A1 DE 102004009887 A1 DE102004009887 A1 DE 102004009887A1 DE 102004009887 A DE102004009887 A DE 102004009887A DE 102004009887 A DE102004009887 A DE 102004009887A DE 102004009887 A1 DE102004009887 A1 DE 102004009887A1
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- Germany
- Prior art keywords
- production
- thermoplastic polymer
- spraying
- electrostatic spinning
- powder
- 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.)
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Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/0023—Electro-spinning characterised by the initial state of the material the material being a polymer melt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B5/00—Electrostatic spraying apparatus; Spraying apparatus with means for charging the spray electrically; Apparatus for spraying liquids or other fluent materials by other electric means
- B05B5/001—Electrostatic spraying apparatus; Spraying apparatus with means for charging the spray electrically; Apparatus for spraying liquids or other fluent materials by other electric means incorporating means for heating or cooling, e.g. the material to be sprayed
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B5/00—Electrostatic spraying apparatus; Spraying apparatus with means for charging the spray electrically; Apparatus for spraying liquids or other fluent materials by other electric means
- B05B5/025—Discharge apparatus, e.g. electrostatic spray guns
- B05B5/0255—Discharge apparatus, e.g. electrostatic spray guns spraying and depositing by electrostatic forces only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B5/00—Electrostatic spraying apparatus; Spraying apparatus with means for charging the spray electrically; Apparatus for spraying liquids or other fluent materials by other electric means
- B05B5/16—Arrangements for supplying liquids or other fluent material
- B05B5/1683—Arrangements for supplying liquids or other fluent material specially adapted for particulate materials
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Nonwoven Fabrics (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von Mikrofasern oder Pulvern durch elektrostatisches Verspinnen oder Versprühen einer Schmelze von Polymeren und deren Verwendung.The The invention relates to a process for the production of microfibers or powders by electrostatic spinning or spraying a Melting of polymers and their use.
Die
Herstellung von Mikrofasern durch elektrostatisches Verspinnen von
Polymeren wie Polystyrol, PVC oder Polycarbonat aus der Lösung ist
bekannt (
Nachteilig an den bekannten Verfahren ist, dass die Polymere zum Verspinnen zunächst gelöst werden müssen, so dass schlecht lösliche thermoplastische Polymere nur bedingt eingesetzt werden können. Der zusätzliche Schritt des Lösens ist darüber hinaus zeitaufwendig und teuer, sowie eine nicht zu unterschätzende Fehlerquelle.adversely in the known processes, the polymers are for spinning first solved Need to become, so that is poorly soluble thermoplastic polymers can be used only conditionally. The additional Step of solving is about it also time consuming and expensive, as well as a not to be underestimated source of error.
Aufgabe ist es daher ein alternatives Verfahren zum Verspinnen von thermoplastischen Polymeren zu entwickeln. Die Aufgabe wird durch das erfindungsgemäße Verfahren dadurch gelöst, dass die Polymere als Schmelze eingesetzt und so elektrostatisch versponnen werden können.task Thus, it is an alternative method for spinning thermoplastic To develop polymers. The object is achieved by the method according to the invention solved by that the polymers used as a melt and so electrostatic can be spun.
Gegenstand der Erfindung ist daher ein Verfahren zur Herstellung von Fasern oder Pulvern mit einem Durchmesser < 50 μm durch elektrostatisches Verspinnen (Elektrospinning) oder Versprühen einer Schmelze von mindestens einem thermoplastischen Polymeren.object The invention is therefore a process for producing fibers or powders with a diameter <50 microns by electrostatic spinning (electrospinning) or spraying a Melt of at least one thermoplastic polymer.
Zur
Durchführung
des erfindungsgemäßen Verfahrens
wird eine Apparatur verwendet (
Die Apparatur besteht aus einer zylinderförmigen Probenkammer, die nach oben offen und nach unten von einer Düse abgeschlossen wird. Es können verschiedene Düsen mit unterschiedlichen Durchmessern verwendet werden, der Düsendurchmesser beträgt im allgemeinen 0,2–1,0 mm. Die Probenkammer wird von einem beheizbaren Ofen umschlossen. Nach Befüllung der Probenkammer mit dem Polymer wird dieses auf eine Temperatur oberhalb seiner Schmelztemperatur gebracht und dadurch aufgeschmolzen.The Apparatus consists of a cylindrical sample chamber, which after is open at the top and down by a nozzle. There can be different nozzles with different diameters are used, the nozzle diameter is generally 0.2-1.0 mm. The sample chamber is enclosed by a heatable oven. After filling the sample chamber with the polymer is this to a temperature brought above its melting temperature and thereby melted.
Es kann darüber hinaus auf das Polymer durch Auflegen eines geeigneten Stempels definierter Masse Druck ausgeübt und somit der Schmelzevorschub und dadurch die Homogenität der Fasern beeinflusst werden.It can over it on the polymer by placing a suitable stamp defined mass pressure applied and thus the melt feed and thereby the homogeneity of the fibers to be influenced.
An der Düse liegt gegen Erde ein elektrisches Feld mit Spannungen von 1 bis 100 kV an, bevorzugt 5 bis 60 kV, besonders bevorzugt 10 bis 55 kV.At the nozzle is against earth an electric field with voltages from 1 to 100 kV, preferably 5 to 60 kV, particularly preferably 10 to 55 kV.
Bevorzugt wird das erfindungsgemäße Verfahren in einer Kammer unter Schutzgas, vorzugsweise Stickstoff, ausgeführt, was dadurch gewährleistet ist, dass die gesamte Apparatur mit entsprechenden Gasanschlüssen versehen und eingekapselt wird. Unter Gleichstrombedingungen wird die Polymerschmelze im elektrischen Feld beschleunigt und streckt sich zu einem Faden oder reißt ab zu Tropfen, die dann Pulverpartikel bilden.Prefers becomes the method according to the invention in a chamber under inert gas, preferably nitrogen, carried out what thereby ensured is that the entire apparatus provided with appropriate gas connections and encapsulated. Under DC conditions, the polymer melt accelerated in the electric field and stretches to a thread or rips down to drops, which then form powder particles.
Der Durchmesser der erhaltenen Fasern beträgt im allgemeinen < 50 μm, vorzugsweise < 20 μm, bevorzugt < 10 μm, ganz besonders bevorzugt < 5 μm, insbesondere < 1 μm.Of the Diameter of the fibers obtained is generally <50 .mu.m, preferably <20 .mu.m, preferably <10 .mu.m, very particularly preferably <5 .mu.m, in particular <1 .mu.m.
Besonders geeignete thermoplastische Polymere für das erfindungsgemäße Verfahren sind Polyester, Polyarylsulfide, Polyacetale und/oder Cycloolefincopolymere.Especially suitable thermoplastic polymers for the process according to the invention are polyesters, polyaryl sulfides, polyacetals and / or cycloolefin copolymers.
Unter Polyestern sind thermoplastische Polymere mit sich wiederholenden Estergruppen in der Hauptkette zu verstehen. Beispiele sind Polykondenssationsprodukte der Terephthalsäure, der Isophthalsäure, der Naphthalindicarbonsäure, der Adipinsäure oder ihrer Ester mit zweiwertigen Alkoholen wie Ethylenglykol, Butandiol usw.Under Polyesters are thermoplastic polymers with repeating ones To understand ester groups in the main chain. Examples are polycondensation products terephthalic acid, the isophthalic acid, the naphthalenedicarboxylic acid, adipic acid or their esters with dihydric alcohols such as ethylene glycol, butanediol etc.
Besonders bevorzugt verwendet wird Polybutylenterephthalat (PBT).Especially Polybutylene terephthalate (PBT) is preferably used.
Unter Polyarylsulfiden sind thermoplastische Polymere mit sich wiederholenden Schwefelgruppen in der weitgehend aromatischen Hauptkette zu verstehen. Sie umfassen sowohl Homo- als auch Copolymere.Under Polyaryl sulfides are repeating thermoplastic polymers To understand sulfur groups in the largely aromatic main chain. They include both homo- and copolymers.
Besonders bevorzugt ist Polyphenylensulfid (PPS).Especially preferred is polyphenylene sulfide (PPS).
Unter Polyacetalen sind Polymere, die als Wiederholeinheit hauptsächlich Oxymethlen-Gruppen (CH2O-) aufweisen. Sie umfassen Polyoxymethylen- (POM) Homopolymere, -Copolymere, -Terpolymere und -Blockpolymere.Among polyacetals are polymers which have as a repeating unit mainly Oxymethlen groups (CH 2 O-). They include polyoxymethylene (POM) homopolymers, copolymers, terpolymers and block polymers.
Unter Cycloolefincopolymeren sind Copolymere auf der Basis von cyclischen und linearen Olefinen, beispielsweise Norbornen, Ethylidennorbornen und unverzweigten α-Olefinen, zu verstehen. Besonders bevorzugt sind Copolymere aus Norbornen und Ethylen (COC).Under Cycloolefin copolymers are copolymers based on cyclic ones and linear olefins, for example norbornene, ethylidenenorbornene and unbranched α-olefins, to understand. Particularly preferred are copolymers of norbornene and ethylene (COC).
Es können auch Mischungen der vorgenannten Polymere untereinander oder mit anderen thermoplastischen Polymeren verwendet werden.It can also mixtures of the aforementioned polymers with each other or with other thermoplastic polymers are used.
Die vorgenannten thermoplastischen Polymere und ihre Herstellung sind in der Fachliteratur, wie beispielsweise in James M. Margolis, 1985, Engineering Thermoplastics, New York: Dekker, beschrieben, worauf Bezug genommen wird.The aforementioned thermoplastic polymers and their preparation in the literature, such as in James M. Margolis, 1985, Engineering Thermoplastics, New York: Dekker, describes what reference is taken.
Darüber hinaus sind PBT, PPS, POM und COC beispielsweise als Celanex®, Fortron®, Hostaform® oder Topas® im Handel erhältlich.In addition, PBT, PPS, POM and COC for example, are available as Celanex ®, Fortron ®, Hostaform ® and Topas ® commercially.
Bevorzugt sind die eingesetzten Polymere additiviert mit üblichen Zusätzen, die beispielsweise in H. Zweifel: Plastics Additives Handbook, 5th edition, Hanser Verlag 2000, beschrieben sind, worauf ausdrücklich Bezug genommen wird.The polymers used are preferably additized with customary additives which are described, for example, in H. Zweifel: Plastics Additives Handbook, 5 th edition, Hanser Verlag 2000, to which reference is expressly made.
Bevorzugt werden für das erfindungsgemäße Verfahren PBT, PPS, POM und/oder COC, ganz besonders bevorzugt PPS, POM und/oder COC, eingesetzt.Prefers be for the inventive method PBT, PPS, POM and / or COC, very particularly preferably PPS, POM and / or COC, used.
Die nach dem erfindungsgemäßen Verfahren hergestellten Fasern mit einem Durchmesser < 50 μm können zur Herstellung eines Vliesmaterials verwendet werden, welches beispielsweise zur Aufbereitung von Wasser aus Kraftstoff, zum Beispiel Flugbenzin, eingesetzt werden kann.The according to the inventive method produced fibers with a diameter <50 .mu.m can for Production of a nonwoven material may be used, for example for the treatment of water from fuel, for example jet fuel, can be used.
Darüber hinaus können die nach dem erfindungsgemäßen Verfahren hergestellten Fasern mit einem Durchmesser < 50 μm zur Herstellung von mikrofeinen Pulvern verwendet werden. Besonders bevorzugt werden die Fasern hierzu fein gemahlen. Auch können mit dem beschriebenen Verfahren direkt Pulver hergestellt werden. Pulver aus den genannten Polymeren können beispielsweise zur Beschichtung oder als Additive in Farben und Lacken oder zur Mischung mit anderen Polymeren eingesetzt werden.Furthermore can those according to the inventive method produced fibers with a diameter <50 microns be used for the production of microfine powders. Especially Preferably, the fibers are finely ground for this purpose. Also can with The method described directly powder are produced. powder from the polymers mentioned can for example, for coating or as additives in paints and Paints or for mixing with other polymers.
Darüber hinaus erläutern die nachfolgenden Beispiele die Erfindung ohne diese darauf zu begrenzen.Furthermore explain the following examples, the invention without limiting it thereto.
Für die in Tab. 1 aufgeführten Beispiele 1–4 wurde unter Stickstoffatmosphäre Elektrospinning von POM (Hostaform FG45U01) aus der Schmelze unter den in der Tabelle angegebenen Bedingungen durchgeführt.For the in Tab. 1 listed Examples 1-4 was under nitrogen atmosphere Electrospinning of POM (Hostaform FG45U01) from the melt below carried out in the conditions specified in the table.
Tabelle 1 Table 1
Es zeigt sich, dass der mittlere Faserdurchmesser der Beispiele 1–4 nur 1,50–8,00 μm beträgt.It shows that the average fiber diameter of Examples 1-4 is only 1.50-8.00 microns.
In den Beispielen 5–11 (Tabelle 2) wurde Elektrospinning von PPS (Fortron 0203) aus der Schmelze in einer Stickstoffatmosphäre durchgeführt.In Examples 5-11 (Table 2) was electrospinning of PPS (Fortron 0203) from the Melt carried out in a nitrogen atmosphere.
Tabelle 2 Table 2
Es zeigt sich, dass der mittlere Durchmesser der erhaltenen PPS-Fasern teilweise sogar kleiner als 1 μm ist.It shows that the average diameter of the obtained PPS fibers sometimes even less than 1 micron is.
In den Beispielen 12–16 (Tabelle 3) wurde Elektrospinning von COC (Topas TM CM 600384) aus der Schmelze unter den angegebenen Bedingungen (kein Inertgas) durchgeführt.In Examples 12-16 (Table 3) was electrospinning of COC (Topas ™ CM 600384) the melt under the specified conditions (no inert gas) performed.
Tabelle 3 Table 3
Es zeigt sich, dass der mittlere Faserdurchmesser bimodal verteilt ist und Faserdicken mit ca. 0,5 μm und ca. 3 μm enthält.It shows that the average fiber diameter distributed bimodal is and fiber thicknesses of about 0.5 microns and approx. 3 μm contains.
In den Beispielen 17–19 (Tabelle 4) wurde Elektrospinning von 2 verschiedenen PPS-Typen (Fortron-Typ 0203 und 0205) aus der Schmelze unter den angegebenen Bedingungen (kein Inertgas) durchgeführt.In Examples 17-19 (Table 4) was electrospinning of 2 different PPS types (Fortron type 0203 and 0205) from the melt below the specified Conditions (no inert gas) performed.
Tabelle 4 Table 4
Es zeigt sich dass, der mittlere Faserdurchmesser 3–20 μm beträgt.It shows that the average fiber diameter is 3-20 microns.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102004009887A DE102004009887A1 (en) | 2004-02-26 | 2004-02-26 | Production of microfine fibres or powder for use e.g. in non-wovens or coating powders, involves electrostatic spinning or spraying from a thermoplastic polymer melt, e.g. polybutylene terephthalate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102004009887A DE102004009887A1 (en) | 2004-02-26 | 2004-02-26 | Production of microfine fibres or powder for use e.g. in non-wovens or coating powders, involves electrostatic spinning or spraying from a thermoplastic polymer melt, e.g. polybutylene terephthalate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE102004009887A1 true DE102004009887A1 (en) | 2005-07-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE102004009887A Withdrawn DE102004009887A1 (en) | 2004-02-26 | 2004-02-26 | Production of microfine fibres or powder for use e.g. in non-wovens or coating powders, involves electrostatic spinning or spraying from a thermoplastic polymer melt, e.g. polybutylene terephthalate |
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|---|---|
| DE (1) | DE102004009887A1 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102006048292A1 (en) * | 2006-10-12 | 2008-04-17 | Irema-Filter Gmbh | Process to form produce a non-woven fleece from molten polymer spun onto to a ribbon substrate under high voltage |
| DE102007027014A1 (en) | 2007-06-08 | 2008-12-18 | Rainer Busch | Spinning nano- and micro-fibers, rapidly accelerates stratified polymers and polymer solutions whilst applying electrical field to modify physical- and surface properties |
| WO2010015709A2 (en) | 2008-08-08 | 2010-02-11 | Basf Se | Fibrous surface structure containing active ingredients with controlled release of active ingredients, use thereof and method for the production thereof |
| WO2010072665A1 (en) | 2008-12-23 | 2010-07-01 | Basf Se | Modification of nano- or mesofibers or textile fabrics manufactured by way of electrospinning using amphiphilic proteins |
| US8298471B2 (en) | 2007-12-11 | 2012-10-30 | Basf Se | Process for producing nano- and mesofibers by electrospinning colloidal dispersions comprising at least one essentially water-insoluble polymer |
| EP2684562A1 (en) | 2008-08-08 | 2014-01-15 | Basf Se | Fibre layer with an active substance on the basis of bio-polymers, applications of same and method for their manufacture |
| WO2021008681A1 (en) * | 2019-07-15 | 2021-01-21 | Symrise Ag | Coaxial fibers containing liquid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4402857A1 (en) * | 1994-01-31 | 1995-08-03 | Freudenberg Carl Fa | Fibre-bonded fabric prodn. esp. for air or liq. filters |
| DE10106913A1 (en) * | 2001-02-15 | 2002-09-05 | Sandler Helmut Helsa Werke | Electrostatically spinning polymers, comprises adding a substance to a polymer melt or solution before spinning it, to alter the surface tension and polymer throughput |
-
2004
- 2004-02-26 DE DE102004009887A patent/DE102004009887A1/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4402857A1 (en) * | 1994-01-31 | 1995-08-03 | Freudenberg Carl Fa | Fibre-bonded fabric prodn. esp. for air or liq. filters |
| DE10106913A1 (en) * | 2001-02-15 | 2002-09-05 | Sandler Helmut Helsa Werke | Electrostatically spinning polymers, comprises adding a substance to a polymer melt or solution before spinning it, to alter the surface tension and polymer throughput |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102006048292A1 (en) * | 2006-10-12 | 2008-04-17 | Irema-Filter Gmbh | Process to form produce a non-woven fleece from molten polymer spun onto to a ribbon substrate under high voltage |
| DE102007027014A1 (en) | 2007-06-08 | 2008-12-18 | Rainer Busch | Spinning nano- and micro-fibers, rapidly accelerates stratified polymers and polymer solutions whilst applying electrical field to modify physical- and surface properties |
| US8298471B2 (en) | 2007-12-11 | 2012-10-30 | Basf Se | Process for producing nano- and mesofibers by electrospinning colloidal dispersions comprising at least one essentially water-insoluble polymer |
| WO2010015709A2 (en) | 2008-08-08 | 2010-02-11 | Basf Se | Fibrous surface structure containing active ingredients with controlled release of active ingredients, use thereof and method for the production thereof |
| EP2684562A1 (en) | 2008-08-08 | 2014-01-15 | Basf Se | Fibre layer with an active substance on the basis of bio-polymers, applications of same and method for their manufacture |
| WO2010072665A1 (en) | 2008-12-23 | 2010-07-01 | Basf Se | Modification of nano- or mesofibers or textile fabrics manufactured by way of electrospinning using amphiphilic proteins |
| WO2021008681A1 (en) * | 2019-07-15 | 2021-01-21 | Symrise Ag | Coaxial fibers containing liquid |
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Owner name: TRANSMIT GESELLSCHAFT FUER TECHNOLOGIETRANSFER MBH, |
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| 8127 | New person/name/address of the applicant |
Owner name: PHILIPPS-UNIVERSITAET MARBURG, 35037 MARBURG, DE |
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Inventor name: REIL, FRANK, SINGAPORE, SG Inventor name: SCHNELLER, ARNOLD, DR., 64342 SEEHEIM-JUGENHEI, DE Inventor name: REISINGER, THOMAS, DR., 55218 INGELHEIM, DE Inventor name: GREINER, ANDREAS, PROF. DR., 35287 AMOENEBURG, DE |
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