EP0727249A1 - Static mixer for very viscous liquids - Google Patents
Static mixer for very viscous liquids Download PDFInfo
- Publication number
- EP0727249A1 EP0727249A1 EP95810073A EP95810073A EP0727249A1 EP 0727249 A1 EP0727249 A1 EP 0727249A1 EP 95810073 A EP95810073 A EP 95810073A EP 95810073 A EP95810073 A EP 95810073A EP 0727249 A1 EP0727249 A1 EP 0727249A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mixing element
- mixing
- webs
- sector
- flow direction
- 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.)
- Granted
Links
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
- B01F25/40—Static mixers
- B01F25/42—Static mixers in which the mixing is affected by moving the components jointly in changing directions, e.g. in tubes provided with baffles or obstructions
- B01F25/43—Mixing tubes, e.g. wherein the material is moved in a radial or partly reversed direction
- B01F25/431—Straight mixing tubes with baffles or obstructions that do not cause substantial pressure drop; Baffles therefor
- B01F25/4316—Straight mixing tubes with baffles or obstructions that do not cause substantial pressure drop; Baffles therefor the baffles being flat pieces of material, e.g. intermeshing, fixed to the wall or fixed on a central rod
- B01F25/43161—Straight mixing tubes with baffles or obstructions that do not cause substantial pressure drop; Baffles therefor the baffles being flat pieces of material, e.g. intermeshing, fixed to the wall or fixed on a central rod composed of consecutive sections of flat pieces of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
Definitions
- the invention relates to a static mixing device for highly viscous media, in particular for plastic melts, according to the preamble of claim 1.
- the invention also relates to a mixing element of such a mixing device and to the use of this device.
- the mixing element of this device has a structure which is composed of interlocking, intersecting webs, the webs forming two groups of structural elements aligned in parallel.
- the mixing element 10 of FIG. 1 is composed of the crossing webs 3 and 30.
- the reference symbol 30 is assigned to the marginal webs.
- An adjacent mixing element 10 ' is indicated by dash-dotted lines.
- the elliptical lines 35 and 36 indicate the edges of surfaces that are spanned by webs, not shown. The surfaces with the edges 35 and 36 cross each other.
- the two mixing elements 10 and 10 ' are the same, but one is arranged rotated by 90 ° with respect to the other about the longitudinal axis.
- the longitudinal axis runs in the direction of arrow 4, which represents the main direction of flow.
- marginal webs 30 are omitted according to the invention, two open, segment-shaped marginal regions are formed which lie between the side edges of the lateral webs 31 (see FIG. 3) and the tube wall 2.
- the medium can flow axially uninhibited through the segment-shaped edge regions. As has been shown experimentally, this measure remains with regard to the mixing quality without a significant negative effect.
- the marginal webs 30 have been removed and replaced by ribs 5.
- the reinforcing ribs 5 can have the length of the mixing element 1 (shown in solid lines) or they can have extensions 5a (indicated by dash-dotted lines) which protrude into the adjacent mixing elements 1 'and 1' '.
- FIG. 4 shows the second case.
- FIG. 4 where, in addition to the mixing element 1 of FIG. 3, two adjacent mixing elements 1 'and 1' '(with the associated reinforcing ribs 5' and 5 '') can be seen.
- 5a and 5b the ribs 5, as provided in the mixing elements of FIGS. 3 and 4, are shown as separate parts.
- the ribs 5 are connected at the points 51 to the side webs 31 (welded in the present example).
- the ribs 5 can also be formed in the form of continuous bars extending over the entire length of the mixing device.
- all the webs 3, 31 of the mixing element 1 are of the same width.
- the distance between the lateral webs 31 and the tube wall 2 in the two segment-shaped edge regions is not greater than a web width.
- the node lines 32a and 32b which are given by intersections of the webs 3 and 31 (cf. FIG. 1), are advantageously ground in a wedge shape (see FIG. 3). This wedge shape results in a slightly lower pressure gradient during the mixing process.
- the webs 3 and 31 are advantageously cut to length and through to the crossing points a weld seam joined together. The reason for this measure is the same as for the omission of the marginal webs 30.
- the modification to the lateral node lines 33 has the additional effect that the pressure gradient is further reduced. There is practically no adverse effect on the mixing quality.
- FIG. 6 shows an example in which the rib 5 has a transverse extension 50 in its center.
- the cross section of this extension 50 fills a sector 60 of the segment-shaped edge region between mixing element 1 and tube 2 (cf. FIG. 4).
- the sector 60 is delimited by an arc 61 of the tube wall, by a partial section 62 of the side surface of the mixing element 1 and by two connecting sections 63 and 64.
- the mixing element 1 shown in the drawings is provided for a tube 2 with a circular cross section.
- the invention can of course also be correspondingly applied to mixing devices with other cross-sectional shapes.
- the mixing element - including the reinforcing ribs - can also be provided as a casting instead of in the form of a welded construction.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Mixers Of The Rotary Stirring Type (AREA)
Abstract
Description
Die Erfindung betrifft eine statische Mischvorrichtung für hochviskose Medien, insbesondere für Kunststoffschmelzen, gemäss Oberbegriff von Anspruch 1. Die Erfindung bezieht sich auch auf ein Mischelement einer derartigen Mischvorrichtung und auf eine Verwendung dieser Vorrichtung.The invention relates to a static mixing device for highly viscous media, in particular for plastic melts, according to the preamble of
Eine solche Vorrichtung ist aus den Patentschriften CH 642 564 (= P.5473) oder DE 28 08 854 (= P.5285) bekannt. Das Mischelement dieser Vorrichtung weist eine Struktur auf, die sich aus ineinandergreifenden, sich kreuzenden Stegen aufbaut, wobei die Stege zwei Gruppen von parallel ausgerichteten Strukturelementen bilden.Such a device is known from the patent specifications CH 642 564 (= P.5473) or DE 28 08 854 (= P.5285). The mixing element of this device has a structure which is composed of interlocking, intersecting webs, the webs forming two groups of structural elements aligned in parallel.
Durch die Stege, die am Rand des Mischelements angeordnet sind und dort mit ihrer Aussenkante an der Rohrwand anliegen oder zumindest in deren Nähe liegen, ergibt sich ein Problem: Im Bereich dieser Stege fliesst das zu mischende Medium wesentlich langsamer als im Innenbereich des Mischelements. In den Eckbereichen zwischen den randständigen Stegen und der Rohrwand weist daher das Medium eine relativ lange Verweilzeit auf, die - wie die Praxis gezeigt hat - zu Qualitätseinbussen bei den aus den gemischten Medien erzeugten Produkten führen kann.A problem arises from the webs which are arranged at the edge of the mixing element and lie there with their outer edge against the tube wall or at least lie in the vicinity thereof: in the region of these webs, the medium to be mixed flows much more slowly than in the interior of the mixing element. In the corner areas between the marginal webs and the pipe wall, the medium therefore has a relatively long dwell time, which - like that Practice has shown - can lead to a loss of quality in the products produced from the mixed media.
Es ist daher die Aufgabe der Erfindung, Mittel zu schaffen, mit denen die festgestellten Qualitätseinbussen beseitigt oder zumindest verringert werden können. Diese Aufgabe wird mit den im Anspruch 1 genannten Merkmalen gelöst. Die abhängigen Ansprüche 2 bis 6 beziehen sich auf besondere Ausführungsformen und vorteilhafte Weiterbildungen der erfindungsgemässen Mischvorrichtung. Eine solche Weiterbildung besteht darin, dass Verstärkungsrippen anstelle der randständigen Stege vorgesehen sind. Derartige Verstärkungen sind beim Mischen von hochviskosen Medien besonders vorteilhaft, da die Mischelemente sehr grossen Kräften aufgrund hoher axialer Druckgradienten ausgesetzt sind. Die Ansprüche 7 und 8 betreffen das Mischelement bzw. die Verwendung der erfindungsgemässen Vorrichtung für das Mischen und Homogenisieren einer Kunststoffschmelze.It is therefore the object of the invention to provide means with which the ascertained quality losses can be eliminated or at least reduced. This object is achieved with the features mentioned in
Nachfolgend wird die Erfindung anhand der Zeichnungen erläutert. Es zeigen:
- Fig. 1
- ein bekanntes Mischelement in perspektivischer Darstellung,
- Fig. 2
- die Randzone des Mischelements von Fig.1 mit angedeuteten Strömungsverhältnissen,
- Fig. 3
- ein erfindungsgemässes Mischelement, das sich durch eine Änderung des Mischelements von Fig.1 ergibt,
- Fig. 4
- eine Seitenansicht auf erfindungsgemässe, in Serie angeordnete Mischelemente,
- Fig.5a,b
- zwei Verstärkungsrippen und
- Fig. 6
- eine Verstärkungsrippe mit vergrössertem Mittelteil.
- Fig. 1
- a known mixing element in a perspective view,
- Fig. 2
- the edge zone of the mixing element of Figure 1 with indicated flow conditions,
- Fig. 3
- a mixing element according to the invention, which results from a change in the mixing element of Figure 1,
- Fig. 4
- 2 shows a side view of mixing elements according to the invention arranged in series,
- Fig.5a, b
- two reinforcing ribs and
- Fig. 6
- a reinforcing rib with an enlarged middle section.
Das Mischelement 10 der Fig.1 setzt sich aus den sich kreuzenden Stegen 3 und 30 zusammen. Das Bezugszeichen 30 ist den randständigen Stegen zugeordnet. Ein benachbartes Mischelement 10' ist strichpunktiert angedeutet. Die elliptischen Linien 35 bzw. 36 geben die Ränder von Flächen an, die durch nicht dargestellte Stege aufgespannt werden. Die Flächen mit den Rändern 35 bzw. 36 kreuzen einander. Die zwei Mischelemente 10 und 10' sind gleich, aber das eine ist um 90° gegenüber dem anderen um die Längsachse gedreht angeordnet. Die Längsachse verläuft in Richtung des Pfeils 4, der die Hauptströmungsrichtung darstellt.The
Fig.2 zeigt die kritischen Bereiche zwischen den randständigen Stegen 30 und der Rohrwand 2. Durch die dünnen Pfeile 4b ist die schwach ausgebildete Strömung in der Randregion dargestellt, während die breiten Pfeile 4a die stärkere Strömung im Innern des Mischelements 10 angeben. In den Eckbereichen 40 zwischen Rohrwand 2 und randständigen Stegen 30, die in Fig.2 durch eine Vielzahl von Punkten markiert sind, kommt die Bewegung des zu mischenden Mediums praktisch zum Erliegen.2 shows the critical areas between the
Werden die randständigen Stege 30 gemäss der Erfindung weggelassen, so entstehen zwei offene, segmentförmige Randbereiche, die zwischen den Seitenkanten der seitlichen Stege 31 (siehe Fig.3) und der Rohrwand 2 liegen. Durch die segmentförmigen Randbereiche kann das Medium axial ungehemmt durchströmen. Wie sich experimentell gezeigt hat, bleibt diese Massnahme bezüglich der Mischgüte ohne einen ins Gewicht fallenden negativen Effekt.If the
Bei dem Mischelement 1 der Fig.3 sind die randständigen Stege 30 entfernt und durch Rippen 5 ersetzt worden. Mit den Rippen 5 erhält das Mischelement 1 eine Verstärkung in axialer Richtung. Die Verstärkungsrippen 5 können gerade die Länge des Mischelements 1 haben (ausgezogen dargestellt) oder sie können Verlängerungen 5a aufweisen (strichpunktiert angedeutet), die in die benachbarten Mischelemente 1' und 1'' hineinragen. Der zweite Fall ist in Fig.4 dargestellt, wo neben dem Mischelement 1 der Fig.3 zwei benachbarte Mischelemente 1' und 1'' (mit den zugeordneten Verstärkungsrippen 5' und 5'') zu sehen sind. In den Figuren 5a und 5b sind die Rippen 5, wie sie in den Mischelementen der Figuren 3 bzw. 4 vorgesehen sind, als separate Teile abgebildet. Die Rippen 5 sind an den Stellen 51 mit den seitlichen Stegen 31 verbunden (verschweisst im vorliegenden Beispiel). Die Rippen 5 können auch in Form von durchgehenden, über die gesamte Länge der Mischvorrichtung sich erstreckende Balken gebildet sein.In the
Bei dem gezeigten Ausführungsbeispiel sind alle Stege 3, 31 des Mischelements 1 gleich breit. Der Abstand zwischen den seitlichen Stegen 31 und der Rohrwand 2 in den beiden segmentförmigen Randbereichen ist nicht grösser als eine Stegbreite.In the embodiment shown, all the
Mit Vorteil werden die Knotenlinien 32a und 32b, die durch Kreuzungsstellen der Stege 3 und 31 gegeben sind (vgl. Fig.1), keilförmig zugeschliffen (siehe Fig.3). Dank dieser Keilform ergibt sich ein etwas geringerer Druckgradient während des Mischvorgangs. Auch an den seitlichen Knotenlinien 33 werden die Stege 3 und 31 mit Vorteil bis zu den Kreuzungsstellen abgelängt und durch eine Schweissnaht miteinander verbunden. Der Grund für diese Massnahme ist der gleiche wie für das Weglassen der randständigen Stege 30. Die Modifikation an den seitlichen Knotenlinien 33 hat den zusätzlichen Effekt, dass der Druckgradient weiter verkleinert wird. Ein nachteiliger Effekt auf die Mischgüte ist praktisch nicht vorhanden.The node lines 32a and 32b, which are given by intersections of the
Für die Formgebung der Verstärkungsrippen 5 bestehen weitere Möglichkeiten. In Fig.6 ist ein Beispiel dargestellt, bei dem die Rippe 5 in ihrer Mitte eine transversale Erweiterung 50 aufweist. Der Querschnitt dieser Erweiterung 50 füllt einen Sektor 60 des segmentförmigen Randbereichs zwischen Mischelement 1 und Rohr 2 aus (vgl. Fig.4). Dabei ist der Sektor 60 durch einen Bogen 61 der Rohrwand, durch eine Teilstrecke 62 der Seitenfläche des Mischelements 1 sowie durch zwei Verbindungsstrecken 63 und 64 umgrenzt. Die Höhe des Sektors 60, gemessen senkrecht zu der durch die seitlichen Stege 31 aufgespannten Seitenfläche des Mischelements 1, ist kleiner als die Breite des Sektors (= Länge der Teilstrecke 62).There are further possibilities for the shape of the reinforcing
Das in den Zeichnungen dargestellte Mischelement 1 ist für ein Rohr 2 mit kreisförmigem Querschnitt vorgesehen. Selbstverständlich lässt sich die Erfindung entsprechend auch auf Mischvorrichtungen mit anderen Querschnittsformen anwenden. Ebenso ist die Erfindung auf eine Vorrichtung anwendbar, die in der europäischen Patentanmeldung Nr. 93810701.8 (= P.6600) offenbart ist und bei der das Mischelement einen flanschartigen Ring aufweist. Das Mischelement - einschliesslich der Verstärkungsrippen - kann statt in Form einer Schweisskonstruktion auch als Gussstück vorgesehen sein.The mixing
Claims (8)
dadurch gekennzeichnet, dass der Rohrquerschnitt durch das Mischelement nicht vollständig abgedeckt ist, derart nämlich, dass zwei segmentförmige Randbereiche, die zwischen den Seitenkanten von seitlichen Stegen (31) des Mischelements und der Rohrwand liegen, keine schräg zur Hauptfliessrichtung angeordnete Stege (30) aufweisen.Static mixing device for highly viscous media, which comprises a tube (2) and at least one mixing element (10) arranged in the tube, the tube defining a main flow direction (4) of the medium to be mixed, the structural elements of the mixing element essentially webs (3, 31) and the webs enclose an angle with the main flow direction,
characterized in that the pipe cross-section is not completely covered by the mixing element, namely in such a way that two segment-shaped edge regions which lie between the side edges of lateral webs (31) of the mixing element and the pipe wall do not have webs (30) arranged obliquely to the main flow direction.
Priority Applications (13)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE59505843T DE59505843D1 (en) | 1995-02-02 | 1995-02-02 | Static mixing device for highly viscous media |
EP95810073A EP0727249B1 (en) | 1995-02-02 | 1995-02-02 | Static mixer for very viscous liquids |
ES95810073T ES2132575T3 (en) | 1995-02-02 | 1995-02-02 | STATIC MIXER FOR VERY VISCOUS LIQUIDS. |
AT95810073T ATE179630T1 (en) | 1995-02-02 | 1995-02-02 | STATIC MIXING DEVICE FOR HIGH VISCOSITY MEDIA |
CA002165375A CA2165375C (en) | 1995-02-02 | 1995-12-15 | Static mixer apparatus for highly viscous media |
JP33507495A JP3845466B2 (en) | 1995-02-02 | 1995-12-22 | Static mixer device for high viscosity medium |
KR1019960000474A KR100403881B1 (en) | 1995-02-02 | 1996-01-12 | Static mixer device for high viscous media |
US08/585,817 US5620252A (en) | 1995-02-02 | 1996-01-16 | Static mixer apparatus for highly viscous media |
CZ1996271A CZ288772B6 (en) | 1995-02-02 | 1996-01-30 | Static mixing device for high-viscosity media |
PL96312556A PL179318B1 (en) | 1995-02-02 | 1996-01-31 | Stationary mixer for mixing highly viscous media and agitator |
BR9600283A BR9600283A (en) | 1995-02-02 | 1996-01-31 | Static mixing equipment for highly viscous media and mixing element |
CN96105911A CN1047741C (en) | 1995-02-02 | 1996-02-01 | Static mixer apparatus for highly viscous media |
MX9600453A MX9600453A (en) | 1995-02-02 | 1996-02-01 | Static mixture device for highly viscous media. |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP95810073A EP0727249B1 (en) | 1995-02-02 | 1995-02-02 | Static mixer for very viscous liquids |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0727249A1 true EP0727249A1 (en) | 1996-08-21 |
EP0727249B1 EP0727249B1 (en) | 1999-05-06 |
Family
ID=8221697
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95810073A Expired - Lifetime EP0727249B1 (en) | 1995-02-02 | 1995-02-02 | Static mixer for very viscous liquids |
Country Status (13)
Country | Link |
---|---|
US (1) | US5620252A (en) |
EP (1) | EP0727249B1 (en) |
JP (1) | JP3845466B2 (en) |
KR (1) | KR100403881B1 (en) |
CN (1) | CN1047741C (en) |
AT (1) | ATE179630T1 (en) |
BR (1) | BR9600283A (en) |
CA (1) | CA2165375C (en) |
CZ (1) | CZ288772B6 (en) |
DE (1) | DE59505843D1 (en) |
ES (1) | ES2132575T3 (en) |
MX (1) | MX9600453A (en) |
PL (1) | PL179318B1 (en) |
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US6595679B2 (en) * | 2000-02-08 | 2003-07-22 | Bayer Aktiengesellschaft | Static mixer with at least three interleaved grids |
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US5971603A (en) * | 1998-03-06 | 1999-10-26 | The Madison Group: Polymer Processing Research Corp. | Static mixer head |
US6224833B1 (en) * | 1998-12-15 | 2001-05-01 | Koch-Glitsch, Inc. | Apparatus for contacting of gases and solids in fluidized beds |
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EP0226879A1 (en) * | 1985-12-11 | 1987-07-01 | GebràDer Sulzer Aktiengesellschaft | Static mixer for fluids containing or composed of solid particles |
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CH664505A5 (en) * | 1984-03-05 | 1988-03-15 | Sulzer Ag | STATIC MIXING DEVICE, ESPECIALLY FOR MACHINES PROCESSING HIGH VISCOSE PLASTIC MELTING. |
-
1995
- 1995-02-02 DE DE59505843T patent/DE59505843D1/en not_active Expired - Lifetime
- 1995-02-02 EP EP95810073A patent/EP0727249B1/en not_active Expired - Lifetime
- 1995-02-02 ES ES95810073T patent/ES2132575T3/en not_active Expired - Lifetime
- 1995-02-02 AT AT95810073T patent/ATE179630T1/en active
- 1995-12-15 CA CA002165375A patent/CA2165375C/en not_active Expired - Fee Related
- 1995-12-22 JP JP33507495A patent/JP3845466B2/en not_active Expired - Fee Related
-
1996
- 1996-01-12 KR KR1019960000474A patent/KR100403881B1/en not_active IP Right Cessation
- 1996-01-16 US US08/585,817 patent/US5620252A/en not_active Expired - Lifetime
- 1996-01-30 CZ CZ1996271A patent/CZ288772B6/en not_active IP Right Cessation
- 1996-01-31 PL PL96312556A patent/PL179318B1/en not_active IP Right Cessation
- 1996-01-31 BR BR9600283A patent/BR9600283A/en not_active IP Right Cessation
- 1996-02-01 MX MX9600453A patent/MX9600453A/en not_active IP Right Cessation
- 1996-02-01 CN CN96105911A patent/CN1047741C/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4062524A (en) * | 1973-06-06 | 1977-12-13 | Bayer Aktiengesellschaft | Apparatus for the static mixing of fluid streams |
EP0226879A1 (en) * | 1985-12-11 | 1987-07-01 | GebràDer Sulzer Aktiengesellschaft | Static mixer for fluids containing or composed of solid particles |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6595679B2 (en) * | 2000-02-08 | 2003-07-22 | Bayer Aktiengesellschaft | Static mixer with at least three interleaved grids |
US7199242B2 (en) | 2001-08-02 | 2007-04-03 | Lg Life Sciences Limited | Processes for the production of amino-protected derivatives of 4-aminomethylene-pyrrolidin-3-one and/or 4-aminomethylene-pyrrolidin-3-alkoxyimino derivatives and/or gemifloxacin or a salt thereof |
EP2158027B2 (en) † | 2007-06-22 | 2016-04-27 | Sulzer Chemtech AG | Static mixing element |
EP2629039A1 (en) | 2012-02-17 | 2013-08-21 | Armacell Enterprise GmbH | Extensional flow heat exchanger for polymer melts |
CN105377410A (en) * | 2013-04-19 | 2016-03-02 | Emd密理博公司 | Flexible film baffle in single use bioreactor |
US10723990B2 (en) | 2013-04-19 | 2020-07-28 | Emd Millipore Corporation | Flexible film in single use bioreactor |
CN105377410B (en) * | 2013-04-19 | 2020-10-09 | Emd密理博公司 | Flexible membrane partition in a single-use bioreactor |
EP3338882A1 (en) | 2016-12-14 | 2018-06-27 | Felix Streiff | Mixing element with high strength and mixing effect |
Also Published As
Publication number | Publication date |
---|---|
DE59505843D1 (en) | 1999-06-10 |
ES2132575T3 (en) | 1999-08-16 |
CZ288772B6 (en) | 2001-08-15 |
KR100403881B1 (en) | 2004-01-07 |
PL179318B1 (en) | 2000-08-31 |
JPH08309170A (en) | 1996-11-26 |
JP3845466B2 (en) | 2006-11-15 |
CN1047741C (en) | 1999-12-29 |
US5620252A (en) | 1997-04-15 |
CA2165375C (en) | 2000-04-04 |
MX9600453A (en) | 1997-01-31 |
EP0727249B1 (en) | 1999-05-06 |
BR9600283A (en) | 1997-12-23 |
CA2165375A1 (en) | 1996-08-03 |
KR960030986A (en) | 1996-09-17 |
CZ27196A3 (en) | 1996-08-14 |
PL312556A1 (en) | 1996-08-05 |
ATE179630T1 (en) | 1999-05-15 |
CN1140098A (en) | 1997-01-15 |
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