EP0609544B2 - Verfahren zum Erhöhen von Glanz und/oder Glätte einer Materialbahn - Google Patents

Verfahren zum Erhöhen von Glanz und/oder Glätte einer Materialbahn Download PDF

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Publication number
EP0609544B2
EP0609544B2 EP93120500A EP93120500A EP0609544B2 EP 0609544 B2 EP0609544 B2 EP 0609544B2 EP 93120500 A EP93120500 A EP 93120500A EP 93120500 A EP93120500 A EP 93120500A EP 0609544 B2 EP0609544 B2 EP 0609544B2
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EP
European Patent Office
Prior art keywords
steam
web
temperature
smoothness
nip
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.)
Expired - Lifetime
Application number
EP93120500A
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German (de)
English (en)
French (fr)
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EP0609544A1 (de
EP0609544B1 (de
Inventor
Stefan H. Winheim
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
VIB Apparatebau GmbH
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VIB Apparatebau GmbH
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Filing date
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Application filed by VIB Apparatebau GmbH filed Critical VIB Apparatebau GmbH
Publication of EP0609544A1 publication Critical patent/EP0609544A1/de
Publication of EP0609544B1 publication Critical patent/EP0609544B1/de
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Publication of EP0609544B2 publication Critical patent/EP0609544B2/de
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Classifications

    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21FPAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
    • D21F7/00Other details of machines for making continuous webs of paper
    • D21F7/008Steam showers
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21GCALENDERS; ACCESSORIES FOR PAPER-MAKING MACHINES
    • D21G1/00Calenders; Smoothing apparatus
    • D21G1/0073Accessories for calenders
    • D21G1/0093Web conditioning devices

Definitions

  • the invention relates to a method for increasing the gloss and / or smoothness of a material web, in particular a paper web, in which a wetted by means of steam material web is passed through a nip and pressurized there, wherein the vapor is condensed on the material web.
  • Gloss and smoothness are characteristics of a material web, which influence not only their appearance but also their further processability. For certain applications, high gloss and / or smoothness values are desired, which should also be reproducible as uniformly as possible.
  • WO-A-90/12920 shows a steam applicator which applies superheated steam to a paper web in front of a nip.
  • a heater is provided in order to keep the steam in the overheated state.
  • the device contacts the paper web or is located at a very small distance from the paper web to direct as hot a vapor as possible to the paper web.
  • the paper web should then be passed through a nip before it has cooled.
  • EP-A-0 296 044 discloses an apparatus for controlling cross-machine direction gloss with two steam blow boxes each adjacent to the side of the paper web to be provided with increased gloss in a subsequent nip. Behind the last nip, a gloss sensor is arranged, which is connected to a control for the steam blow boxes. These can be controlled zone by zone in the transverse direction.
  • the invention is therefore based on the object to simplify the gloss and / or smoothness increase.
  • the web more precisely its surface, has already been treated in the nip.
  • the steam is thus applied only immediately before the entry of the material web into the nip.
  • the surface of the web is still at a relatively high temperature and has a relatively high humidity, so that the increase of gloss and / or smoothness is performed even at low pressures and low temperatures in the nip.
  • the railway takes no significant overall Amount of moisture, so that expensive post-treatments omitted.
  • the energies needed to reshape the surface are held in the area that is to be reshaped, ie smoothed.
  • the remaining railway parts are not affected or only to a small extent.
  • the predetermined value is in the range of 12% to 25%, in particular in the range of 16% to 25%. It is the surface so relatively much moisture supplied. However, since this supply is limited to the surface and a thin layer underneath, there is no appreciable volume loss due to the reshaping and no great overall moisture increase of the web.
  • the material web is guided into the nip before the temperature in the middle third of the thickness of the web has reached 1 / e times the surface temperature. This allows a sufficient distance of the steaming of the web from the nip, which can not be lowered to zero for design reasons.
  • the difference between the middle and the outer third of the web in terms of temperature is still so large that the deformation is limited to the outer third, as far as the temperature has an influence here.
  • the influence of moisture is limited to even thinner surface areas because the temperature penetrates faster than the moisture.
  • the steam is kept free of water droplets until it strikes the material web. It is therefore on the one hand ensured that the steam itself contains no drops of water. Furthermore, but also not allowed that form water droplets in the steam. This can be achieved for example by heating the steam until the end immediately before hitting the material web. In this way, it is ensured that the total heat contained in the vapor can be transferred to the surface of the material web during the condensation, in order to lead to the desired temperature increase, which is accompanied by the increase in moisture at the surface. Before the impact of the steam on the web here no fog, so that the ambient atmosphere does not accumulate so strong with moisture.
  • the steam is first distributed in a distribution space on an outlet surface having a predetermined extent in the running direction of the material web and then moved at a high speed in a predetermined area in the direction of the material web.
  • the speed can control the amount of steam that is condensed on the web.
  • this speed depends on the speed of the material web. It is generally 15 m / s or more.
  • the fact that the steam is first distributed in a distribution space there is the advantage that the loading of the web over the width can be made relatively uniform.
  • the speed of the steam can be controlled by the pressure in the distribution space.
  • gloss and / or smoothness and / or a corresponding parameter of the material web is determined behind the nip and the steam output is set as a function of a difference between the determined actual value and a predetermined desired value.
  • the gloss and / or smoothness generation thus takes place in a closed loop in which the steam is used as an actuator.
  • a further heating of one or both rollers forming the nip can take place.
  • the steam is applied in the web transverse direction in a plurality of zones, wherein the steam output in each zone is separately adjustable.
  • gloss and smoothness differences can be achieved not only in the longitudinal direction, i. in the direction of the material web, but also in the transverse direction of the web evenly, if necessary.
  • a homogenization in the longitudinal direction is then z. B. effected by controlling the total discharge amount of the steam.
  • the control in the transverse direction is effected by the zone-wise adjustment of the steam discharge amount.
  • the supply of steam is substantially limited to an amount per time that can condense on the web.
  • the supplied steam is therefore essentially completely consumed, so that practically no steam can escape and lead to an increase in the humidity in the ambient atmosphere.
  • the temperature of at least one of the rolls forming the nip is additionally adjusted.
  • the steaming which also comes with an increase in temperature of the web, with a temperature control of the roller, the desired gloss and / or smoothness values can be adjusted with high accuracy.
  • the roller is heated on its surface. By limiting the heating to the surface of the roll, relatively fast reaction times can be achieved. In addition, the energy consumption is kept small.
  • the temperature setting is carried out in a control loop which is subordinate to a control loop which controls the steam delivery.
  • the temperature control loop is thus underlaid by the steam delivery control loop.
  • the steam delivery loop enjoys the higher priority, so that the coarse adjustment can be made much faster than the fine adjustment.
  • the steam discharge device is arranged so close to the nip that the conditional by a steam application temperature and humidity increase of the web is not balanced when the web passes through the nip.
  • Such a steam blower box is known from the German patent application P 41 25 062 not previously published.
  • the use of such a vapor delivery device in connection with the increase of gloss and smoothness of the material web has the advantage that it is thereby possible to apply a virtually water-drop-free vapor to the material web. Any condensing out of the steam in the steam blast chamber is avoided because the steam blast chamber is heated. It is therefore maintained in the interior of the steam chamber, a state in which the vapor can be present only in the gaseous state.
  • the heating of the steam blast chamber has the additional advantage that a restart of the device after interruptions in operation, such as may occur in a Walzenwechel easier.
  • the free housing wall and the material web include a vaporization space, which is largely completed laterally by housing parts of the steam delivery device. This ensures on the one hand that the output from the steam delivery device steam can not escape freely into the environment. Rather, it remains in the evaporation chamber, where it can be removed from the material web. On the other hand, the evaporation chamber is also mitbeannet especially when the free housing wall is heated, so that the steam is kept until the last to the necessary temperature. The steam can thus cause the necessary increase in temperature of the surface of the material web during condensation on the material web.
  • a steam-operated heater for heating, wherein the steam valve and the heater are connected to the same supply port.
  • the heater thus operates at a temperature which substantially corresponds to the steam temperature.
  • the steam chamber and also the steaming chamber is maintained at a temperature corresponding to the temperature of the steam to be conveyed to the web.
  • a matched heating is achieved with relatively simple means.
  • the steam to be dispensed always finds an environment substantially corresponding to its temperature. Possible negative phenomena, which could occur due to temperature jumps, to which the steam is exposed, could be avoided.
  • the heater and the steam valve are arranged in series.
  • the steam first heats the steam blast chamber with the aid of the heating device before it enters the steam blast chamber heated by itself.
  • the heater thus always has a slightly higher temperature than the steam entering the steam blast chamber. It is thus able to transfer energy back to the steam to reliably prevent the formation of water droplets in the steam blast chamber.
  • the temperature of the steam but also lower so far that the steam can condense on the material web to the desired extent. If the steam is too hot, although there is also a heat transfer from the steam to the surface of the material web. However, heat transfer is significantly better if the vapor can condense on the surface of the web. In this case, the desired moisture level on the surface also sets in at the same time.
  • the heating device has a steam drying section.
  • the drying section water droplets that may possibly form during transport of the steam from a steam generator to the steam dispenser are reliably eliminated.
  • the steam valve is thus supplied only dry steam, so that the risk of damage to the passing material web is not only reduced by impinging water droplets, but practically turned off.
  • a front wall of the steam delivery device adjacent to a roller is inclined with respect to the free housing wall.
  • the entire steam delivery device is thus wedge-shaped at least in this area.
  • the steam delivery device can thus be brought very close to the nip, so that the steam is applied immediately before the nip.
  • neither temperature nor moisture has practically had opportunity to spread into the interior of the web.
  • this area is treated in the nip, i. smoothed or provided with a higher gloss.
  • the angle of inclination between 35 ° and 55 °.
  • this range of angles allows the steam delivery device to bring the steam up to a very small distance in front of the nip.
  • it allows a sufficient height that a steam blast chamber can be formed with a sufficient height for the propagation of the vapor.
  • the steam-blow chamber is subdivided transversely to the running direction of the material web into zones which have separately controllable steam valves.
  • the amount of steam applied to the web is, so at least partially control can be transverse to the direction of the web.
  • a gloss or smoothness measuring device is provided in the running direction of the material web behind the nip, which is connected to a control device, which in turn controls the steam valves in dependence on gloss or smoothness setpoints.
  • the steam is thus applied in a closed loop. If the actual values of gloss and smoothness fall below a specified setpoint value, the steam valve of the corresponding zone is actuated to bring the values back to their specifications. If the actual value rises above the setpoint, the steam valve is influenced in the other direction.
  • the steam valves on outlet openings which are arranged at an angle to the free housing wall so that no steam jet is directed directly at the free housing wall. This achieves a relatively even expansion of the steam passing through the free housing wall. Partial steam velocity increases, as would occur when a jet of steam exits the valve directly through an exit port, are reliably avoided.
  • each steam jet emerging from the steam valves is directed at an angle not equal to 90 ° to a chamber wall. So it can not happen that a jet of steam is reflected in itself, which could lead to turbulence, which no longer ensure a uniform expansion of steam from the outlet openings.
  • U-shaped profiles are mounted on the free housing wall in the evaporation chamber between the steam outlet openings, whose openings are covered by the free housing wall and form the channels as part of the heating device. These channels thus run in the evaporation chamber. They not only heat the free housing wall and above it the steam chamber. They also heat the vaporization space, so that until the very end an environment is maintained in which the vapor retains its gaseous form. The condensation of the steam thus actually takes place only immediately on the material web.
  • the steam has a temperature in the range of 102 ° C to 110 ° C.
  • a steam temperature ensures that the steam can condense completely on the material web and cause the desired temperature and humidity increase of the surface there.
  • the distance of the steam delivery device from the nip is variable.
  • this measure makes it possible to control how deep the temperature and the moisture can penetrate into the material web before the material web enters the nip. In this way, too, a change in gloss and smoothness can be effected, which can optionally also be included in the control loop.
  • a respective steam discharge device is arranged on both sides of the material web in front of the nip.
  • the material web is acted upon here from both sides simultaneously with steam. This is particularly advantageous in single-calenders, in which only a single nip is provided.
  • a device 1 for increasing the smoothness and / or gloss of a material web has two rollers 2, 3, which form a nip 4, through which the material web 5 is guided.
  • this device 1 one side of the material web 5, here the upper side, is smoothed and / or provided with gloss.
  • a corresponding device 1 ' is provided for the underside of the material web 5.
  • the corresponding parts have the same reference numerals, which are deleted for the purpose of distinction.
  • the device 1 'for the underside of the web 5 is discussed only if deviations from the device 1 result.
  • the rollers 2, 3 can form a so-called machine calender.
  • One or both rollers 2, 3 can be heated by a heater 40.
  • the heating can also be done from the inside.
  • a web of paper will be considered below as a material web. However, it may u.a. Other cellulosic or cellulosic materials may be used.
  • the paper web is unwound from a supply roll 6 and wound after passing through the device 1 on a receiving roller, not shown. However, the paper web 5 can also be removed directly from a paper machine.
  • a steam discharge device 7 which is displaceable on a stand 8. It can be brought closer or further away from the nip 4 in or against the paper feed direction 9.
  • the steam discharge device which will be described in more detail in connection with FIGS. 2 to 4, gives off steam in the direction of the material web which condenses there.
  • a measuring device 10 for determining gloss or smoothness-actual values is provided in the paper running direction 9 behind the nip 4.
  • This measuring device 10 may extend over the entire width de paper web 5. However, it is equally possible for it to move transversely to the paper web 5 during the course of the paper, and in so doing to continuously determine gloss and / or smoothness over the entire paper web, albeit not simultaneously. Expediently, the measuring device 10 is arranged behind the nip 4 'for the second material web side.
  • the measuring device 10 is connected to a controller 11, which in turn controls the steam delivery device 7, as a function of a difference between the measured values determined by the measuring device 10 and further desired values supplied via a setpoint input 12.
  • the controller 11 may also control the device 40.
  • the steam discharge device 7 for the upper side of the paper web 5 is above, the steam discharge device 7 'for the underside of the paper web is mounted below the paper web 5, so that the paper web 5 is applied temporally and spatially offset from both surfaces with steam. Behind each dispensing device 7, 7 'follows in any case first a Walzenpsalt 4, 4'. If only one side of the paper web 5 is to be treated, only one steam discharge device 7 or 7 'is provided. In the following, therefore, only one steam discharge device 7 will be described in more detail. The other steam delivery device 7 'speaks her mirror image.
  • the steam discharge device 7 has a steam blast chamber 13, which is delimited by a free housing wall 14 and further housing walls 15, 16, 17, 18, 19.
  • the free housing wall 14 has steam outlet openings 20 which have a diameter which is smaller than the thickness of the free housing wall. These openings 20 are therefore only shown as a dash.
  • Each steam chamber also has a steam valve 21.
  • the steam valve allows steam, which it receives via a feed channel 22, to enter the steam blast chamber 13.
  • valve openings 23 are directed so that all exiting the steam valve steam jets 24 are directed neither directly to the free housing wall 14 at an angle of 90 ° to another housing wall. This avoids that from the steam valve 21 exiting steam jets 24 can pass directly through openings 20 in the free housing wall 14. On the other hand, it avoids a reflection of the steam jets on the other housing walls, which could lead to an undesirable turbulence of the steam in the steam blast chamber 13.
  • the free housing wall 14 includes with the paper web 5 and further housing parts 25, 26, 27, 28 a vapor deposition chamber 29 a. Of course, a small gap between the paper web 5 and the other housing parts 25-28 is provided. The paper web 5 should not rub on the housing parts.
  • the evaporation chamber 29 substantially U-shaped plates 30 are applied to the free housing wall 14, the opening of which is covered by the free housing wall 14.
  • the plates 30 together with the free housing wall 14 heating channels 31.
  • the free housing wall 14 and thus the steam blast chamber 13 is heated.
  • the evaporation chamber 29 is heated.
  • the outlet openings 20 in the free housing wall are in this case arranged between the sheets 30.
  • the housing wall 15 is heated by the supply channel 22, in which also is hot steam.
  • the housing wall 17 is heated by a steam channel 32.
  • This steam channel 32 is formed as a steam drying section. It is connected to a steam connection 33, via which steam is supplied by a steam generator, not shown.
  • Side channels 34, 35 are provided at the two end faces of the steam discharge device, so that the steam discharge device 7 is also heated at its two end faces.
  • the one side channel 35 has at its end, i. just before the mouth into the feed channel 22, a throttle 36. This throttle causes a pressure difference between the left side channel 35 and the right side channel 35.
  • Steam which is supplied via the steam connection 33, flows, as indicated by arrows, first through the steam channel 32, where it is dried, i. Water droplets that may still be present in the steam are eliminated here and can be removed via a condensate drain 37.
  • the steam then continues to flow through the right side channel 35 and, due to the pressure difference between the left side channel 34 and the right side channel 35 created by the throttle 36, through the channels 31 to the left side channel 34. Another portion of the steam flows into the feed channel 32, where he comes to the steam valves 21.
  • the steam blast chamber 13 is not heated by all, but from many sides. In the steam blast chamber 13, therefore, a temperature can be maintained without difficulty even after interruptions in operation, in which the steam can not condense.
  • each steam blast chamber 13 has its own steam valve 21.
  • Each steam valve 21 is controlled separately from the controller 11. Gloss and / or smoothness can thus be set transversely to the paper direction 9 in four areas separated from each other.
  • the vapor delivery means 7 has the shape of a wedge in cross-section, i. the wall 15 or its corresponding outer wall 39 is beveled with respect to the free housing wall 14. It has an angle in the range between 35 ° and 55 °, in the present case it is about 45 °.
  • the steam can be applied to the paper web 5 relatively late before the nip, so that although he condenses there, the condensation caused by the temperature and humidity increase in the paper web 5 but not yet penetrated into the interior of the paper web and a Compensation has led, when the paper web 5 is exposed to the pressure in the nip 4.
  • the device operates as follows: The steam delivery device 7 is brought as close as possible to the nip 4, wherein the distance can be adjusted depending on the speed with which the paper web 5 passes through the nip 4.
  • the dispenser 7 is now heated by means of steam. If it is so hot that there is a temperature in the steam blast chamber 13 that precludes condensation of the steam, say, a temperature in the range of 102 ° C to 110 ° C, operation may begin.
  • the paper web 5 is moved through the nip.
  • steam is supplied to the steam discharge device 7 via the steam connection 33.
  • the steam valves 21 open and allow steam to enter the steam blast chamber 13 where it spreads and then flows through the apertures 20 into the vaporization space 29 at a relatively uniform pressure and, above all, a uniform high velocity of 15 m / s or more the paper web 5 to come into contact.
  • the steam valves 21 open and allow steam to enter the steam blast chamber 13 where it spreads and then flows through the apertures 20 into the vaporization space 29 at a relatively uniform pressure and, above all, a uniform high velocity of 15 m / s or more the paper web 5 to come into contact.
  • the steam comes into contact with the relatively cold paper web 5
  • the paper web 5 is about 30 ° C. cold, the surface will be about 90 ° C. after the condensation of the vapor.
  • the condensed vapor forms a moisture film 41 whose thickness is preferably approximately in the range of one thousandth of a millimeter.
  • the paper web has a uniform temperature distribution.
  • the homogenization of the moisture takes a little longer.
  • the moisture 42 penetrates slower than the temperature in the paper web 5. Therefore, a surface area 43 of the paper web 5 has a much higher relative humidity. The further the moisture penetrates into the interior 44 of the paper web 5, the more the relative humidity decreases.
  • the treatment takes place in the nip 4.
  • the web treated namely, the surface of the web, which still has the increased temperature and Fechttechnik, smoothed or provided with increased gloss.
  • the further inward areas 44 of the paper web 5 are not significantly changed by the nip.
  • the controller 11 If the controller 11 now determines that the actual gloss values or smoothness values determined by the measuring device 10 do not coincide with target specifications 12, it actuates the steam valves 21 until the difference between the actual values and the setpoint values has fallen below a predetermined value. This can be carried out in zones, so that different gloss or smoothness values can be compensated over the width of the paper web 5. At the same time, in a subordinate or subordinate control loop, the controller 11 can control the temperature of the roll surface by means of the heating device 40 in order to achieve a fine adjustment of the gloss and / or smoothness values.
  • Fig. 6 shows a second embodiment of a device 1 ', in which only one nip 4 is present.
  • the rollers 2, 3 form a single-calender.
  • the formation of the rollers 2, 3 as hard or soft rolls is determined by the circumstances.
  • a steam discharge device 7 or 7 ' is provided on both sides of the paper web in front of the nip.
  • the application of steam takes place simultaneously on both sides of the paper web 5.
  • the gloss and / or smoothness values are determined by the two measuring devices 10, 10 'on both sides of the paper web 5 and forwarded to the controller 11, which now both steam dispensers 7, 7' controls.
  • a paper web 5 was used.
  • the method and the device are also suitable for other material webs comprising pulp fibers, for example Cardboard or cardboard.
  • both gloss and / or smoothness control of the web in the machine direction i. in the direction of the web 5, as well as a control of these values in the transverse direction.
  • the control in the longitudinal direction can take place via a control of the steam delivery devices 7, 7 'supplied amount of steam.
  • the control in the transverse direction is carried out by a zone-wise control of the steam discharge quantity, ie by adjusting the ratio of the votes in the individual zones of steam quantities.

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EP93120500A 1993-01-16 1993-12-20 Verfahren zum Erhöhen von Glanz und/oder Glätte einer Materialbahn Expired - Lifetime EP0609544B2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4301023 1993-01-16
DE4301023A DE4301023C3 (de) 1993-01-16 1993-01-16 Vorrichtung zum Erhöhen von Glanz und/oder Glätte einer Papierbahn

Publications (3)

Publication Number Publication Date
EP0609544A1 EP0609544A1 (de) 1994-08-10
EP0609544B1 EP0609544B1 (de) 1997-04-16
EP0609544B2 true EP0609544B2 (de) 2007-04-18

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ID=6478315

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93120500A Expired - Lifetime EP0609544B2 (de) 1993-01-16 1993-12-20 Verfahren zum Erhöhen von Glanz und/oder Glätte einer Materialbahn

Country Status (6)

Country Link
US (2) US5914008A (fi)
EP (1) EP0609544B2 (fi)
JP (1) JP2672256B2 (fi)
CA (1) CA2110786C (fi)
DE (2) DE9320455U1 (fi)
FI (1) FI100671B (fi)

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EP0957202B1 (de) * 1998-05-08 2004-03-31 V.I.B. Systems GmbH Verfahren und Vorrichtung zur Online-Herstellung von SC-A-Papier
DE19824170A1 (de) 1998-05-29 1999-12-02 Voith Sulzer Papiertech Patent Einrichtung zum Befeuchten einer Materialbahn
DE19824804A1 (de) * 1998-06-03 1999-12-09 Voith Sulzer Papiertech Patent Verfahren und Vorrichtung zur Oberflächenbehandlung einer Papierbahn
EP1105570B1 (en) 1998-07-10 2004-03-17 Metso Paper, Inc. Method for manufacturing calendered paper
DE19835989C5 (de) 1998-08-08 2010-04-01 V.I.B. Systems Gmbh Verfahren und Vorrichtung zur Online-Kalandrierung von Papier
DE19901400A1 (de) 1999-01-15 2000-07-20 Voith Sulzer Papiertech Patent Trocknungs- und Glättungseinheit für Faserstoffbahnen
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DE19905824A1 (de) * 1999-02-12 2000-09-07 Weitmann & Konrad Fa Vorrichtung zum Befeuchten von bahnförmigem Material
FI113072B (fi) * 1999-09-29 2004-02-27 Metso Paper Inc Menetelmä monitelakalanteria varten ja monitelakalanteri
DE19958295A1 (de) * 1999-12-03 2001-06-13 Weitmann & Konrad Fa Druckvorrichtung und Befeuchtungsstation für eine Druckvorrichtung
FI109040B (fi) * 2000-01-28 2002-05-15 Metso Paper Inc Menetelmä paperi- tai kartonkirainan kalanteroinnissa ja kalanteri
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DE202010017942U1 (de) 2010-09-30 2013-04-08 Voith Patent Gmbh Vorrichtung zum Befeuchten der Oberflächenschicht einer Faserstoffbahn
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EP0609544A1 (de) 1994-08-10
JP2672256B2 (ja) 1997-11-05
CA2110786C (en) 1997-09-16
DE4301023C3 (de) 2001-07-26
FI100671B (fi) 1998-01-30
EP0609544B1 (de) 1997-04-16
CA2110786A1 (en) 1994-07-17
US6260481B1 (en) 2001-07-17
DE9320455U1 (de) 1994-08-25
DE4301023C2 (de) 1996-08-22
DE4301023A1 (de) 1994-07-21
JPH06235187A (ja) 1994-08-23
FI940102A0 (fi) 1994-01-10
FI940102A (fi) 1994-07-17
US5914008A (en) 1999-06-22

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