EP2893079A1 - Bande de pressage dans une machine à papier - Google Patents

Bande de pressage dans une machine à papier

Info

Publication number
EP2893079A1
EP2893079A1 EP13753636.3A EP13753636A EP2893079A1 EP 2893079 A1 EP2893079 A1 EP 2893079A1 EP 13753636 A EP13753636 A EP 13753636A EP 2893079 A1 EP2893079 A1 EP 2893079A1
Authority
EP
European Patent Office
Prior art keywords
press belt
press
silicon dioxide
plastic matrix
polydimethylsiloxane
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.)
Withdrawn
Application number
EP13753636.3A
Other languages
German (de)
English (en)
Inventor
Delphine Delmas
Uwe Matuschczyk
Hermann Reichert
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.)
Voith Patent GmbH
Original Assignee
Voith Patent GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Voith Patent GmbH filed Critical Voith Patent GmbH
Publication of EP2893079A1 publication Critical patent/EP2893079A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21FPAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
    • D21F1/00Wet end of machines for making continuous webs of paper
    • D21F1/0027Screen-cloths
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21FPAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
    • D21F3/00Press section of machines for making continuous webs of paper
    • D21F3/02Wet presses
    • D21F3/0209Wet presses with extended press nip
    • D21F3/0218Shoe presses
    • D21F3/0227Belts or sleeves therefor
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21FPAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
    • D21F3/00Press section of machines for making continuous webs of paper
    • D21F3/02Wet presses
    • D21F3/0209Wet presses with extended press nip
    • D21F3/0218Shoe presses
    • D21F3/0227Belts or sleeves therefor
    • D21F3/0236Belts or sleeves therefor manufacturing methods
    • 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
    • D21F7/08Felts
    • D21F7/086Substantially impermeable for transferring fibrous webs
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21GCALENDERS; ACCESSORIES FOR PAPER-MAKING MACHINES
    • D21G1/00Calenders; Smoothing apparatus
    • D21G1/0066Calenders; Smoothing apparatus using a special calendering belt

Definitions

  • the invention relates to a press belt for a shoe press device with the features of the upper grip of claim 1. Furthermore, the invention relates to a method for producing a plastic matrix for a press belt of a shoe press device with the features of the preamble of claim 12.
  • Press belts which may be formed, for example, as a closed jacket of a shoe press roll or as a transfer belt, which is guided between the fibrous web and the jacket of the counter-roller as an endlessly circulating belt, are exposed to high mechanical, thermal and chemical stresses.
  • press belts consist of a polyurethane matrix which is fiber-reinforced.
  • the polyurethane matrix can be formed in one or more layers, so that the press belt can have multiple layers or layers.
  • the outer surface of the respective press belt may be provided with a structure such as grooves, blind holes or the like to optimize drainage in the press. Due to the high mechanical loads cracks can form in the press belts, which also due to the high mechanical stress, a further growth of the cracks can occur.
  • This occurrence of crack growth can increasingly occur even with press belts with grooves or blind holes. Due to crack growth, structural and / or functional failure of the press belt may occur. In addition, the press belts are also exposed to enormous mechanical dynamic loads, so that the press belts are also subject to high abrasion. In addition, the press belts in the paper machine are also exposed to strong chemical stresses due to the different media appearing in the paper machine. For example, the press belts can come into contact with water, oil, acids, alkalis, solvents or the like and are at least partially attacked by these media.
  • DE19702138 A1 discloses a press jacket whose hardness and wear resistance have been increased by additives from rock flour, ceramic or carbon.
  • DE441 1620 A1 proposes only one To provide outer layer of the press jacket with wear resistance-increasing additives.
  • US2005287373 and US200601 18261 disclose press belts comprising polydimethylsiloxane.
  • the paper machine belts of WO2005090429 and US2008081179 have nanoparticles, for example, to improve the resistance to crack growth, hardness or abrasion resistance.
  • EP2330249 describes paper machine belts which have silicon dioxide microparticles.
  • the present invention is concerned with the problem of providing for a press belt of a shoe press apparatus, as well as a method for producing a plastic matrix for such a press belt an improved or at least one alternative embodiment, in particular by a higher abrasion resistance, a low or at least not impaired tendency for cracking and crack growth and / or lower sensitivity to the media occurring in a paper machine.
  • a press belt for a shoe press device for dewatering or smoothing a fibrous web, in particular a paper, board or tissue web, in which the press belt comprises a fiber-reinforced plastic matrix.
  • the fiber-reinforced plastic matrix may have a polyurethane at least in a partial area and polydimethylsiloxane and silicon dioxide microparticles as additives.
  • the chemical resistance to the media occurring in the paper machine can be increased by the combination of the additives polydimethylsiloxane and silica microparticles.
  • the abrasion resistance can be improved, and the tendency to cracking and crack growth are kept low.
  • the swelling behavior of the press belt is not or only slightly changed by adding the additive combination.
  • the additive combination leads to improved abrasion resistance and increased chemical resistance.
  • the sole use of silica microparticles leads to a deteriorated dispersibility of the reactants of the plastic matrix and thereby possibly to an increased tendency to crack in the finished press belt.
  • press belts with only silica microparticles as additive had a significantly reduced abrasion resistance.
  • a press belt Under a press belt is a band or a coat to understand, which is guided together with a fibrous web through a shoe press nip formed between a stationary pressing element, the so-called press shoe, and a cylindrical counter-roller.
  • the press shoe rests on a fixed yoke and is hydraulically pressed against the counter roller.
  • one or more endlessly circulating felts and / or further endlessly circulating press belts can be guided through the press nip.
  • the press belt can be designed as a press jacket of the shoe press roll, that is, it is held as a closed shell of two side clamping disks and rotates about the stationary press shoe.
  • the press belt In order to reduce the friction of the press belt on the press shoe, oil is applied to the inside of the press belt for lubrication.
  • the press belt instead of the guide through the two side clamping disks, the press belt, as is the case with open shoe presses, can be guided over the press shoe and a plurality of guide rollers.
  • the surface of press jackets may be provided with grooves and / or blind holes.
  • the press belt can also be designed as a transfer belt, which is guided between the fibrous web and the mantle of the counter-roller as an endlessly circulating belt in order to transport the fibrous web through the shoe press nip.
  • the fibrous web is then removed after the shoe press nip using a suction roll from the press belt, taken on another fabric and fed to the following machine group.
  • the surface of the transfer belt has sufficient adhesion to the fibrous web to guide it safely and if the surface of the transfer belt has good smoothness and low tendency to marring. On the other hand, it is also advantageous if the fibrous web can be pulled off again.
  • a fiber-reinforced plastic matrix is understood as meaning a plastic matrix in which 1, 2 or 3-dimensional fiber structures are embedded.
  • the term 1-dimensional fiber structure encompasses fibers, continuous fibers, yarns, fiber bundles, fiber strands, filaments, filament bundles, rovings or mixed forms.
  • the term 2-dimensional fiber structure includes woven, knitted, knitted, nonwoven, scrim, unidirectional laid-down fibrous layers, multi-axial scrims, mats, knits, spacer fabrics, braided sleeving, embroidery, sewing fabrics, tear-off fabrics or blends.
  • the term 3-dimensional fiber structure is essentially to be understood as meaning a plurality of two-dimensional fiber structures stacked on top of each other. In this case, the 2-dimensional fiber structure can be designed differently.
  • a unidirectional fiber layer to be followed by a nonwoven fabric as the next layer, while a woven fabric terminates the 3-dimensional fiber structure.
  • a woven fabric terminates the 3-dimensional fiber structure.
  • the unidirectional 2-dimensional fiber structures can be the same orientation or differently oriented with respect to their direction. In the latter case, there is a multiaxial clutch.
  • glass fibers As materials for fiber structures, glass fibers, carbon fibers, synthetic fibers, aramid fibers, PBO fibers, polyethylene fibers, polyester fibers, polyamide fibers, natural fibers, basalt fibers, quartz fibers, alumina fibers, silicon carbide fibers or mixed forms can be used.
  • Additives are materials that are added to the plastic matrix to alter their properties in the desired manner.
  • additives are added to the plastic matrix to provide, for example, abrasion resistance, low tendency to crack, low crack growth, high resistance to paper machine media such as water, oil, acids, alkalis, solvents or the like.
  • desired surface properties such as the adhesion to a fibrous web, the hardness or the like to influence targeted. It can also be influenced by the additives properties that are achieved by the fiber reinforcement.
  • pigments, microfibers such as carbon fibers, glass fibers or the like, glass powder, carbon black, clay, montmorillonite, saponite, hectorite, mica, vermiculite, bentonite, nontronite, beidellite, volkonskoite, manadiite, kenyaite, Smectite, bederite, silicon carbide, silicic acid salts, metal oxides or any mixtures of the abovementioned compounds.
  • a fibrous web is meant a scrim of fibers comprising wood fibers, plastic fibers, glass fibers, carbon fibers, additives, additives or the like.
  • the fibrous web can be designed as a paper, cardboard or tissue web, which essentially consists of wood consist of fibers, with small amounts of other fibers or additives and additives are present.
  • At least one further subregion of the fiber-reinforced plastic matrix can be formed as foam.
  • a higher elasticity and softness of the press belt can be produced by forming a further portion of the fiber-reinforced plastic matrix as foam.
  • the contact pressure can be adjusted more precisely.
  • the contact force fluctuates less in uneven areas in the fibrous web or other components of the paper machine. This is understood by a foam bubbles, which are separated by walls. If the foam is open-pored, the walls are at least partially broken, while in a closed foam, the individual bubbles are closed by the walls.
  • the subregion of the at least polyurethane and as additive polydimethylsiloxane and silicon dioxide microparticles, or the further portion which is formed as a foam, z. B. comprise a layer of the press belt, a surface layer of the press belt, an edge region of the press belt or an inner layer of the press belt.
  • the press belt can be provided with the desired surface property, but nevertheless be provided with differently advantageous internal properties by differently formed internal layers of the press belt.
  • the abrasion resistance, an advantageous cracking behavior, as well as a high resistance to media occurring in the paper machine can be achieved, while a sufficiently high elasticity and tear resistance can be produced by inner layers.
  • An inner layer, for example formed of a foam can positively influence the elasticity behavior and the softness of the press belt, without impairing the required high resistance of the surface of the press belt.
  • a layer or position of the press belt is understood to mean a region that can be delimited in the thickness direction from other layers or layers.
  • the delimitation can be carried out, for example, by the fiber reinforcement, by the structure of the plastic matrix, by the additive components and / or by mechanical properties.
  • the polydimethylsiloxane used can have a viscosity of 100 to 100,000 mPa * s. It is also possible to use polydimethylsiloxane having a viscosity of from 500 to 50,000 mPa * s, if appropriate from 1 to 10,000 mPa * s, in particular from 1,500 to 5,000 mPa * s and, for example, from 2,000 to 3,000 mPa * s , This refers to a temperature of 25 ° C.
  • the at least one subregion may comprise from 0.1 to 10% by weight of polydimethylsiloxane. It is also conceivable for the at least one subregion to contain 0.1 to 8% by weight, in particular 0.1 to 5% by weight, if appropriate 0.1 to 3% by weight and, for example, 0.2 to 1, 5 wt .-% polydimethylsiloxane has.
  • the aforementioned advantages can be achieved by such a proportion of polydimethylsiloxane.
  • the silica microparticles may have an average particle size of 2 to 800 ⁇ m. It is also conceivable to use silicon dioxide microparticles which have an average particle size of from 5 to 500 ⁇ m, in particular from 5 to 50 ⁇ m, for example from 10 to 30 ⁇ m, and if appropriate from 10 to 20 ⁇ m.
  • the dispersibility of the educts of the plastic matrix can advantageously be improved by such an average particle size of the silica microparticles.
  • the at least one subarea can have from 0.01 to 10% by weight of silicon dioxide microparticles.
  • the aforementioned advantages can be achieved by such a proportion of silica microparticles.
  • silicon dioxide nanoparticles can be used in the at least one subregion with an average particle size of 10 to 80 nm. It is also conceivable to use silicon dioxide nanoparticles which have an average particle size of 12 to 60 nm, in particular 14 to 40 nm, for example 16 to 30 nm, and optionally 18 to 25 nm.
  • the tendency to crack formation can be reduced by the use of silicon dioxide nanoparticles. The tendency to crack growth may also be reduced.
  • the sole use of silicon dioxide nanoparticles improves the tendency to crack, but leads to a deterioration of the abrasion resistance. In the combination of the additives, the abrasion resistance of the at least one subregion is increased
  • the at least one subarea can have from 0.01 to 10% by weight of silicon dioxide nanoparticles.
  • the at least one polyurethane can be produced at least from a polyurethane prepolymer and a crosslinker.
  • the polyurethane prepolymer may be formed as MDI prepolymer and / or as PPDI prepolymer with polyether and / or polycarbonates and / or polycaprolactones as polyol component.
  • the desired durability and resistance to wear of the press belt can be produced by such a design of the polyurethane component of the plastic matrix.
  • such a plastic matrix is characterized by a high resistance to the media occurring in the paper machine.
  • the crosslinker may contain at least one polyether polyol. It is also conceivable that a linear polyether polyol is used and, for example, also linear polypropylene ether polyol. By means of such crosslinkers, the properties of the plastic matrix can be advantageously influenced with regard to the elasticity, the hardness and the resistance to media occurring in the paper machine.
  • a method for producing a plastic matrix for a press belt of a shoe press device for dewatering or smoothing a fibrous web, in particular a paper, board or tissue web as described above is proposed.
  • the plastic matrix is produced from at least one polyurethane prepolymer, at least one crosslinker, polydimethylsiloxane and silicon dioxide microparticles.
  • press belts can be produced which have the advantages mentioned above.
  • silica nanoparticles may be mixed with at least a portion of the crosslinker to form a nanoparticle blend containing 20 to 60 wt% silica nanoparticles. It is also conceivable that the nanoparticle mixture 25 to 55 wt .-%, for example, 30 to 50 wt .-%, in particular 35 to 45 wt .-% and optionally 38 to 42 wt .-% silicon dioxide nanoparticles.
  • a good dispersibility can be achieved by such a process control. If silicon dioxide nanoparticles which have arisen from a sol-gel process are used, it being possible for the OH groups on the surface of the particles to be blocked by means of silanization, then the dispersibility of the educts of the plastic matrix can be further improved. Furthermore, the nanoparticle mixture can completely replace the crosslinker or 5 to 40% in subsequent process steps. Furthermore, it is also conceivable that the nanoparticle mixture replaces the crosslinker to 6 to 35%, in particular to 7 to 30%, for example to 9 to 30% and optionally to 10 to 25%. By such a procedure, the dispersibility of the educts of the plastic matrix can also be further improved.
  • the silica microparticles can be mixed with the polydimethylsiloxane and optionally with further additives to form an additive mixture. This can subsequently be mixed with at least part of the crosslinker. It is conceivable that silica nanoparticles have been previously mixed into the crosslinker.
  • the mean particle size can be determined, for example, by means of laser scattered light methods or by means of dynamic image analysis. By means of dynamic image analysis, particle sizes of 1 ⁇ m to 30 mm can be determined.
  • the laser Light scattering methods allow a particle size analysis of 0.3 nm to 1 ⁇ .
  • the mean particle size is defined according to the respective measuring method used for its size range.
  • Fig. 1 is a view of a shoe press with a press cover according to an embodiment of the present invention
  • FIG. 2 shows an overview of a press section comprising a shoe press and a conveyor belt of a paper machine according to an exemplary embodiment of the present invention.
  • FIG. 1 shows a shoe press 10 which comprises a shoe roll 12 and a counter roll 14. While the counter-roller 14 consists of a rotating cylindrically shaped roller, the shoe roller 12 is composed of a shoe 16, a supporting yoke 18 carrying it and a press cover 20. In this case, the shoe 16 is supported by the yoke 18 and pressed against not shown, hydraulic pressing elements on this rotating press cover 20. Due to the concave configuration of the shoe 16 on its opposite side of the counter-roller 14 results in a relatively long press nip 22.
  • the shoe press 10 is particularly suitable for dewatering fibrous webs 24.
  • the shoe press In the operation of the shoe press is a fibrous web 24 with one or two press films 26, 26 'guided by the press nip 22, wherein the due to the force exerted in the press nip 22 on the fibrous web 24 pressure from the fibrous web 24 exiting liquid which contains dissolved and undissolved compounds in addition to water, such as fibers, fiber fragments, additives and / or additives , of the or the press felts 26,26 'and temporarily provided by depressions (not shown) provided in the press shell surface.
  • the liquid picked up by the press jacket 20 is thrown off the press jacket 20 before the press jacket 20 again enters the press nip 22.
  • the water taken up by the press felt 26, 26 ' is removed after leaving the press nip 22 with suction elements.
  • FIG. 2 shows a section of a press section of a paper machine 30, which comprises a shoe press 10.
  • the shoe press 10 as in the embodiment shown in FIG. 1, comprises a shoe roll 12 having a press jacket 20 and a pressing element or shoe 16 and a counter roll 14, a press nip being formed between the shoe 16 and the counter roll 14 ,
  • this part of the paper machine comprises two suction rolls 28, 28 'and two deflection rolls 30, 30'.
  • a felt 26 guided by the suction rolls 28, 28 ' which receives the fibrous web 24 at the suction roll 28, is guided through the press nip.
  • the transfer belt 32 in the press nip takes the fibrous web 24 of the felt 26 and on the guide roller 30' removed from the press nip. Due to the pressure exerted in the press nip on the fibrous web 24 pressure exits from the fibrous web 15 liquid which contains dissolved and undissolved compounds in addition to water, such as fibers, fiber fragments, additives and / or additives, which of the felt 26 and is temporarily received by recesses provided in the press cover surface.
  • the liquid picked up by the press cover 20 is thrown off the press cover 20 before the press cover 20 re-enters the press nip.
  • the water taken up by the felt 26 is removed after leaving the press nip with suction elements provided on the suction roll 28 '. Because of the concave design of the shoe 16 comparatively long press nip 25 is achieved with such a shoe press compared to a press consisting of two rotating rollers a much better dewatering of the fibrous web 24, so that the subsequent thermal drying can be correspondingly shorter. In this way, a particularly gentle dewatering of the fibrous web 24 is achieved.
  • the abrasion resistance is significantly improved by the addition of polydimethylsiloxane-silica microparticles, especially after storage in water.
  • the tendency for cracking is Growth essentially unchanged.
  • the abrasion resistance can be improved with almost unchanged tendency to crack growth.
  • An MDI-polyether prepolymer with an NCO content of about 6% is used.
  • the crosslinker used is MCDEA and PTHF200 and the crosslinking is carried out at a temperature of 90.degree.
  • the prepolymer, MCDEA and PTHF2000 are separately degassed with a vacuum evaporator.
  • Polydimethylsiloxane-SiO 2 microparticles are added to the crosslinker. Then all components are mixed in a vortex mixer. The mixture is poured into steel molds and tempered.
  • the abrasion resistance was carried out according to DIN 5316 and ISO 4649. For this purpose, a sample piece with a diameter of 16 mm with a test load of 10 N was applied. The grinding length was 40 m at an angular speed of 40 revolutions per minute. Determination of the mean value of the crack growth:
  • the crack growth is carried out in a BW machine (bending change machine).
  • BW machine bending change machine
  • the sample is bent 1, 000 000 times at a frequency of 7.5 Hz at an angle of +/- 40 °.
  • a section in the sample has a width of 6 mm and a depth of 2.5 mm.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Paper (AREA)

Abstract

Bande de pressage pour une presse à pince allongée (10) destinée à égoutter ou à lisser une bande de matière fibreuse, en particulier une bande de papier, de carton ou de papier ouaté, ladite bande de pressage (20, 32) comportant une matrice en plastique renforcé par des fibres. Du fait que la matrice en plastique renforcée par des fibres comporte au moins dans une zone au moins un polyuréthane et en tant qu'additifs du polydiméthylsiloxane et des microparticules de dioxyde de silicium, la résistance à l'usure, la propension à la formation de fissures et à la propagation de fissures et/ou la résistance vis à vis des substances présentes dans une machine à papier s'en trouvent améliorées.
EP13753636.3A 2012-09-04 2013-08-29 Bande de pressage dans une machine à papier Withdrawn EP2893079A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102012215612 2012-09-04
PCT/EP2013/067858 WO2014037268A1 (fr) 2012-09-04 2013-08-29 Bande de pressage dans une machine à papier

Publications (1)

Publication Number Publication Date
EP2893079A1 true EP2893079A1 (fr) 2015-07-15

Family

ID=49080881

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13753636.3A Withdrawn EP2893079A1 (fr) 2012-09-04 2013-08-29 Bande de pressage dans une machine à papier

Country Status (5)

Country Link
US (1) US20150211177A1 (fr)
EP (1) EP2893079A1 (fr)
CN (1) CN104603358A (fr)
CA (1) CA2883016A1 (fr)
WO (1) WO2014037268A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6674698B2 (ja) * 2015-04-07 2020-04-01 ヤマウチ株式会社 シュープレス用ベルト
FI20216016A1 (en) * 2021-09-30 2023-03-31 Valmet Technologies Oy Band

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4830905A (en) * 1988-08-22 1989-05-16 Appleton Mills Papermaker's felt incorporating a closed cell polymeric foam layer
JP3831851B2 (ja) * 1999-09-29 2006-10-11 イチカワ株式会社 シュープレス用ベルト
US20040014383A1 (en) * 2002-07-19 2004-01-22 Atsushi Ishino Belt for papermaking machine and manufacturing method therefor
JP4133433B2 (ja) * 2003-02-26 2008-08-13 イチカワ株式会社 抄紙用プレスフェルト
US7156956B2 (en) * 2003-08-11 2007-01-02 Albany International Corp. Paper industry process belt with a surface structure composed of a porous membrane
PT1725599E (pt) * 2004-03-16 2010-10-22 Albany Int Corp Correias revestidas com poliuretano compreendendo nanoenchedores
JP2006037328A (ja) * 2004-06-25 2006-02-09 Ichikawa Co Ltd 製紙機械用ベルト
US20060118261A1 (en) * 2004-11-16 2006-06-08 Ichikawa Co., Ltd. Shoe press belt
JP2006144139A (ja) * 2004-11-16 2006-06-08 Ichikawa Co Ltd シュープレス用ベルト
DE102007019960A1 (de) * 2007-04-27 2008-11-06 Voith Patent Gmbh Verbesserungen bei Transferbändern, Hintergrund der Erfindung
FI121015B (fi) * 2007-07-05 2010-06-15 Tamfelt Pmc Oy Kenkäpuristinhihna
JP4616403B1 (ja) * 2009-11-27 2011-01-19 イチカワ株式会社 抄紙用プロセスベルト

Non-Patent Citations (1)

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Title
See references of WO2014037268A1 *

Also Published As

Publication number Publication date
US20150211177A1 (en) 2015-07-30
CN104603358A (zh) 2015-05-06
CA2883016A1 (fr) 2014-03-13
WO2014037268A1 (fr) 2014-03-13

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