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WO1992010607A1 - Improvements in and relating to paper machine clothing - Google Patents

Improvements in and relating to paper machine clothing Download PDF

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Publication number
WO1992010607A1
WO1992010607A1 PCT/GB1991/002158 GB9102158W WO9210607A1 WO 1992010607 A1 WO1992010607 A1 WO 1992010607A1 GB 9102158 W GB9102158 W GB 9102158W WO 9210607 A1 WO9210607 A1 WO 9210607A1
Authority
WO
WIPO (PCT)
Prior art keywords
sheet
article
layer
polyfluorocarbon
paper
Prior art date
Application number
PCT/GB1991/002158
Other languages
French (fr)
Inventor
Sandra Krohto Barlow
Maryann Kenney
Ludmilla Konopasek
Michael Glenn Moriarty
Original Assignee
Albany International Corp.
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 Albany International Corp. filed Critical Albany International Corp.
Priority to AU90232/91A priority Critical patent/AU660632B2/en
Priority to BR919107208A priority patent/BR9107208A/en
Priority to JP4500504A priority patent/JPH06506020A/en
Priority to KR1019930701681A priority patent/KR100243849B1/en
Publication of WO1992010607A1 publication Critical patent/WO1992010607A1/en
Priority to NO93931995A priority patent/NO931995L/en

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
    • D21F1/0063Perforated sheets
    • 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
    • D21F1/0036Multi-layer screen-cloths
    • 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
    • D21F7/083Multi-layer felts

Definitions

  • This invention relates to paper machine clothing and has particular reference to paper machine clothing for use in the pressing and drying sections of a paper machine, although the invention described herein is equally applicable in other sections of a paper making machine.
  • a conventional paper making machine forms a web by depositing a slurry of pulp fibres to be formed into a paper sheet onto, for example, a travelling Foudrinier wire. After initial dewatering on the Foudrinier wire, the forming paper sheet or web is transferred to a press section where the web passes through one or more nips comprised of either roll or shoe combinations. During this time, the sheet is consolidated and further properties of the sheet may be developed. Thereafter, the web passes over a series of heated dryer drums (and optionally through a calender) and is then wound onto a roll.
  • a series of heated dryer drums and optionally through a calender
  • the web In such a machine, the web usually arrives at the press section with about 80% wet base moisture (a ratio of water to fibre + water) and leaves the press section with approximately 60% moisture ratio (or 40% dryness). The remaining moisture has to be removed by thermal evaporation in the dryer section as the web passes over a series of heated drums.
  • a significant number of dryer drums will be employed, sometimes on the order of 50 to 70 drums per machine.
  • Each dryer drum is expensive to construct and to operate and requires a provision of steam fittings and a supply of steam or other heat source for each drum.
  • Impulse drying is a method of dewatering a paper sheet by incorporating both high temperature and pressure in a press section of a paper making machine.
  • the surface of the press roll is usually heated to a temperature of 150°C or greater, and is in direct contact with the paper.
  • the resulting paper sheet dryness is significantly increased to 60% or higher.
  • the effectiveness of such a system is such that the number of dryer drums in a paper making machine can be substantially reduced.
  • impulse drying The principle of operation underlying impulse drying is believed to be that the heated roll forms a zone of steam in the paper sheet during pressing of the sheet which drives out liquid water as the steam passes through the sheet. Generation of this steam front, and high temperature of the press roll provides rather severe conditions for the press fabric.
  • the press fabric In order to withstand this high temperature, the press fabric should have sufficient thermal resistance to allow continued exposure to high temperature steam and occasional exposure to the high temperature press roll directly during breaks in the paper sheet passing therethrough.
  • this press fabric should adequately release the paper sheet after the nip to provide for acceptable sheet runnability. Also the press fabric should minimize rewet of the sheet as it exits the nip to produce a sheet with maximum dryness. These properties should be combined with sufficient mechanical durability to withstand the severe conditions of the impulse drying process. According to traditional pressing theory, a press fabric should also provide and maintain adequate permeability for the water leaving the sheet.
  • an article of paper machine clothing which comprises a first woven base layer and a second sheet contacting layer carried thereby, characterised in that the sheet contacting surface of said second layer comprises a polyfluorocarbon polymer.
  • the polyfluorocarbon polymer may be in a fibrous form.
  • the said second layer may comprise a fibrous structure of batt or staple fibre which is needled to the base layer.
  • the second layer may typically comprise a batt of 100% polyfluorocarbon polymers or may be a blend of fibres of polyfluorocarbon with any high temperature resistant fibres such, for example, as polyamide, polyaramid, polyester, polyimide, polyetherketone. polybenzimidazole or polyether imide.
  • the polyfluorocarbon may be polytetrafluoroethylene of the type commercially available under the trade name "TEFLON" (PTFE) .
  • the sheet contacting surface may contain an effective amount of polyfluorocarbon to achieve the desirable properties for the impulse drying process.
  • the effective amount of polyfluorocarbon may be in the form of a discrete surface layer, a coating on the surface on the fibres constituting the said second layer, a pre-formed nonwoven layer of polyfluorocarbon, or a finely woven polyfluorocarbon fabric, each of which can be needled or otherwise bonded to the surface to incorporate it as part of the surface layer.
  • the surface layer incorporating polyfluorocarbon may be in a form other than a textile form.
  • the sheet contacting surface of said second layer may comprise a film of polyfluorocarbon.
  • the layer may for example be formed by bonding, laminating or otherwise attaching a polyfluorocarbon polymer film, to the remainder of the second layer.
  • a surface layer can also be formed by coating with a fluorocarbon emulsion or suspension, by spraying, dipping or other suitable methods.
  • the surface layer may also be formed by direct application of a fluorocarbon in particulate form.
  • Figures 1 (a), (b) and (c) are a series of graphs relating to Example 2.
  • Figure 2 is a photomicrograph of the sheet contacting surface of a PTFE surfaced press fabric of Example 3.
  • EXAMPLE 1 An experimental pilot press fabric, made up of 11 test sections, was prepared using conventional carding and needling processes. Each experimental section represented either a candidate fibre or a test structure. Each candidate fibre was prepared into a carded web and a total of eight card web layers were combined to construct each experimental section. All sections were needled onto a common woven base fabric. The experimental felt was installed on a pilot impulse drying machine and run at the following conditions:
  • the paper stock used for these tests was 100% Bleached Softwood Kraft with a 500 CSF prepared into 50 g/m 2 handsheets with an ingoing dryness of 36%.
  • the ingoing felt moisture ratio for each fabric was 0.35.
  • final paper dryness and felt moisture gain were determined.
  • each felt's air permeability after conditioning was also measured.

Landscapes

  • Paper (AREA)

Abstract

The present invention is concerned with paper machine clothing and in particular paper machine clothing for use in a pressing section of a paper machine, suitable for use in high temperature pressing or impulse drying. A particular feature of this invention is a sheet contacting surface comprising a polyfluorocarbon polymer which may be in the form of fibrous sheets.

Description

IMPROVEMENTS IN AND RELATING TO PAPER MACHINE CLOTHING
DESCRIPTION
This invention relates to paper machine clothing and has particular reference to paper machine clothing for use in the pressing and drying sections of a paper machine, although the invention described herein is equally applicable in other sections of a paper making machine.
A conventional paper making machine forms a web by depositing a slurry of pulp fibres to be formed into a paper sheet onto, for example, a travelling Foudrinier wire. After initial dewatering on the Foudrinier wire, the forming paper sheet or web is transferred to a press section where the web passes through one or more nips comprised of either roll or shoe combinations. During this time, the sheet is consolidated and further properties of the sheet may be developed. Thereafter, the web passes over a series of heated dryer drums (and optionally through a calender) and is then wound onto a roll. There are many variations in the various sections of the machine such as the forming or press sections. In such a machine, the web usually arrives at the press section with about 80% wet base moisture (a ratio of water to fibre + water) and leaves the press section with approximately 60% moisture ratio (or 40% dryness). The remaining moisture has to be removed by thermal evaporation in the dryer section as the web passes over a series of heated drums. In a typical paper making machine, such as that manufacturing newsprint, a significant number of dryer drums will be employed, sometimes on the order of 50 to 70 drums per machine. Each dryer drum is expensive to construct and to operate and requires a provision of steam fittings and a supply of steam or other heat source for each drum.
In recent years, the principle of impulse drying has introduced. Impulse drying is a method of dewatering a paper sheet by incorporating both high temperature and pressure in a press section of a paper making machine. During this process, the surface of the press roll is usually heated to a temperature of 150°C or greater, and is in direct contact with the paper. With such a process, the resulting paper sheet dryness is significantly increased to 60% or higher. The effectiveness of such a system is such that the number of dryer drums in a paper making machine can be substantially reduced.
The principle of operation underlying impulse drying is believed to be that the heated roll forms a zone of steam in the paper sheet during pressing of the sheet which drives out liquid water as the steam passes through the sheet. Generation of this steam front, and high temperature of the press roll provides rather severe conditions for the press fabric.
In order to withstand this high temperature, the press fabric should have sufficient thermal resistance to allow continued exposure to high temperature steam and occasional exposure to the high temperature press roll directly during breaks in the paper sheet passing therethrough.
In addition, this press fabric should adequately release the paper sheet after the nip to provide for acceptable sheet runnability. Also the press fabric should minimize rewet of the sheet as it exits the nip to produce a sheet with maximum dryness. These properties should be combined with sufficient mechanical durability to withstand the severe conditions of the impulse drying process. According to traditional pressing theory, a press fabric should also provide and maintain adequate permeability for the water leaving the sheet.
According to the present invention, therefore, there is provided an article of paper machine clothing which comprises a first woven base layer and a second sheet contacting layer carried thereby, characterised in that the sheet contacting surface of said second layer comprises a polyfluorocarbon polymer.
The polyfluorocarbon polymer may be in a fibrous form. The said second layer may comprise a fibrous structure of batt or staple fibre which is needled to the base layer. The second layer may typically comprise a batt of 100% polyfluorocarbon polymers or may be a blend of fibres of polyfluorocarbon with any high temperature resistant fibres such, for example, as polyamide, polyaramid, polyester, polyimide, polyetherketone. polybenzimidazole or polyether imide. The polyfluorocarbon may be polytetrafluoroethylene of the type commercially available under the trade name "TEFLON" (PTFE) .
In an alternative aspect of the present invention, the sheet contacting surface may contain an effective amount of polyfluorocarbon to achieve the desirable properties for the impulse drying process. The effective amount of polyfluorocarbon may be in the form of a discrete surface layer, a coating on the surface on the fibres constituting the said second layer, a pre-formed nonwoven layer of polyfluorocarbon, or a finely woven polyfluorocarbon fabric, each of which can be needled or otherwise bonded to the surface to incorporate it as part of the surface layer.
In another aspect of the present invention, the surface layer incorporating polyfluorocarbon may be in a form other than a textile form. The sheet contacting surface of said second layer may comprise a film of polyfluorocarbon. The layer may for example be formed by bonding, laminating or otherwise attaching a polyfluorocarbon polymer film, to the remainder of the second layer.
Either a monolithic, perforated or microporous film can be employed. A surface layer can also be formed by coating with a fluorocarbon emulsion or suspension, by spraying, dipping or other suitable methods. The surface layer may also be formed by direct application of a fluorocarbon in particulate form.
In the practice of this invention, it has been noted that after multiple compressions within the press nip press fabrics have significantly reduced air permeability, yet surprisingly still continue to produce high sheet dryness values; the more so since traditional press fabrics having such low air permeabilities do not normally dewater the sheet effectively.
Following is a description by way of example only and with reference to the accompanying drawings of methods of carrying the invention into effect. In the drawings:-
Figures 1 (a), (b) and (c) are a series of graphs relating to Example 2.
Figure 2 is a photomicrograph of the sheet contacting surface of a PTFE surfaced press fabric of Example 3.
EXAMPLE 1 An experimental pilot press fabric, made up of 11 test sections, was prepared using conventional carding and needling processes. Each experimental section represented either a candidate fibre or a test structure. Each candidate fibre was prepared into a carded web and a total of eight card web layers were combined to construct each experimental section. All sections were needled onto a common woven base fabric. The experimental felt was installed on a pilot impulse drying machine and run at the following conditions:
Nip pressure: 375 pli Roll temperature: 160°C (320°F) Fabric speed: 107 fpm The handsheets used during this test were a newsprint grade comprised of 71% groundwood, 29% high yield sulfite. Five of the eleven test sections in the experimental felt were constructed with a paper contacting surface comprised of at least 50% by weight Teflon. Of the 11 sections tested during this study, all five Teflon containing felts produced paper sheets with the highest dryness, ranging between 70% and 75% dryness. All of the other high temperature resistant materials tested (such as polyaramid, polyetheretherketone, and an aromatic polyamide 6T) , produced paper sheets with lower dryness values (between 61% and 69%).
EXAMPLE 2
A series of experimental press fabrics were constructed with varying percentages of Teflon fibre in the paper contacting layers of the fabric. The blends ranged from 0% Teflon to 100% Teflon, in increments of 25%. Each fabric sample was conditioned at 21°C for 500 cycles at 1000 psi, and then tested on a laboratory impulse dryer tester at the following conditions: Pressure: 5500 KPa
Nip Residence: 45 msec
Upper Platen Temp: 190°C
The paper stock used for these tests was 100% Bleached Softwood Kraft with a 500 CSF prepared into 50 g/m2 handsheets with an ingoing dryness of 36%. The ingoing felt moisture ratio for each fabric was 0.35. During testing, final paper dryness and felt moisture gain were determined. In addition, each felt's air permeability after conditioning was also measured.
Results of the study clearly show that as the percentage of Teflon fibre in the paper contacting layer increases, both paper dryness and felt moisture gain increase significantly, while the press fabric's air permeability decreases. Traditionally, lower air permeability in a press fabric usually relates to lower dewatering capability; however, in this case, the trend is opposite. Under the test conditions discussed above, approximately 10% higher paper dryness values are achieved with the sample having a 100% Teflon paper contacting layer compared to the sample containing 0% Teflon, while at the same time air permeability decreased from 12.2 cfm for the 0% Teflon sample to 4.2 cfm for the 100% Teflon sample.
The results of this study are shown below in Table 1 and are displayed in Figure 1 of the accompanying drawings.
Table 1. Teflon Blend Press Fabric Structure Study
Figure imgf000012_0001
An experimental press fabric containing a 100% Teflon paper contacting layer was tested on a pilot paper machine with an impulse drying roll and an extended nip press shoe. The conditions used for this trial were as follows: Maximum nip pressure: 600 pli
Machine speed: 820 m/min (2500fpm)
Hot Roll Temperature: 177°C (350°F)
Paper basis weight: 45-50 g/m2 Ingoing paper dryness: 25-36%
During this trial, a final paper dryness greater than 60% was obtained. Subsequent to this trial, a sample of the used press fabric was returned to the laboratory and examined. Visual examination showed that the surface was heavily sealed and glazed. An SEM photomicrograph of this surface (see Figure 2 of the accompanying drawings) confirmed this condition. A specimen was removed from this area of the fabric and subsequently tested on a laboratory impulse dryer tester for dewatering using 50 g/m2 handsheets at 36% initial dryness. Regardless of this sealed surface, the results, surprisingly, showed paper dryness as high as 65%. Through our experience, any other press fabrics having a similar glazed or sealed surface would be expected to produce a very low level of dewatering, thus low paper dryness.

Claims

1. An article of paper machine clothing characterised by having a sheet-contacting surface
5 comprising a polyfluorocarbon polymer.
2. An article as claimed in claim 1 characterised in that the polyfluorocarbon polymer is present in one or more of fibres, sheet or coating.
10
3. An article as claimed in claim 1 or claim 2 characterised in that the sheet contacting surface is fibrous and comprises a batt structure of staple fibre.
15 4. An article as claimed in any preceding claim characterised in that the sheet-contacting surf ce comprises a distinct layer carried by a base layer or substrate.
20 5. An article as claimed in claim 4 characterised in that the base layer or substrate is a woven layer.
6. An article as claimed in any preceding claim characterised in that the sheet-contacting surface is part of a sheet contacting layer, said layer being secured to the base layer.
7. An article as claimed in claim 6 characterised in that the sheet-contacting layer is a batt fibre structure comprising a polyfluorocarbon polymer.
8. An article as claimed in any one of claims 3 to 7 characterised in that the batt structure includes a proportion of high temperature resistance fibres, selected from polyamide, polyaramid, polyester, polyimide, polyetherketone and polybenzelmidizole and polyetherimide.
9. An article as claimed in any preceding claim characterised in that the polyfluorocarbon is present in sheet form as a discrete surface layer or a surface coating on fibres.
10. An article as claimed in any one of claims 2 to 9 wherein the polyfluorocarbon is a finely woven polyfluorocarbon fabric needled or bonded to a substrate.
11. An article as claimed in any one of claims 2 to 9 characterised in that the sheet contacting surface comprises a polyfluorocarbon film or sheet further characterised in that said film or sheet is monolithic, perforated or microporous.
PCT/GB1991/002158 1990-12-05 1991-12-05 Improvements in and relating to paper machine clothing WO1992010607A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
AU90232/91A AU660632B2 (en) 1990-12-05 1991-12-05 Improvements in and relating to paper machine clothing
BR919107208A BR9107208A (en) 1990-12-05 1991-12-05 MACHINE COATING ARTICLE FOR PAPER MANUFACTURING
JP4500504A JPH06506020A (en) 1990-12-05 1991-12-05 Improvements in papermaking tools and related improvements
KR1019930701681A KR100243849B1 (en) 1990-12-05 1991-12-05 Thermostable paper machine clothing product
NO93931995A NO931995L (en) 1990-12-05 1993-06-02 A paper machine fabric

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB909026475A GB9026475D0 (en) 1990-12-05 1990-12-05 Improvements in and relating to paper machine clothing
GB9026475.5 1990-12-05

Publications (1)

Publication Number Publication Date
WO1992010607A1 true WO1992010607A1 (en) 1992-06-25

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1991/002158 WO1992010607A1 (en) 1990-12-05 1991-12-05 Improvements in and relating to paper machine clothing

Country Status (10)

Country Link
EP (1) EP0564474A1 (en)
JP (1) JPH06506020A (en)
KR (1) KR100243849B1 (en)
AU (1) AU660632B2 (en)
BR (1) BR9107208A (en)
CA (1) CA2097834A1 (en)
FI (1) FI932593A0 (en)
GB (1) GB9026475D0 (en)
MX (1) MX9102362A (en)
WO (1) WO1992010607A1 (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0547816A1 (en) * 1991-12-05 1993-06-23 Albany International Corp. Improvements in and relating to paper machine clothing
EP0620874A1 (en) 1992-09-25 1994-10-26 Albany International Corp. Novel fabrics for high temperature pressing applications
WO1995028519A1 (en) * 1994-04-15 1995-10-26 Scapa Group Plc Papermachine clothing
US5569358A (en) * 1994-06-01 1996-10-29 James River Corporation Of Virginia Imprinting felt and method of using the same
EP0908542A2 (en) * 1997-10-07 1999-04-14 Asten, Inc. Yarns and industrial fabrics made from a fluoropolymer blend
EP0995835A1 (en) * 1998-10-19 2000-04-26 Shakespeare Company Fibers having improved dewatering characteristics for press felts
DE19854732C1 (en) * 1998-11-26 2000-09-14 Inventa Ag Core-jacket bicomponent fiber and its use

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6284380B1 (en) * 1997-02-25 2001-09-04 Albany International Corp. Paper machine clothing and a method of coating same
JP4522212B2 (en) * 2004-09-29 2010-08-11 イチカワ株式会社 Paper transport felt and press machine of paper machine equipped with the paper transport felt

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3121660A (en) * 1961-02-13 1964-02-18 Jr Edward H Hall Fourdrinier wire and method of making the same
GB1455843A (en) * 1973-01-31 1976-11-17 Scapa Porritt Ltd Paper makers wet felts
US4457968A (en) * 1983-08-02 1984-07-03 Niagara Lockport Industries, Inc. Process for manufacture of a poly (perfluoroolefin) belt and a belt made thereby
EP0211471A1 (en) * 1985-07-08 1987-02-25 Asten Group, Inc. Laminated spiral mesh papermakers fabric

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4697397A (en) * 1985-08-10 1987-10-06 Shimizu Construction Co. Ltd. Trussed girder, roof framing using the trussed girder and method of constructing the roof framing of a building using the trussed girder

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3121660A (en) * 1961-02-13 1964-02-18 Jr Edward H Hall Fourdrinier wire and method of making the same
GB1455843A (en) * 1973-01-31 1976-11-17 Scapa Porritt Ltd Paper makers wet felts
US4457968A (en) * 1983-08-02 1984-07-03 Niagara Lockport Industries, Inc. Process for manufacture of a poly (perfluoroolefin) belt and a belt made thereby
EP0211471A1 (en) * 1985-07-08 1987-02-25 Asten Group, Inc. Laminated spiral mesh papermakers fabric

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WORLD PATENTS INDEX Section Ch, Week 8018, Derwent Publications Ltd., London, GB; Class A, AN 80-32068& JP,A,55 040 841 (NIPPON FELT KK) 23 March 1980 see abstract *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0547816A1 (en) * 1991-12-05 1993-06-23 Albany International Corp. Improvements in and relating to paper machine clothing
EP0620874A1 (en) 1992-09-25 1994-10-26 Albany International Corp. Novel fabrics for high temperature pressing applications
WO1995028519A1 (en) * 1994-04-15 1995-10-26 Scapa Group Plc Papermachine clothing
US5569358A (en) * 1994-06-01 1996-10-29 James River Corporation Of Virginia Imprinting felt and method of using the same
US5591305A (en) * 1994-06-01 1997-01-07 The James River Corporation Of Virginia Imprinting felt and method of using the same
EP0908542A2 (en) * 1997-10-07 1999-04-14 Asten, Inc. Yarns and industrial fabrics made from a fluoropolymer blend
EP0908542A3 (en) * 1997-10-07 1999-09-22 Asten, Inc. Yarns and industrial fabrics made from a fluoropolymer blend
US6136437A (en) * 1997-10-07 2000-10-24 Astenjohson, Inc. Industrial fabric and yarn made from an improved fluoropolymer blend
EP0995835A1 (en) * 1998-10-19 2000-04-26 Shakespeare Company Fibers having improved dewatering characteristics for press felts
DE19854732C1 (en) * 1998-11-26 2000-09-14 Inventa Ag Core-jacket bicomponent fiber and its use
US6207276B1 (en) 1998-11-26 2001-03-27 Ems-Chemie Ag Sheath-core bicomponent fiber and its applications

Also Published As

Publication number Publication date
JPH06506020A (en) 1994-07-07
MX9102362A (en) 1992-06-01
FI932593A (en) 1993-06-07
FI932593A0 (en) 1993-06-07
GB9026475D0 (en) 1991-01-23
AU660632B2 (en) 1995-07-06
EP0564474A1 (en) 1993-10-13
BR9107208A (en) 1993-11-03
CA2097834A1 (en) 1992-06-06
AU9023291A (en) 1992-07-08
KR100243849B1 (en) 2000-02-01

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