EP0398434A1 - Process for the manufacture of stretched rope - Google Patents

Process for the manufacture of stretched rope Download PDF

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Publication number
EP0398434A1
EP0398434A1 EP90201216A EP90201216A EP0398434A1 EP 0398434 A1 EP0398434 A1 EP 0398434A1 EP 90201216 A EP90201216 A EP 90201216A EP 90201216 A EP90201216 A EP 90201216A EP 0398434 A1 EP0398434 A1 EP 0398434A1
Authority
EP
European Patent Office
Prior art keywords
rope
filaments
strength
stretched
stretching
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
Application number
EP90201216A
Other languages
German (de)
French (fr)
Other versions
EP0398434B1 (en
Inventor
Eric Henricus Maria Hogenboom
Christiaan Henri Peter Dirks
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.)
Koninklijke DSM NV
DSM IP Assets BV
Original Assignee
Stamicarbon BV
DSM NV
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Filing date
Publication date
Application filed by Stamicarbon BV, DSM NV filed Critical Stamicarbon BV
Priority to AT90201216T priority Critical patent/ATE101215T1/en
Publication of EP0398434A1 publication Critical patent/EP0398434A1/en
Application granted granted Critical
Publication of EP0398434B1 publication Critical patent/EP0398434B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B5/00—Making ropes or cables from special materials or of particular form
    • D07B5/12—Making ropes or cables from special materials or of particular form of low twist or low tension by processes comprising setting or straightening treatments
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B1/00—Constructional features of ropes or cables
    • D07B1/02—Ropes built-up from fibrous or filamentary material, e.g. of vegetable origin, of animal origin, regenerated cellulose, plastics
    • D07B1/025—Ropes built-up from fibrous or filamentary material, e.g. of vegetable origin, of animal origin, regenerated cellulose, plastics comprising high modulus, or high tenacity, polymer filaments or fibres, e.g. liquid-crystal polymers
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2205/00—Rope or cable materials
    • D07B2205/20—Organic high polymers
    • D07B2205/201—Polyolefins
    • D07B2205/2014—High performance polyolefins, e.g. Dyneema or Spectra

Definitions

  • the invention relates to a process for the manufacture of a rope comprising polymeric filaments manufactured according to the gel spinning process.
  • 'rope' is understood in the present application: rope, cord, cable, string and similar structures comprising filaments or filaments and fibres.
  • the gel spinning process as known from GB-A-2,042,414 and GB-A-2,051,667 substantially consists in preparing a solution of a polymer, transforming the solution to filaments above the dissolution temperature of the polymer, cooling the filaments to below the dissolution temperature so that gelation occurs, and complete or partial removal of the solvent.
  • the filaments can subsequently be stretched while the rest of the solvent is removed.
  • Such filaments show a high stiffness and a high tensile strength compared with filaments manufactured in a different manner from the same polymer by spinning.
  • a rope containing filaments that have been manufactured according to the gel spinning process also shows a high stiffness and a high strength. That is precisely why such a rope is used in situations where these properties are of much importance. It is therefore desirable to increase the stiffness and the strength of the rope still further.
  • the object of the invention is to provide a process for the manufacture of a rope containing polymeric filaments manufactured according to the gel spinning process, with a higher stiffness and a higher tensile strength that the known ropes. This is achieved by stretching a rope containing polymeric filaments manufactured according to the gel spinning process.
  • Such a rope shows a stiffness and a tensile strength which, depending on the degree of stretching, are significantly higher than the stiffness and the tensile strength of the original rope.
  • the tensile strength and the stiffness of the filaments increase with increasing degree of stretching during the spinning process.
  • the degree of stretching cannot be augmented unrestrictedly because rupture of the filaments during the production process occurs with increasing frequency as the degree of stretching is increased. It is easy to determine experimentally at what degree of stretching rupture of the filaments occurs with such a frequency that the corresponding frequency with which the process has to be interrupted is acceptable. This degree of stretching is called the maximum degree of stretching of the filaments.
  • yarns can be manufactured by the known processes for that purpose, such as bundling, twisting and/or twining.
  • a rope can be manufactured by the known processes for that purpose, such as twisting, twining, plaiting and/or laying up.
  • the rope may also contain other filaments or fibres.
  • the stretching is preferably effected at elevated temperature, but below the melting point of the filaments. At elevated temperature the stretching can be effected with less force or, using the same force, a higher rate of stretching is achieved.
  • the stretching of the rope can also be effected in several steps.
  • Polymers that can be processed to filaments with good results by means of the gel spinning process are for instance polyalkenes, polyvinylalcohol and polyacrylonitrile.
  • the polyalkenes preferably have a weight average molecular weight higher than 400,000.
  • PE polyethylene
  • This PE may contain a minor quantity, preferably at most 5 mol.%, of one or more alkenes that can copolymerize with it, such as propene, butene, pentene, hexene, octene and 4-methylpentene, and possess 1 to 10, preferably 2-6, methyl or ethyl groups per 1000 carbon atoms.
  • polyalkenes can also be considered, such as for instance propene homo- and copolymers. Further, the polyalkenes used may contain minor quantities of one or more other polymers, in particular alkene-1 polymers.
  • 'polyvinylalcohol' are also understood copolymers containing vinylalcohol and minor quantities, preferably at most 5 mol.%, of one or more other monomers, such as vinylacetate, ethene and other alkenes.
  • 'polyacrylonitrile' are also understood copolymers containing acrylonitrile and minor quantities, preferably at most 5 mol.%, of one or more other monomers, such as methacrylates, acrylates, vinylacetate.
  • rope manufactured from not maximally stretched filaments preferably manufactured from filaments with a degree of stretching of 50% or more, significantly gains stiffness and strength when stretched, and can be given the same stiffness and strength as the rope manufactured from maximally stretched filaments and subsequently stretched.
  • the invention will be elucidated in the following by means of a number of examples with ropes made from polyethylene, polypropene and Kevlar (TM).
  • Rope 1 is laid up using 1600 denier polyethylene yarn, type Dyneema (TM) SK 60, manufactured according to the gel spinning process, and has the following structure: 7 x 19 x 2 x 1600.
  • the strength of the rope, measured according to DIN 83305, is 73.8 kN.
  • the tensile strength of the yarn, measured according to DIN 53834, is 3.20 GPa.
  • Rope 2 is laid up using 2000 denier polyethylene yarn, type Dyneema (TM) SK 60, manufactured according to the gel spinning process, the filaments not being stretched maximally but to 80%.
  • Rope 2 has the following structure: 7 x 19 x 2 x 2000.
  • Rope 3 is laid up using Kevlar (TM) 29 1600 denier yarn and has the following structure: 7 x 19 x 2 x 1600. The strength of the rope is 51.7 kN.
  • TM Kevlar
  • Rope 4 is a randomly chosen rope made of polypropene filaments; it has a strength of 9.78 kN.
  • Rope 1 is clamped in in a Zwick (TM) tensile tester.
  • the clamp-to-clamp distance is 60 cm.
  • the rope is loaded at room temperature to 50% of the measured strength for 10 days. At the end of that period the rope shows an elongation of 5% and its strength is 99 kN.
  • Rope 1 is stretched at 120°C at a rate of 20 mm/min until the elongation of the rope is 5%.
  • the subsequent strength of the rope is 87.8 kN.
  • Rope 1 is stretched at 140°C at a rate of 5 mm/min until the elongation of the rope is 5%.
  • the subsequent strength of the rope is 90.9 kN.
  • Rope 1 is stretched at 140°C at a rate of 5 mm/min until the elongation of the rope is 7.5%.
  • the subsequent strength of the rope is 102 kN.
  • Rope 1 is loaded 5000 times for a few seconds to 50% of its measured strength.
  • the subsequent strength is 87.2 kN.
  • Rope 2 is stretched at 140°C at a rate of 5 mm/min until the elongation of the rope is 23%.
  • the subsequent strength of the rope is 91 kN.
  • Rope 3 is for 10 days loaded to 50% of its measured strength. The subsequent strength is 51.3 kN.
  • Rope 3 is loaded 5000 times for a few seconds to 50% of its measured strength.
  • the subsequent strength is 49.6 kN.
  • Rope 4 is stretched at 150°C at a rate of 1 mm/min until the elongation of the rope is 5%.
  • the subsequent strength of the rope is 9.06 kN.
  • Examples I, II, II, IV and V show that stretching of Rope 1 causes the initial strength to increase from 73.8 kN to 99, 87.8, 90.8, 102 and 87.2 kN respectively. It is clear that at elevated temperatures higher tensile strengths can be reached faster.
  • Example VI shows that yarns made of the polyethylene filaments which initially have not been stretched to their maximum strength can be laid up to form Rope 2, which after stretching at the same temperature and with the same rate of stretching as in Example III has acquired a similar higher tensile strength as Rope 1 in Example III, the filaments of which had been maximally stretched before manufacture of the rope.
  • the polypropene Rope 4 of Example IX also shows a decrease in tensile strength, from 9.78 to 9.06.
  • the strength of Dyneema (TM) SK 60 1600 denier yarn is determined according to DIN 53834.
  • the strength of the yarn is 3.20 GPa.
  • the yarn is stretched at 120°C at a rate of 20 mm/min until the elongation is 5%.
  • the strength then is 3.28 GPa. The stretching has not brought about a significant increase in the strength of the yarn, nor consequently in that of the filaments.
  • the rope stretched as described in Example II is unravelled, so that the 1600 denier yarn is obtained again.
  • the strength of the yarn is 3.18 GPa. It appears that the strength of the yarn has not increased relative to the original yarn, while the strength of the rope has increased substantially as a result of the stretching.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Artificial Filaments (AREA)
  • Ropes Or Cables (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Abstract

The stiffness and the tensile strength of a rope containing polymeric filaments manufactured according to the gel spinning process are substantially increased by stretching it. The stretching is preferably carried out at elevated temperature but below the melting point of the filaments.

Description

  • The invention relates to a process for the manufacture of a rope comprising polymeric filaments manufactured according to the gel spinning process.
  • By 'rope' is understood in the present application: rope, cord, cable, string and similar structures comprising filaments or filaments and fibres.
  • The gel spinning process as known from GB-A-2,042,414 and GB-A-2,051,667 substantially consists in preparing a solution of a polymer, transforming the solution to filaments above the dissolution temperature of the polymer, cooling the filaments to below the dissolution temperature so that gelation occurs, and complete or partial removal of the solvent. The filaments can subsequently be stretched while the rest of the solvent is removed.
  • Such filaments show a high stiffness and a high tensile strength compared with filaments manufactured in a different manner from the same polymer by spinning.
  • A rope containing filaments that have been manufactured according to the gel spinning process also shows a high stiffness and a high strength. That is precisely why such a rope is used in situations where these properties are of much importance. It is therefore desirable to increase the stiffness and the strength of the rope still further.
  • The object of the invention is to provide a process for the manufacture of a rope containing polymeric filaments manufactured according to the gel spinning process, with a higher stiffness and a higher tensile strength that the known ropes. This is achieved by stretching a rope containing polymeric filaments manufactured according to the gel spinning process.
  • Such a rope shows a stiffness and a tensile strength which, depending on the degree of stretching, are significantly higher than the stiffness and the tensile strength of the original rope.
  • It is surprising that the stretching causes the stiffness and the tensile strength of the rope to increase because the filaments of which the rope is made are already stretched maximally during the spinning.
  • The tensile strength and the stiffness of the filaments increase with increasing degree of stretching during the spinning process.
  • The degree of stretching cannot be augmented unrestrictedly because rupture of the filaments during the production process occurs with increasing frequency as the degree of stretching is increased. It is easy to determine experimentally at what degree of stretching rupture of the filaments occurs with such a frequency that the corresponding frequency with which the process has to be interrupted is acceptable. This degree of stretching is called the maximum degree of stretching of the filaments.
  • It is possible to stretch such filaments somewhat further under very special conditions, for instance at a very low rate, but such further stretching hardly yields an increase in the stiffness and the strength of the filaments.
  • From the maximally stretched filaments thus obtained, yarns can be manufactured by the known processes for that purpose, such as bundling, twisting and/or twining.
  • From the yarns a rope can be manufactured by the known processes for that purpose, such as twisting, twining, plaiting and/or laying up.
  • Besides filaments produced according to the gel spinning process, the rope may also contain other filaments or fibres.
  • By stretching the rope its stiffness and tensile strength increase. The stretching is preferably effected at elevated temperature, but below the melting point of the filaments. At elevated temperature the stretching can be effected with less force or, using the same force, a higher rate of stretching is achieved.
  • The stretching of the rope can also be effected in several steps.
  • Polymers that can be processed to filaments with good results by means of the gel spinning process are for instance polyalkenes, polyvinylalcohol and polyacrylonitrile.
  • The polyalkenes preferably have a weight average molecular weight higher than 400,000.
  • Good results are obtained if polyethylene (PE) is chosen as polyalkene. This PE may contain a minor quantity, preferably at most 5 mol.%, of one or more alkenes that can copolymerize with it, such as propene, butene, pentene, hexene, octene and 4-methylpentene, and possess 1 to 10, preferably 2-6, methyl or ethyl groups per 1000 carbon atoms.
  • Other polyalkenes can also be considered, such as for instance propene homo- and copolymers. Further, the polyalkenes used may contain minor quantities of one or more other polymers, in particular alkene-1 polymers.
  • By 'polyvinylalcohol' are also understood copolymers containing vinylalcohol and minor quantities, preferably at most 5 mol.%, of one or more other monomers, such as vinylacetate, ethene and other alkenes. By 'polyacrylonitrile' are also understood copolymers containing acrylonitrile and minor quantities, preferably at most 5 mol.%, of one or more other monomers, such as methacrylates, acrylates, vinylacetate.
  • Further, is has surprisingly been found that rope manufactured from not maximally stretched filaments, preferably manufactured from filaments with a degree of stretching of 50% or more, significantly gains stiffness and strength when stretched, and can be given the same stiffness and strength as the rope manufactured from maximally stretched filaments and subsequently stretched.
  • The invention will be elucidated in the following by means of a number of examples with ropes made from polyethylene, polypropene and Kevlar (TM).
  • Rope 1 is laid up using 1600 denier polyethylene yarn, type Dyneema (TM) SK 60, manufactured according to the gel spinning process, and has the following structure: 7 x 19 x 2 x 1600. The strength of the rope, measured according to DIN 83305, is 73.8 kN. The tensile strength of the yarn, measured according to DIN 53834, is 3.20 GPa.
  • Rope 2 is laid up using 2000 denier polyethylene yarn, type Dyneema (TM) SK 60, manufactured according to the gel spinning process, the filaments not being stretched maximally but to 80%. Rope 2 has the following structure: 7 x 19 x 2 x 2000.
  • Rope 3 is laid up using Kevlar (TM) 29 1600 denier yarn and has the following structure: 7 x 19 x 2 x 1600. The strength of the rope is 51.7 kN.
  • Rope 4 is a randomly chosen rope made of polypropene filaments; it has a strength of 9.78 kN.
    • Example I
  • Rope 1 is clamped in in a Zwick (TM) tensile tester. The clamp-to-clamp distance is 60 cm.
  • The rope is loaded at room temperature to 50% of the measured strength for 10 days. At the end of that period the rope shows an elongation of 5% and its strength is 99 kN.
    • Example II
  • Rope 1 is stretched at 120°C at a rate of 20 mm/min until the elongation of the rope is 5%. The subsequent strength of the rope is 87.8 kN.
    • Example III
  • Rope 1 is stretched at 140°C at a rate of 5 mm/min until the elongation of the rope is 5%. The subsequent strength of the rope is 90.9 kN.
    • Example IV
  • Rope 1 is stretched at 140°C at a rate of 5 mm/min until the elongation of the rope is 7.5%. The subsequent strength of the rope is 102 kN.
    • Example V
  • Rope 1 is loaded 5000 times for a few seconds to 50% of its measured strength. The subsequent strength is 87.2 kN.
    • Example VI
  • Rope 2 is stretched at 140°C at a rate of 5 mm/min until the elongation of the rope is 23%. The subsequent strength of the rope is 91 kN.
    • Example VII
  • Rope 3 is for 10 days loaded to 50% of its measured strength. The subsequent strength is 51.3 kN.
    • Example VIII
  • Rope 3 is loaded 5000 times for a few seconds to 50% of its measured strength. The subsequent strength is 49.6 kN.
    • Example IX
  • Rope 4 is stretched at 150°C at a rate of 1 mm/min until the elongation of the rope is 5%. The subsequent strength of the rope is 9.06 kN.
  • Examples I, II, II, IV and V show that stretching of Rope 1 causes the initial strength to increase from 73.8 kN to 99, 87.8, 90.8, 102 and 87.2 kN respectively. It is clear that at elevated temperatures higher tensile strengths can be reached faster.
  • Example VI shows that yarns made of the polyethylene filaments which initially have not been stretched to their maximum strength can be laid up to form Rope 2, which after stretching at the same temperature and with the same rate of stretching as in Example III has acquired a similar higher tensile strength as Rope 1 in Example III, the filaments of which had been maximally stretched before manufacture of the rope.
  • The Kevlar Rope 3 of Example VII, treated in the same way as Rope 1 of Example I, after stretching shows a decrease in tensile strength from 51.7 to 51.3 kN.
  • The polypropene Rope 4 of Example IX also shows a decrease in tensile strength, from 9.78 to 9.06.
  • It is surprising that the ropes according to the invention gain tensile strength, while other ropes even show a decrease in tensile strength. This cannot be attributed to further stretching of the filaments, as appears from the following tests.
    • Test I
  • The strength of Dyneema (TM) SK 60 1600 denier yarn is determined according to DIN 53834. The strength of the yarn is 3.20 GPa. The yarn is stretched at 120°C at a rate of 20 mm/min until the elongation is 5%. The strength then is 3.28 GPa. The stretching has not brought about a significant increase in the strength of the yarn, nor consequently in that of the filaments.
    • Test II
  • The rope stretched as described in Example II is unravelled, so that the 1600 denier yarn is obtained again. The strength of the yarn is 3.18 GPa. It appears that the strength of the yarn has not increased relative to the original yarn, while the strength of the rope has increased substantially as a result of the stretching.

Claims (9)

1. Process for the manufacture of a rope containing polymeric filaments manufactured according to the gel spinning process, characterized in that the rope is stretched.
2. Process according to claim 1, characterized in that the stretching is carried out at elevated temperature, but below the melting temperature of the filaments.
3. Process according to claim 1 or 2, characterized in that the filaments are manufactured from polyalkene with a weight average molecular weight higher than 400,000.
4. Process according to claim 3, characterized in that polyethylene is used as polyalkene.
5. Process according to claim 1 or 2, characterized in that the filaments are manufactured from polyvinylalcohol.
6. Process according to claim 1 or 2, characterized in that the filaments are manufactured from polyacrylonitrile.
7. Process according to any one of the claims 1-6, characterized in that the rope is manufactured from unstretched filaments and subsequently stretched.
8. Process according to any one of the claims 1-6, characterized in that the rope is manufactured from partially stretched filaments and subsequently stretched.
9. Process according to any one of the claims 1-6, characterized in that the rope is manufactured from maximally stretched filaments and subsequently stretched.
EP90201216A 1989-05-19 1990-05-15 Process for the manufacture of stretched rope Expired - Lifetime EP0398434B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT90201216T ATE101215T1 (en) 1989-05-19 1990-05-15 METHOD OF MANUFACTURING DRAFT ROPES.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL8901266A NL8901266A (en) 1989-05-19 1989-05-19 METHOD FOR MANUFACTURING A STRETCHED ROPE
NL8901266 1989-05-19

Publications (2)

Publication Number Publication Date
EP0398434A1 true EP0398434A1 (en) 1990-11-22
EP0398434B1 EP0398434B1 (en) 1994-02-02

Family

ID=19854683

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90201216A Expired - Lifetime EP0398434B1 (en) 1989-05-19 1990-05-15 Process for the manufacture of stretched rope

Country Status (5)

Country Link
EP (1) EP0398434B1 (en)
JP (1) JP3105225B2 (en)
AT (1) ATE101215T1 (en)
DE (2) DE69006390T2 (en)
NL (1) NL8901266A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992022701A1 (en) * 1991-06-11 1992-12-23 Dsm N.V. Roping
US5510072A (en) * 1993-06-21 1996-04-23 Shell Oil Company Process for the manufacture of elastic articles from poly(monovinylaromatic/conjugated diene) block copolymers and elastic articles obtainable therewith
WO2014114793A2 (en) 2013-01-25 2014-07-31 Dsm Ip Assets B.V. Method of manufacturing a drawn multifilament yarn

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7473391B2 (en) 2001-03-13 2009-01-06 Ngk Insulators, Ltd. Methods for making molding material, molded body, and sintered body
US7081298B2 (en) 2001-10-29 2006-07-25 Yoz-Ami Corporation Specific gravity-adjustable yarns with low elongation rate and excellent abrasion resistance

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3266232A (en) * 1963-06-03 1966-08-16 Grace W R & Co Polypropylene rope stabilization process
FR2053180A1 (en) * 1969-07-26 1971-04-16 Dunlop Co Ltd Textile reinforcement for rubber tyres
GB2042414A (en) * 1979-02-08 1980-09-24 Stamicarbon Dry-spinning polymer filaments
GB2051667A (en) * 1979-06-27 1981-01-21 Stamicarbon Preparing polyethylene filaments

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2911384A (en) * 1957-02-05 1959-11-03 Sun Oil Co Oxygenated crystalline polypropylene, method of making, and wax composition containing same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3266232A (en) * 1963-06-03 1966-08-16 Grace W R & Co Polypropylene rope stabilization process
FR2053180A1 (en) * 1969-07-26 1971-04-16 Dunlop Co Ltd Textile reinforcement for rubber tyres
GB2042414A (en) * 1979-02-08 1980-09-24 Stamicarbon Dry-spinning polymer filaments
GB2051667A (en) * 1979-06-27 1981-01-21 Stamicarbon Preparing polyethylene filaments

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992022701A1 (en) * 1991-06-11 1992-12-23 Dsm N.V. Roping
US5510072A (en) * 1993-06-21 1996-04-23 Shell Oil Company Process for the manufacture of elastic articles from poly(monovinylaromatic/conjugated diene) block copolymers and elastic articles obtainable therewith
WO2014114793A2 (en) 2013-01-25 2014-07-31 Dsm Ip Assets B.V. Method of manufacturing a drawn multifilament yarn
EP3051010A1 (en) 2013-01-25 2016-08-03 DSM IP Assets B.V. Method of manufacturing a drawn multifilament yarn

Also Published As

Publication number Publication date
DE69006390D1 (en) 1994-03-17
DE4034919A1 (en) 1992-05-07
ATE101215T1 (en) 1994-02-15
JPH038830A (en) 1991-01-16
EP0398434B1 (en) 1994-02-02
JP3105225B2 (en) 2000-10-30
DE69006390T2 (en) 1994-08-25
NL8901266A (en) 1990-12-17

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