WO1994026491A1 - Composition de moulage - Google Patents

Composition de moulage Download PDF

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Publication number
WO1994026491A1
WO1994026491A1 PCT/GB1994/001028 GB9401028W WO9426491A1 WO 1994026491 A1 WO1994026491 A1 WO 1994026491A1 GB 9401028 W GB9401028 W GB 9401028W WO 9426491 A1 WO9426491 A1 WO 9426491A1
Authority
WO
WIPO (PCT)
Prior art keywords
organic material
plastics
moulding composition
composition
moulding
Prior art date
Application number
PCT/GB1994/001028
Other languages
English (en)
Inventor
John S. Wood
Original Assignee
Stemform Products Limited
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 Stemform Products Limited filed Critical Stemform Products Limited
Priority to AU66545/94A priority Critical patent/AU6654594A/en
Publication of WO1994026491A1 publication Critical patent/WO1994026491A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
    • B29B7/7461—Combinations of dissimilar mixers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/82—Heating or cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/86—Component parts, details or accessories; Auxiliary operations for working at sub- or superatmospheric pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/90—Fillers or reinforcements, e.g. fibres
    • B29B7/905—Fillers or reinforcements, e.g. fibres with means for pretreatment of the charges or fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/90—Fillers or reinforcements, e.g. fibres
    • B29B7/92—Wood chips or wood fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • B29B9/14—Making granules characterised by structure or composition fibre-reinforced
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/16—Auxiliary treatment of granules
    • B29B2009/163—Coating, i.e. applying a layer of liquid or solid material on the granule
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B29B9/065—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion under-water, e.g. underwater pelletizers

Definitions

  • This invention relates to moulding compositions and in particular to compositions incorporating plastics material and fibre which is of use in machine moulding applications such as injection moulding, compression moulding and extrusion moulding processes.
  • moulding compositions by mixing fibres with thermo-plastics material.
  • Such compositions have been used in ther oset plastics, such as are used in hand lay up moulding.
  • the fibres have been glass fibres, which are relatively expensive, and textile fibres formed into a mat, the fibres being effective in reinforcing the plastics material.
  • An object of the invention is to provide an improved moulding composition and a method of producing such composition for use in a machine moulding operation.
  • the organic material is dried until the moisture content is less than 4% and is preferably in the range 1 - 3%, or more particularly 1.5 - 2%.
  • the moisture content is less than 4% and is preferably in the range 1 - 3%, or more particularly 1.5 - 2%.
  • the material has a tendency to lose its fibrous qualities.
  • the moisture released during heating of the mixture of plastics material and organic material turns into steam and must be released or a hazardous situation comes about. Although the moisture may be vented from the mixture excessive moisture release can give rise to problems.
  • the maximum dimension of the fibre is preferably less than 8mm and more conveniently less than 6mm.
  • the maximum dimension has to have regard to the size of the particles or pieces of the eventual moulding composition and should preferably be no greater than the maximum dimension of such pieces.
  • the pieces are usually in the form of cylindrical pellets of, say, 6mm diameter and less than 6mm in length, preferably 2 - 4mm in length, and the pellets are conveniently formed by cutting continuous lengths of the composition as extruded through circular nozzles.
  • the composition Before use of the moulding composition the composition should be dried to remove any moisture which has become associated therewith.
  • the plastics material with which the fibres are mixed should be of a kind capable of forming a homogeneous mix with the organic fibres which preferably contain cellulosic material. Certain components of the organic material migrate into the plastics material to form the homogeneous composition and this generally occurs using a cellulosic or polymer plastics. Acrylics and epoxy based plastics are not normally suitable. Suitable plastics include polyvinylchloride, polypropylene, polyethylene, polystyrene, polyurethane, vinylchloride, vinylchloride ethylene, polybutene, polyester, ABS, nylon and polycarbonate. Such base plastics may be cross linked to produce the desired characteristics.
  • the invention also provides a moulding composition which comprises organic fibrous material such as straw, haulm, hay and other plant stems and leaf material in admixture with thermo-plastics material to form a homogeneous fibre reinforced plastics material.
  • the proportion of organic fibrous material to plastics depends on the desired characteristics of the moulding composition but can be in the range 5 - 70%, preferably 20 - 60%, fibrous material to plastics material by volume. Greater proportions may, however, be used for some moulding compositions, such as for making moulded board or sheet.
  • the fibrous organic material is often the byproduct of cereals growing or the production of other crops and the resulting straw, haulm, hay, etc., is reduced to the desired size by any convenient means such as by a hammer mill or by grinding. It is advantageous if the process of reducing the size of the organic material also breaks up the harder components of the organic material such as knuckles or joints in the straw.
  • the apparatus is intended for preparing a moulding composition comprising fibrous organic material and plastics material.
  • the fibrous organic material may be selected from a range of materials having fibres such as straw (which may be wheat, barley or other cereal straw) ; the haulm of rape, maize, peas and beans; hay from various grasses; and other organic material; all of which include cellulose in various proportions.
  • the plastics material may be any plastics material which has moulding properties and which is generally a cellulose polymer plastics material capable of forming a homogeneous mixture with cellulose based organic material.
  • the drawing shows the use of cereal straw 1 which is cut by a combine harvester 2 which separates the grain 2A from the straw 3.
  • the straw is fed to a granulator 4 in the form of a grinder or hammer mill which reduces the fibrous material to size suited to the moulding requirements and having regard to the size of the pellets or other pieces of the moulding composition to be formed.
  • the fibrous material should have a maximum length of about 3 - 6mm so that there is a reasonable chance of the organic material being encapsulated within the pellets.
  • the granulator 4 may be located remote from the equipment for producing the composition in which case the fibrous material is conveniently bagged in porous sacks (not shown) for storage and transportation.
  • the comminuted straw passes into a silo 6 through a sieve 5 to prevent straw entering the silo 6 if it is above a predetermined size of, say, 6mm.
  • a further silo 7 is provided into which is discharged virgin plastic pellets and the plastic pellets and straw are mixed together by a mixer/proportioner 8 and fed into a mixer drum 9.
  • Mixed product from the mixer drum is discharged into a heated container 11 in which the organic material is dried.
  • the container 11 is insulated and supplied with dry air from a de- humidifier 10.
  • the de-humidifier 10 supplies air to the container 11 which has been de-humidified by passing the air through desiccant or by other means. Dry air is discharged towards the base of the container 11 and air is extracted from towards the upper end of the container 11 and passed through the de-humidifier in an air re-circulation arrangement.
  • a vacuum pump 11A is used to discharge the contents of the container towards a proportioner 13 which mixes the contents with a supply of virgin plastics from a hopper 12 in the desired ratio. From the proportioner 13 the organic material and plastics is discharged into a hopper 14 and at this point the organic material is in the ratio of 20 - 60% by volume of the mixture.
  • the hopper 14 feeds the mixture of organic material and plastics into an extruder barrel 15 which is heated and contains a screw 15B feeding the mixture towards an extrusion die 16.
  • the extruder barrel contains vents 15A for venting to atmosphere gases or moisture contained within the mixture.
  • the contents of the extruder barrel are made fluid by the heat and the mixture is extruded through the die 16 which includes a plate with a plurality of circular holes.
  • the composition is extruded through the holes and may be cut as it leaves the die to form pellets.
  • the pellets are dropped down through a cascade of water mist into a centrifuge or other container.
  • the material extruded through the die forms a plurality of lengths in the form of spaghetti which are cooled in a water bath or underwater sprays (not shown) .
  • the lengths are fed into a pelletiser 18 which cuts the lengths into pellets of the desired length.
  • the cut pellets are filled into sacks at a bag filler 19, the sacks being paper lined to discourage moisture pick up.
  • Drying of the organic material may be conducted in two stages, the first stage may be, for example, in a cyclone dryer bringing down the moisture content to a predetermined level of say 14% prior to introducing the organic material into the de- humidifier described.
  • the drying process in the de-humidifier is enhanced by adding the plastics to the organic material in relatively low proportions prior to introduction into the de- humidifier.
  • the dried organic material is of a hygroscopic nature and it is important to arrange for the dried material to be introduced into the extruder barrel 15 without it coming into contact with atmospheric air.
  • the vacuum pump 11A draws the material down through the proportioner and directly into the hopper 14.
  • the presence of plastic helps to form a seal to prevent the organic material coming into contact with the atmosphere.
  • the moulding composition produced by the method described is suitable for injection, compression and extrusion moulding processes.
  • Extruded sheet compositions are suitable for vacuum forming or hot press forming for shaped moulded articles.
  • the proportion of fibrous organic material to plastics material can be varied by controlling the rate of discharge of the components from the blender-proportioner 13 to the extruder 15.
  • the fibrous material may by this means have a content of 10 - 70%, preferably 20 - 60%, by volume of the moulding composition thereby giving reinforcing properties to the composition and providing a relatively cheap component for the composition compared with other fibrous materials such as fibreglass or textile fibre.
  • the organic fibrous material is capable of improving the impact strength, tensile strength and/or ductility of moulded products made from the composition and the fibrous material has the effect of providing a homogeneous matrix by a chemical interaction with the plastic material due to the cellulose content of both components.
  • mouldings made from the composition can be coated with fire retardant, when required, and in the event that the mouldings do catch fire a white smoke is produced giving reduced toxicity.
  • the composition can also be used in producing foamed plastics. Materials based upon virgin cellulose polymer plastics of thermoplastic composition are recyclable and environmentally friendly.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Abstract

L'invention concerne une composition de moulage, ainsi qu'un procédé de fabrication de ladite composition, présentant une efficacité particulière pour des opérations de moulage à la machine. La composition incorpore des fibres sous forme de matériau fibreux organique, tel que de la paille, ainsi que de la matière plastique compatible avec la composition de matériau organique, tel qu'un plastique polymère. On déssèche le matériau organique, afin d'abaisser au maximum sa teneur en humidité et on réduit sa dimension à moins de 8mm de dimension maximum avant de le mélanger avec le plastique.
PCT/GB1994/001028 1993-05-14 1994-05-12 Composition de moulage WO1994026491A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU66545/94A AU6654594A (en) 1993-05-14 1994-05-12 Moulding composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB939309917A GB9309917D0 (en) 1993-05-14 1993-05-14 Moulding composition
GB9309917.4 1993-05-14

Publications (1)

Publication Number Publication Date
WO1994026491A1 true WO1994026491A1 (fr) 1994-11-24

Family

ID=10735447

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1994/001028 WO1994026491A1 (fr) 1993-05-14 1994-05-12 Composition de moulage

Country Status (3)

Country Link
AU (1) AU6654594A (fr)
GB (2) GB9309917D0 (fr)
WO (1) WO1994026491A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0747419A2 (fr) * 1995-06-07 1996-12-11 Andersen Corporation Matériau composite à base de polymère et de fibres de bois compatibles
US20220193955A1 (en) * 2019-03-12 2022-06-23 Mixcycling Srl Process for making compounds using wastes of natural origin and fibres of plant or animal origin

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2154149B1 (es) * 1998-05-27 2001-12-01 Serveis De Produccio Empresari Perfeccionamientos en los sistemas transportadores de harina de tablero de fibra.
FR2781492B1 (fr) * 1998-07-24 2001-04-13 Andre Ravachol Nouveau materiau thermoplastique composite contenant des fibres d'origine vegetale et son procede de preparation
US6624217B1 (en) 2000-03-31 2003-09-23 Wang You Tong Plant fiber composite material, its products and a processing method thereof
CA2306959A1 (fr) * 2000-03-31 2001-10-26 Enviro Concept Ltd. Materiau composite en fibres vegetales, produits fabriques avec ce materiau et methode de traitement connexe
EP1142958A1 (fr) * 2000-04-05 2001-10-10 Enviro Concept Ltd. Composites de fibres végétales, leur produits et procédé de préparation
FR2809985A1 (fr) * 2000-06-07 2001-12-14 Epiplast S A Materiau composite thermoplastique comportant une charge de particules de matiere vegetale, et procede et installation de fabrication de ce materiau
DE102004012458B4 (de) * 2004-03-14 2007-09-06 Korger, Horst, Dipl.-Ing. Dreidimensionales Gebilde aus Naturfasern, in Form von Matten, Platten, Hohlkörpern, Formteilen oder dgl.
NZ530339A (en) 2004-06-23 2007-01-26 Nz Forest Research Inst Ltd Method for producing wood fibre pellets
DE102007028374B4 (de) * 2007-06-11 2009-04-23 Ava - Anhaltinische Verfahrens- Und Anlagentechnik Gmbh Verfahren zur Herstellung eines Holz-Kunststoff-Verbundwerkstoffes
CA3003848C (fr) 2015-11-17 2023-09-19 Stora Enso Oyj Procede de production de composites fibre-polymere

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Publication number Priority date Publication date Assignee Title
DE3021455A1 (de) * 1980-06-06 1981-12-17 Bison-Werke Bähre & Greten GmbH & Co KG, 3257 Springe Herstellungsverfahren fuer plattenfoermige werkstoffe
JPS60192744A (ja) * 1984-03-13 1985-10-01 Sekisui Chem Co Ltd 塩化ビニル系樹脂成形品及びその成形方法
US4746688A (en) * 1987-05-21 1988-05-24 Ford Motor Company Remoldable, wood-filled acoustic sheet
CN87101538A (zh) * 1987-04-15 1988-12-28 吉林省白城地区农业科学研究所 向日葵秸秆人造木材制品
JPH01230672A (ja) * 1988-03-10 1989-09-14 Kyuzo Yamaoka 木目風の模様を現出することが出来る成型材料の製造方法
GB2235645A (en) * 1989-09-08 1991-03-13 Agrifibre Dev Ltd Method and apparatus for press moulding articles
GB2244059A (en) * 1990-05-16 1991-11-20 Fosse Ltd Cellulosic product, process for the production thereof and uses thereof

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GB213016A (en) * 1922-12-30 1924-03-27 Columbia Graphophone Mfg Co Improvements in thermoplastic compositions and the process of compounding the same
JPS5087439A (fr) * 1973-12-07 1975-07-14
LU73279A1 (fr) * 1975-08-29 1977-04-20
US4279790A (en) * 1979-07-05 1981-07-21 Kabushiki Kaisha Mikuni Seisakusho Composite material compositions using wasterpaper and method of producing same
IT1251723B (it) * 1991-10-31 1995-05-23 Himont Inc Compositi poliolefinici e procedimento per la loro preparazione

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Publication number Priority date Publication date Assignee Title
DE3021455A1 (de) * 1980-06-06 1981-12-17 Bison-Werke Bähre & Greten GmbH & Co KG, 3257 Springe Herstellungsverfahren fuer plattenfoermige werkstoffe
JPS60192744A (ja) * 1984-03-13 1985-10-01 Sekisui Chem Co Ltd 塩化ビニル系樹脂成形品及びその成形方法
CN87101538A (zh) * 1987-04-15 1988-12-28 吉林省白城地区农业科学研究所 向日葵秸秆人造木材制品
US4746688A (en) * 1987-05-21 1988-05-24 Ford Motor Company Remoldable, wood-filled acoustic sheet
JPH01230672A (ja) * 1988-03-10 1989-09-14 Kyuzo Yamaoka 木目風の模様を現出することが出来る成型材料の製造方法
GB2235645A (en) * 1989-09-08 1991-03-13 Agrifibre Dev Ltd Method and apparatus for press moulding articles
GB2244059A (en) * 1990-05-16 1991-11-20 Fosse Ltd Cellulosic product, process for the production thereof and uses thereof

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DATABASE WPI Section Ch Week 8948, Derwent World Patents Index; Class AFB, AN 89-348371 C48! *
PATENT ABSTRACTS OF JAPAN vol. 10, no. 43 (C - 329) 20 February 1986 (1986-02-20) *
PATENT ABSTRACTS OF JAPAN vol. 13, no. 556 (C - 664) 11 December 1989 (1989-12-11) *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0747419A2 (fr) * 1995-06-07 1996-12-11 Andersen Corporation Matériau composite à base de polymère et de fibres de bois compatibles
EP0747419A3 (fr) * 1995-06-07 1997-07-30 Andersen Corp Matériau composite à base de polymère et de fibres de bois compatibles
US20220193955A1 (en) * 2019-03-12 2022-06-23 Mixcycling Srl Process for making compounds using wastes of natural origin and fibres of plant or animal origin

Also Published As

Publication number Publication date
GB2278365A (en) 1994-11-30
GB2278365B (en) 1997-10-15
GB9409769D0 (en) 1994-07-06
GB9309917D0 (en) 1993-06-30
AU6654594A (en) 1994-12-12

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