EP2673538A1 - Composite material with pps fibres, epoxy resin and/or furan resin - Google Patents

Composite material with pps fibres, epoxy resin and/or furan resin

Info

Publication number
EP2673538A1
EP2673538A1 EP12707224.7A EP12707224A EP2673538A1 EP 2673538 A1 EP2673538 A1 EP 2673538A1 EP 12707224 A EP12707224 A EP 12707224A EP 2673538 A1 EP2673538 A1 EP 2673538A1
Authority
EP
European Patent Office
Prior art keywords
composite material
composite
material according
resin
alkaline
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Withdrawn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
EP12707224.7A
Other languages
German (de)
French (fr)
Inventor
Michael Rohlmann
Dieter Rossberg
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.)
ThyssenKrupp Nucera AG and Co KGaA
Original Assignee
ThyssenKrupp Uhde 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 ThyssenKrupp Uhde GmbH filed Critical ThyssenKrupp Uhde GmbH
Publication of EP2673538A1 publication Critical patent/EP2673538A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L9/00—Rigid pipes
    • F16L9/12—Rigid pipes of plastics with or without reinforcement
    • F16L9/127—Rigid pipes of plastics with or without reinforcement the walls consisting of a single layer
    • F16L9/128—Reinforced pipes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D85/00—Containers, packaging elements or packages, specially adapted for particular articles or materials
    • B65D85/70—Containers, packaging elements or packages, specially adapted for particular articles or materials for materials not otherwise provided for
    • B65D85/84—Containers, packaging elements or packages, specially adapted for particular articles or materials for materials not otherwise provided for for corrosive chemicals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06—Fibrous reinforcements only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/246—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using polymer based synthetic fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/04—Polysulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2063/00—Use of EP, i.e. epoxy resins or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B29K2105/0044—Stabilisers, e.g. against oxydation, light or heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2281/00—Use of polymers having sulfur, with or without nitrogen, oxygen or carbon only, in the main chain, as reinforcement
    • B29K2281/04—Polysulfides, e.g. PPS, i.e. polyphenylene sulfide, or derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0058—Inert to chemical degradation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2023/00—Tubular articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/712—Containers; Packaging elements or accessories, Packages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1362—Textile, fabric, cloth, or pile containing [e.g., web, net, woven, knitted, mesh, nonwoven, matted, etc.]

Definitions

  • the invention relates to a fiber-reinforced plastic structure
  • Plastic structure are made, and their use. Such plastic structures are materials that consist of Verstärkungsfasem, which are embedded in a plastic matrix. These are found in a variety of applications in the form of short fiber reinforced,
  • the subgroup of glass fiber reinforced plastics is a composite of a plastic, such as polyester resin, epoxy or polyamide, and glass fibers.
  • a plastic such as polyester resin, epoxy or polyamide
  • Glass fiber reinforced plastics are standard materials in the industry. Tubes of this type are standardized in the DIN and commercially available.
  • thermoplastic material such as e.g. Polypropylene
  • This chemical protective layer is present on those surfaces which come into contact with the alkaline solutions and is intended to protect the glass fiber reinforced plastics. This additional protective layer is required above all when the alkaline solutions have temperatures of> 40 ° C and thus their corrosive effect is enhanced and surfaces are attacked and destroyed.
  • Lye concentrations can be dispensed with a thermoplastic chemical protective layer and this is instead produced from the plastic matrix itself.
  • the disadvantage of the glass fiber reinforced plastics known in the prior art is that if the chemical protection layer is damaged, the glass fibers are exposed and are exposed directly to a chemical attack by alkali.
  • Glass is a chemically highly resistant material, which is not laugebest depict and massively attacked by alkali and destroyed. By destroying the reinforcing fiber of the entire composite material is attacked, because the mechanical strength of the composite is achieved by the reinforcing fibers. The omission of the mechanical strength leads to the failure of the Material, since the pressure and temperature load, which prevails, for example, when operating an industrial plant, no resistance is opposed.
  • a glass fiber reinforced plastic pipe according to the prior art is known for example from DE 10 2008 033 577 A1.
  • this document teaches a plastic tube which has improved properties in terms of tightness, rigidity, dimensional stability and abrasion in comparison to the prior art.
  • the pipe wall is formed by at least one in the spin and / or
  • Centrifugal casting method produced spin coating and at least one winding layer produced in the winding process. Although such pipes have improved properties, but are very expensive to produce.
  • Object of the present invention is therefore to provide an alternative composite material in which both the matrix material and the fiber material at temperatures> 60 ° C is resistant to alkaline media, and thus reduces the likelihood of the occurrence of the failure described above becomes.
  • the invention has also set itself the task of providing appropriate means and uses of the composite material.
  • the object is achieved by a composite comprising reinforcing fibers and a surrounding matrix of a matrix material, wherein the matrix material contains an epoxy resin and / or a furan resin and the reinforcing fibers contain polyphenylene sulfide.
  • the epoxy resin reacts with a crosslinking partner, generally referred to as a hardener, to a thermoset composite material.
  • a crosslinking partner generally referred to as a hardener
  • the EP resin is based on different approaches, preferred for the use used are a bisphenol A or novolak base.
  • the hardener systems are preferably based on amine systems, using both aliphatic and aromatic amines. However, anhydride hardeners can also be used.
  • the composite material additionally includes the additives that influence the composite properties.
  • additives that influence the composite properties. These are selected from the group of stabilizers adhesion promoters and lubricants and are known in the art from the prior art. These modifiers are based predominantly on aliphatic or aromatic glycidyl ethers. However, aliphatic epoxy ester resins or polyepoxide resins are also used to adjust the properties.
  • the accelerators are imidazole-based systems.
  • the composite preferably comprises 0.05 to 35 parts by weight of additives. These can either be in the matrix material and / or in the
  • the matrix material comprises 95 to 100% by weight of resin and 0 to 5% by weight of additives.
  • Fiber material advantageously comprises 65 to 100% by weight of polyphenylene sulfide and 0 to 35% by weight of additives.
  • the composite material according to the invention is resistant to> 20% - concentrated alkaline media, wherein it is the alkaline medium in particular to> 20% NaOH. It goes without saying that the composite also has resistance to other chemicals.
  • the composite of the present invention is resistant to NaOH and other alkaline media at temperatures> 60 ° C.
  • the present invention also includes means for receiving and / or transporting alkaline liquids comprising the invention
  • the pipes and containers are made by a method known to those skilled in the art from the composite material.
  • the known methods are in detail:
  • Winding process In the winding process, rotating (winding mandrel) and reciprocating (support) movements are combined with each other in order to deposit the resin-impregnated fibers on the mandrel after a certain winding pattern.
  • This process can be carried out both mechanized and manually, with different fiber structures, such as e.g. Continuous filaments such as rovings, fleeces of short fibers, random fiber mats of short and long fibers, woven or knitted fabrics can be used
  • Braiding process In the braiding process, the reinforcing fibers of a slidable braiding machine with a rotating braiding head on one
  • Matrix resin are impregnated.
  • the fiber reinforcement in the form of, for example, nonwovens or fabrics is previously inserted or together with the resin and any additives through the lance, a mobile loading arm; introduced as short fiber in the centrifugal mold.
  • a mobile loading arm introduced as short fiber in the centrifugal mold.
  • the composite material according to the invention finds above all things
  • Piping and / or the containers are brought into contact with alkaline media. Even at elevated temperatures of> 60 ° C of alkaline media, the piping and tanks are used.
  • the composite material In a preferred use of the composite material, it is used in devices of an electrolysis process in which alkaline media are produced and / or supplied.
  • the use is conceivable especially in inflows and outflows, as well as in the reaction chambers of electrolysis cells.
  • Composite material will be explained below. These are, for example, devices of a leaching concentration process in which the concentrations of alkaline media are changed or devices of a process of metal extraction in which alkaline media are supplied and / or used, this advantageously being an aluminum extraction from bauxite. Furthermore, the invention relates generally to apparatuses of methods known in the art in which alkaline media are supplied and / or used.
  • the pipe materials used in the experiment are fiber-reinforced plastics.
  • the matrix materials are epoxy, vinyl ester resins and other resin types that differ in their structure.
  • fiber materials are different glass and polymer fibers, e.g. AR glass, polyamide fiber,
  • Polyphenylene sulfide fibers provided. Test specimens made of pure resin and fibers are supplied by commercial manufacturers. The square test specimens have 30 mm edge length. The individual fibers (without resin) are used as commercially available.
  • test specimens and fibers are stored in 32 wt% NaOH solution in PFA cans with screw caps in a drying oven at 90 ° C for 10 days, to determine a basic stability of the samples used. After these 10 days, the temperature was raised to 250 ° C. The aqueous 32% by weight NaOH solution was completely evaporated to dry 100% NaOH. As a result, all specimens were exposed to the concentration range of 32% to 100% at a temperature of up to 250 ° C.
  • the materials according to the invention ie the matrix materials epoxy resins and furan resins, as well as the reinforcing fibers of polyphenylene sulfide have withstood the extreme conditions of the experimental setup and are thus perfectly suited to the starting task.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • General Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Reinforced Plastic Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Moulding By Coating Moulds (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention relates to a composite material comprising reinforcing fibres and a matrix of matrix material surrounding said reinforcing fibres. The matrix material contains a resin and the reinforcing fibres contain polyphenylene sulfide.

Description

VERBUNDWERKSTOFF MIT PPS FASERN, EPOXYDHARZ UND/ODER FURANHARZ  COMPOSITE MATERIAL WITH PPS FIBERS, EPOXY RESIN AND / OR FURAN RESIN
[0001] Die Erfindung betrifft eine faserverstärkte Kunststoffstruktur The invention relates to a fiber-reinforced plastic structure
(Verbundwerkstoff), Mittel, die aus der erfindungsgemäßen faserverstärkten (Composite material), means made of the fiber-reinforced according to the invention
Kunststoffstruktur gefertigt sind, sowie deren Verwendung. [0002] Derartige Kunststoffstrukturen sind Werkstoffe, die aus Verstärkungsfasem bestehen, welche in einer Kunststoffmatrix eingebettet sind. Diese finden in einer Vielzahl von Anwendungsgebieten in Form von kurzfaserverstärkten, Plastic structure are made, and their use. Such plastic structures are materials that consist of Verstärkungsfasem, which are embedded in a plastic matrix. These are found in a variety of applications in the form of short fiber reinforced,
langfaserverstärkten oder endlosfaserverstärkten Bauteilen Verwendung. Long fiber reinforced or continuous fiber reinforced components use.
[0003] Die Untergruppe der glasfaserverstärkten Kunststoffe ist ein Verbund aus einem Kunststoff, wie beispielsweise Polyesterharz, Epoxidharz oder Polyamid, und Glasfasern. Glasfaserverstärkte Kunststoffe sind Standardwerkstoffe in der Industrie. Rohre dieser Art sind in der DIN genormt und kommerziell erhältlich. The subgroup of glass fiber reinforced plastics is a composite of a plastic, such as polyester resin, epoxy or polyamide, and glass fibers. Glass fiber reinforced plastics are standard materials in the industry. Tubes of this type are standardized in the DIN and commercially available.
[0004] Im Bereich alkalischer Medien werden überwiegend glasfaserverstärkte Kunststoffe eingesetzt, um alkalische Flüssigkeiten aufzunehmen oder zu In the field of alkaline media glass fiber reinforced plastics are mainly used to absorb or to alkaline liquids
transportierten. Diese sind in der Regel mit einem thermoplastischen Material, wie z.B. Polypropylen, als chemische Schutzschicht, versehen. Diese chemische Schutzschicht ist auf denjenigen Oberflächen vorhanden, die mit den alkalischen Lösungen in Berührung kommen und soll die glasfaserverstärkten Kunststoffe schützen. Diese zusätzliche Schutzschicht ist vor allen Dingen dann erforderlich wenn die alkalischen Lösungen Temperaturen von > 40°C aufweisen und damit ihre ätzende Wirkung verstärkt wird und Oberflächen angriffen und zerstört werden. transported. These are typically made with a thermoplastic material, such as e.g. Polypropylene, provided as a chemical protective layer. This chemical protective layer is present on those surfaces which come into contact with the alkaline solutions and is intended to protect the glass fiber reinforced plastics. This additional protective layer is required above all when the alkaline solutions have temperatures of> 40 ° C and thus their corrosive effect is enhanced and surfaces are attacked and destroyed.
[0005] Bei Temperaturen unterhalb von 40°C und geringen At temperatures below 40 ° C and low
Laugenkonzentrationen kann auf eine thermoplastische Chemieschutzschicht verzichtet werden und diese wird stattdessen aus der Kunststoffmatrix selbst erzeugt. [0006] Der Nachteil der im Stand der Technik bekannten glasfaserverstärkten Kunststoffe ist nun, dass bei Beschädigung der Chemieschutzschicht, die Glasfasern freigelegt werden und einem chemischen Angriff durch Lauge direkt ausgesetzt sind. Lye concentrations can be dispensed with a thermoplastic chemical protective layer and this is instead produced from the plastic matrix itself. The disadvantage of the glass fiber reinforced plastics known in the prior art is that if the chemical protection layer is damaged, the glass fibers are exposed and are exposed directly to a chemical attack by alkali.
[0007] Glas ist ein chemisch hochresistenter Werkstoff, der jedoch nicht laugebeständig ist und massiv von Lauge angegriffen und zerstört wird. Durch die Zerstörung der Verstärkungsfaser wird der gesamte Verbundwerkstoff angegriffen, denn die mechanische Festigkeit des Verbundes wird durch die Verstärkungsfasern erreicht. Der Wegfall der mechanischen Festigkeit führt zum Versagen des Werkstoffes, da der Druck- und Temperaturbelastung, die beispielsweise beim Betrieb einer Industrieanlage herrscht, kein Widerstand mehr entgegengesetzt wird. Glass is a chemically highly resistant material, which is not laugebeständig and massively attacked by alkali and destroyed. By destroying the reinforcing fiber of the entire composite material is attacked, because the mechanical strength of the composite is achieved by the reinforcing fibers. The omission of the mechanical strength leads to the failure of the Material, since the pressure and temperature load, which prevails, for example, when operating an industrial plant, no resistance is opposed.
[0008] Ein glasfaserverstärktes Kunststoffrohr nach dem Stand der Technik ist beispielsweise aus DE 10 2008 033 577 A1 bekannt. Diese Schrift lehrt insbesondere ein Kunststoffrohr, das hinsichtlich Dichtigkeit, Steifigkeit, Formstabilität und Abrasion im Vergleich zum Stand der Technik verbesserte Eigenschaften aufweist. Dabei wird die Rohrwand gebildet durch mindestens eine im Schleuder- und/oder A glass fiber reinforced plastic pipe according to the prior art is known for example from DE 10 2008 033 577 A1. In particular, this document teaches a plastic tube which has improved properties in terms of tightness, rigidity, dimensional stability and abrasion in comparison to the prior art. The pipe wall is formed by at least one in the spin and / or
Schleudergussverfahren hergestellte Schleuderschicht und mindestens eine im Wickelverfahren hergestellte Wickelschicht. Derartige Rohre weisen zwar verbesserte Eigenschaften auf, sind aber sehr aufwendig herzustellen. Centrifugal casting method produced spin coating and at least one winding layer produced in the winding process. Although such pipes have improved properties, but are very expensive to produce.
[0009] Aufgabe der vorliegenden Erfindung ist es deshalb einen alternativen Verbundwerkstoff zur Verfügung zu stellen, bei dem sowohl der Matrixwerkstoff als auch der Faserwerkstoff bei Temperaturen > 60°C resistent gegenüber alkalischen Medien ist, und somit die Wahrscheinlichkeit des Eintretens des oben beschriebenen Versagensfalls vermindert wird. Die Erfindung hat sich ebenfalls zur Aufgabe gemacht entsprechende Mittel und Verwendungen des Verbundwerkstoffes bereitzustellen. Object of the present invention is therefore to provide an alternative composite material in which both the matrix material and the fiber material at temperatures> 60 ° C is resistant to alkaline media, and thus reduces the likelihood of the occurrence of the failure described above becomes. The invention has also set itself the task of providing appropriate means and uses of the composite material.
[0010] Die Aufgabe wird gelöst durch einen Verbundwerkstoff umfassend Verstärkungsfasern und einen diese umgebende Matrix aus einem Matrixwerkstoff, wobei der Matrixwerkstoff ein Epoxidharz und/oder ein Furanharz enthält und die Verstärkungsfasern Polyphenylensulfid enthalten. The object is achieved by a composite comprising reinforcing fibers and a surrounding matrix of a matrix material, wherein the matrix material contains an epoxy resin and / or a furan resin and the reinforcing fibers contain polyphenylene sulfide.
[0011] Das Epoxidharz (Kurz EP-Harz) reagiert mit einem Vernetzungspartner, im Allgemeinen als Härter bezeichnet, zu einem duroplastischen Verbundwerkstoff. Das EP-Harz basiert auf unterschiedlichen Ansätzen, bevorzugt für den verwendeten Einsatz sind eine Bisphenol A- oder Novolak-Basis. Die Härtersysteme basieren bevorzugt auf Aminsystemen, wobei sowohl aliphatische wie auch aromatische Amine eingesetzt werden. Es können aber auch Anhydridhärter verwendet werden. The epoxy resin (short EP resin) reacts with a crosslinking partner, generally referred to as a hardener, to a thermoset composite material. The EP resin is based on different approaches, preferred for the use used are a bisphenol A or novolak base. The hardener systems are preferably based on amine systems, using both aliphatic and aromatic amines. However, anhydride hardeners can also be used.
[0012] In vorteilhafter Ausgestaltung der Erfindung umfasst der Verbundwerkstoff ergänzend die Zusatzstoffe, die die Verbundwerkstoffeigenschaften beeinflussen. Diese werden aus der Gruppe der Stabilisatoren Haftvermittler und Gleitmittel ausgewählt und sind dem Fachmann aus dem Stand der Technik bekannt. Diese Modifizierer basieren überwiegend auf aliphatischen oder aromatischen Glycidyl Ethern. Es werden aber auch aliphatische Epoxy Ester Harze oder, Polyepoxide Harze zur Eigenschaftseinstellung verwendet. Als Beschleuniger fungieren Imidazol-basierte Systeme. [0013] Dabei umfasst der Verbundwerkstoff bevorzugt 0,05 bis 35 Gewichtsteile an Zusatzstoffen. Diese können entweder im Matrixwerkstoff und/oder im In an advantageous embodiment of the invention, the composite material additionally includes the additives that influence the composite properties. These are selected from the group of stabilizers adhesion promoters and lubricants and are known in the art from the prior art. These modifiers are based predominantly on aliphatic or aromatic glycidyl ethers. However, aliphatic epoxy ester resins or polyepoxide resins are also used to adjust the properties. The accelerators are imidazole-based systems. In this case, the composite preferably comprises 0.05 to 35 parts by weight of additives. These can either be in the matrix material and / or in the
Faserwerkstoff enthalten sein. Erfindungsgemäß umfasst der Matrixwerkstoff 95 bis 100 % Gewichtsteile Harz und 0 bis 5 % Gewichtsteile Zusatzstoffe. Der Be contained fiber material. According to the invention, the matrix material comprises 95 to 100% by weight of resin and 0 to 5% by weight of additives. Of the
Faserwerkstoff umfasst vorteilhaft 65 bis 100 % Gewichtsteile Polyphenylensulfid und 0 bis 35 % Gewichtsteile Zusatzstoffe. Fiber material advantageously comprises 65 to 100% by weight of polyphenylene sulfide and 0 to 35% by weight of additives.
[0014] Vorteilhaft ist der erfindungsgemäße Verbundwerkstoff gegenüber > 20 %- konzentrierten alkalischen Medien resistent, wobei es sich bei dem alkalischen Medium insbesondere um > 20 % NaOH handelt. Es versteht sich von selbst, dass der Verbundwerkstoff auch eine Resistenz gegenüber anderen Chemikalien aufweist. Advantageously, the composite material according to the invention is resistant to> 20% - concentrated alkaline media, wherein it is the alkaline medium in particular to> 20% NaOH. It goes without saying that the composite also has resistance to other chemicals.
[0015] Der Verbundwerkstoff der vorliegenden Erfindung ist bei Temperaturen > 60°C resistent gegenüber NaOH und anderen alkalischen Medien. The composite of the present invention is resistant to NaOH and other alkaline media at temperatures> 60 ° C.
[0016] Die vorliegende Erfindung umfasst auch Mittel zur Aufnahme und/oder dem Transport von alkalischen Flüssigkeiten, umfassend den erfindungsgemäßen The present invention also includes means for receiving and / or transporting alkaline liquids comprising the invention
Verbundwerkstoff. Dabei handelt es sich vorteilhaft um Rohre oder Behälter. Composite material. These are advantageously pipes or containers.
[0017] Dabei werden die Rohre und Behälter nach einem dem Fachmann aus dem Stand der Technik bekannten Verfahren aus dem Verbundmaterial hergestellt. Die bekannten Verfahren sind im Einzelnen: In this case, the pipes and containers are made by a method known to those skilled in the art from the composite material. The known methods are in detail:
- Wickelverfahren: Beim Wickelverfahren werden drehende (Wickeldorn) und hin- und hergehende (Support) Bewegungen miteinander kombiniert, um die mit Harz getränkten Fasern nach einem bestimmtem Wickelmuster auf dem Dorn ablegen zu können. Dieses Verfahren kann sowohl mechanisiert wie auch händisch ausgeführt werden, wobei unterschiedliche Faserstrukturen, wie z.B. Endlosfäden wie Rovings, Vliese aus Kurzfasern, Wirrfasermatten aus Kurz- und Langfasern, Gewebe oder Gestricke, eingesetzt werden können  - Winding process: In the winding process, rotating (winding mandrel) and reciprocating (support) movements are combined with each other in order to deposit the resin-impregnated fibers on the mandrel after a certain winding pattern. This process can be carried out both mechanized and manually, with different fiber structures, such as e.g. Continuous filaments such as rovings, fleeces of short fibers, random fiber mats of short and long fibers, woven or knitted fabrics can be used
- Flechtverfahren: Beim Flechtverfahren werden die Verstärkungsfasern von einer verschiebbaren Flechtmaschine mit einem rotierenden Flechtkopf auf einem  Braiding process: In the braiding process, the reinforcing fibers of a slidable braiding machine with a rotating braiding head on one
feststehenden Kern abgelegt. Dadurch wird auf dem stationären Kern eine fixed core deposited. As a result, on the stationary core a
gewebeartige Struktur erzeugt, die in einem nachfolgenden Verfahren mit dem fabric-like structure generated in a subsequent process with the
Matrixharz imprägniert werden. Matrix resin are impregnated.
- Schleuderverfahren: Beim Schleuderverfahren wird der Faserverstärkung in Form von z.B. Vliesen oder Geweben vorher eingelegt oder gemeinsam mit dem Harz und eventuellen Zusatzstoffen durch die Lanze, einem beweglichen Beschickungsarm; als Kurzfaser in die Schleuderform eingebracht. Durch die Zentrifugalkraft beim Schleudern entstehen Hohlkörper mit Verstärkungsmittelreichen Außenschichten und harzreichen, chemikalienbeständigen Innenschichten. - Centrifugal method: In the centrifugal process, the fiber reinforcement in the form of, for example, nonwovens or fabrics is previously inserted or together with the resin and any additives through the lance, a mobile loading arm; introduced as short fiber in the centrifugal mold. By the centrifugal force at Slings are formed by hollow bodies with reinforcement-rich outer layers and resin-rich, chemical-resistant inner layers.
[0018] Der erfindungsgemäße Verbundwerkstoff findet vor allen Dingen The composite material according to the invention finds above all things
Verwendung als Werkstoff für Rohrleitungen und/oder Behälter, wobei die Use as a material for pipelines and / or containers, wherein the
Rohrleitungen und/oder die Behälter mit alkalischen Medien in Kontakt gebracht werden. Auch bei erhöhten Temperaturen von > 60°C der alkalischen Medien finden die Rohrleitungen und Behälter Anwendung. Piping and / or the containers are brought into contact with alkaline media. Even at elevated temperatures of> 60 ° C of alkaline media, the piping and tanks are used.
[0019] In einer bevorzugten Verwendung des Verbundwerkstoffs wird dieser in Vorrichtungen eines Elektrolyse-Verfahrens verwendet, in welchem alkalische Medien hergestellt und/oder zugeführt werden. Dabei ist die Verwendung vor allem bei Zu- und Abläufen, sowie in den Reaktionskammern von Elektrolysezellen denkbar. In a preferred use of the composite material, it is used in devices of an electrolysis process in which alkaline media are produced and / or supplied. The use is conceivable especially in inflows and outflows, as well as in the reaction chambers of electrolysis cells.
[0020] Weitere Verwendungsmöglichkeiten des erfindungsgemäßen Further uses of the invention
Verbundwerkstoffes werden nachstehend ausgeführt. Dies sind beispielsweise Vorrichtungen eines Laugeaufkonzentrierungsverfahrens, in dem die Konzentrationen alkalischer Medien verändert werden oder Vorrichtungen eines Verfahrens der Metallgewinnung, in dem alkalische Medien zugeführt und/oder verwendet werden, wobei es sich hierbei vorteilhaft um eine Aluminiumgewinnung aus Bauxit handelt. Des Weiteren bezieht sich die Erfindung ganz allgemein auf Vorrichtungen von Verfahren, wie sie im Stand der Technik bekannt sind, in denen alkalische Medien zugeführt und/oder verwendet werden. Composite material will be explained below. These are, for example, devices of a leaching concentration process in which the concentrations of alkaline media are changed or devices of a process of metal extraction in which alkaline media are supplied and / or used, this advantageously being an aluminum extraction from bauxite. Furthermore, the invention relates generally to apparatuses of methods known in the art in which alkaline media are supplied and / or used.
[0021] Die Erfindung wird nachstehend beispielhaft anhand eines The invention will be described below by way of example with reference to a
Ausführungsbeispiels detailliert erläutert und umfasst eine Untersuchung zur Embodiment explained in detail and includes a study for
Beständigkeit von Rohrwerkstoffen in heißer Natronlauge. Resistance of pipe materials in hot caustic soda.
[0022] Bei den im Versuch eingesetzten Rohrwerkstoffen handelt es sich um Faserverstärkte Kunststoffe. Es sollten zuerst die reinen Grundkomponenten untersucht werden. Die Matrixwerkstoffe sind Epoxid-, Vinylesterharze und andere Harztypen, die sich in ihrer Struktur unterscheiden. Als Fasermaterialien sind unterschiedliche Glas- und Polymerfasern wie z.B. AR-Glas, Polyamidfaser, The pipe materials used in the experiment are fiber-reinforced plastics. First, the pure basic components should be investigated. The matrix materials are epoxy, vinyl ester resins and other resin types that differ in their structure. As fiber materials are different glass and polymer fibers, e.g. AR glass, polyamide fiber,
Polyphenylensulfidfasern vorgesehen. Prüfkörper aus Reinharz und Fasern werden von handelsüblichen Herstellern geliefert. Die quadratischen Prüfkörper haben 30 mm Kantenlänge. Die einzelnen Faserstoffe (ohne Harz) werden, wie handelsüblich ausgeliefert, eingesetzt. Polyphenylene sulfide fibers provided. Test specimens made of pure resin and fibers are supplied by commercial manufacturers. The square test specimens have 30 mm edge length. The individual fibers (without resin) are used as commercially available.
[0023] Die Prüfkörper und Fasern werden in 32 Gew% NaOH-Lösung in PFA- Dosen mit Schraubdeckeln in einem Trockenschrank bei 90°C 10 Tage lang gelagert, um eine Grundbeständigkeit der eingesetzten Proben zu ermitteln. Im Anschluss an diese 10 Tage wurde die Temperatur auf 250 °C erhöht. Die wässerige 32 Gew% NaOH Lösung wurde dabei vollständig zu trockener 100% NaOH verdampft. Dadurch wurden sämtliche Probekörper dem Konzentrationsbereich von 32% bis 100% bei einer Temperatur von bis zu 250°C ausgesetzt. The test specimens and fibers are stored in 32 wt% NaOH solution in PFA cans with screw caps in a drying oven at 90 ° C for 10 days, to determine a basic stability of the samples used. After these 10 days, the temperature was raised to 250 ° C. The aqueous 32% by weight NaOH solution was completely evaporated to dry 100% NaOH. As a result, all specimens were exposed to the concentration range of 32% to 100% at a temperature of up to 250 ° C.
[0024] Ein Teil der Proben wurde durch die hohe Temperatureinwirkung und/oder dem chemischen Angriff zerstört. Die erfindungsgemäßen Werkstoffe, also die Matrixwerkstoffe Epoxydharze und Furanharze sowie die Verstärkungsfasern aus Polyphenylensulfid haben jedoch den extremen Bedingungen des Versuchsaufbau stand gehalten und sind somit der Ausgangsaufgabenstellung vollkommen gerecht geworden.. Some of the samples were destroyed by the high temperature and / or chemical attack. However, the materials according to the invention, ie the matrix materials epoxy resins and furan resins, as well as the reinforcing fibers of polyphenylene sulfide have withstood the extreme conditions of the experimental setup and are thus perfectly suited to the starting task.
[0025] Vorteile, die sich aus der Erfindung ergeben: Advantages resulting from the invention:
Verbundwerkstoff mit guter Alkalibeständigkeit Composite with good alkali resistance
Verbundwerkstoff bei hohen Temperaturen, auch in Gegenwart von alkalischen Medien beständig Composite at high temperatures, even in the presence of alkaline media resistant

Claims

Ansprüche claims
1. Verbundwerkstoff umfassend Verstärkungsfasern und einen diese umgebende Matrix aus einem Matrixwerkstoff, wobei der Matrixwerkstoff ein Epoxydharz und/oder ein Furanharz enthält und die Verstärkungsfasern Polyphenylensulfid enthalten. A composite material comprising reinforcing fibers and a surrounding matrix of a matrix material, wherein the matrix material contains an epoxy resin and / or a furan resin and the reinforcing fibers contain polyphenylene sulfide.
2. Verbundwerkstoff nach Anspruch 1 , dadurch gekennzeichnet, dass der Verbundwerkstoff als Modifizierer die Zusatzstoffe, die aus den Gruppe der Stabilisatoren, Haftvermittler und Gleitmittel ausgewählt werden, umfasst. 2. A composite material according to claim 1, characterized in that the composite material as a modifier, the additives which are selected from the group of stabilizers, adhesion promoters and lubricants comprises.
3. Verbundwerkstoff nach einem der Ansprüche 1 oder 2, dadurch 3. Composite material according to one of claims 1 or 2, characterized
gekennzeichnet, dass der Verbundwerkstoff 0,05 bis 35 % Gewichtsteile an Zusatzstoffen umfasst.  characterized in that the composite comprises 0.05 to 35% by weight of additives.
4. Verbundwerkstoff nach einem der vorstehenden Ansprüche, dadurch 4. Composite material according to one of the preceding claims, characterized
gekennzeichnet, dass der Matrixwerkstoff 95 bis 100 % Gewichtsteile Harz und 0 bis 5 % Gewichtsteile Zusatzstoffe umfasst.  characterized in that the matrix material comprises 95 to 100% by weight of resin and 0 to 5% by weight of additives.
5. Verbundwerkstoff nach einem der vorstehenden Ansprüche, dadurch 5. Composite material according to one of the preceding claims, characterized
gekennzeichnet, dass der Faserwerkstoff 65 bis 100 % Gewichtsteile  characterized in that the fiber material 65 to 100% by weight
Polyphenylensulfid und 0 bis 35 % Gewichtsteile Zusatzstoffe umfasst.  Polyphenylene sulfide and 0 to 35% by weight of additives.
6. Verbundwerkstoff nach einem der vorstehenden Ansprüche, dadurch 6. Composite material according to one of the preceding claims, characterized
gekennzeichnet, dass der Verbundwerkstoff gegenüber > 20 %-konzentrierten alkalischen Medien resistent ist.  characterized in that the composite is resistant to> 20% concentrated alkaline media.
7. Verbundwerkstoff nach Anspruch 6, dadurch gekennzeichnet, dass der 7. Composite material according to claim 6, characterized in that the
Verbundwerkstoff gegenüber > 20 % NaOH resistent ist.  Composite is resistant to> 20% NaOH.
8. Verbundwerkstoff nach einem der vorstehenden Ansprüche, dadurch 8. Composite material according to one of the preceding claims, characterized
gekennzeichnet, dass der Verbundwerkstoff bei Temperaturen > 60°C alkali- resistent ist.  characterized in that the composite material at temperatures> 60 ° C is alkali-resistant.
9. Mittel zur Aufnahme und/oder dem Transport von alkalischen Flüssigkeiten, umfassend den Verbundwerkstoff nach Anspruch 1. 9. An agent for receiving and / or transporting alkaline liquids, comprising the composite material according to claim 1.
10. Mittel zur Aufnahme und/oder dem Transport von alkalischen Flüssigkeiten nach Anspruch 9, dadurch gekennzeichnet, dass es sich um ein Rohr handelt. 10. means for receiving and / or transport of alkaline liquids according to claim 9, characterized in that it is a tube.
11. Mittel zur Aufnahme und/oder dem Transport von alkalischen Flüssigkeiten nach Anspruch 9, dadurch gekennzeichnet, dass es sich um einen Behälter handelt. 11. means for receiving and / or transport of alkaline liquids according to claim 9, characterized in that it is a container.
12. Verwendung des Verbundwerkstoffs nach Anspruch 1 als Werkstoff für 12. Use of the composite material according to claim 1 as a material for
Rohrleitungen und/oder Behälter, wobei die Rohrleitungen und/oder die Behälter mit alkalischen Medien in Kontakt gebracht werden.  Pipelines and / or containers, wherein the pipelines and / or the containers are brought into contact with alkaline media.
13. Verwendung des Verbundwerkstoffs nach Anspruch 1 als Werkstoff für 13. Use of the composite material according to claim 1 as a material for
Rohrleitungen und/oder Behälter, wobei der Verbundwerkstoff mit alkalischen Medien einer Temperatur von > 60°C in Kontakt gebracht wird.  Pipelines and / or containers, wherein the composite material with alkaline media at a temperature of> 60 ° C is brought into contact.
14. Verwendung des Verbundwerkstoffes nach Anspruch 1 in Vorrichtungen von Verfahren, in denen alkalische Medien zugeführt und/oder verwendet werden. 14. Use of the composite material according to claim 1 in apparatuses of processes in which alkaline media are supplied and / or used.
15. Verwendung des Verbundwerkstoffs nach Anspruch 14, wobei es sich bei den Vorrichtungen, um Vorrichtungen eines Elektrolyse-Verfahrens handelt, indem alkalische Medien hergestellt werden und/oder zugeführt werden. 15. The use of the composite according to claim 14, wherein the devices are devices of an electrolysis process in which alkaline media are produced and / or supplied.
16. Verwendung des Verbundwerkstoffes nach Anspruch 14, wobei es sich bei den Vorrichtungen um Vorrichtungen eines Laugeaufkonzentrierungsverfahrens handelt, in dem die Konzentrationen alkalischer Medien verändert werden. 16. The use of the composite of claim 14, wherein the devices are devices of a leach concentration process in which the concentrations of alkaline media are changed.
17. Verwendung des Verbundwerkstoffes nach Anspruch 14, wobei es sich bei den in Vorrichtungen um Vorrichtungen eines Verfahrens der Metallgewinnung handelt, in dem alkalische Medien zugeführt und/oder verwendet werden. The use of the composite of claim 14, wherein the devices are devices of a metal extraction process in which alkaline media are supplied and / or used.
EP12707224.7A 2011-02-07 2012-02-04 Composite material with pps fibres, epoxy resin and/or furan resin Withdrawn EP2673538A1 (en)

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