EP2661461A1 - Résines ou systèmes résine et composites renforcés par des fibres - Google Patents

Résines ou systèmes résine et composites renforcés par des fibres

Info

Publication number
EP2661461A1
EP2661461A1 EP12712616.7A EP12712616A EP2661461A1 EP 2661461 A1 EP2661461 A1 EP 2661461A1 EP 12712616 A EP12712616 A EP 12712616A EP 2661461 A1 EP2661461 A1 EP 2661461A1
Authority
EP
European Patent Office
Prior art keywords
resin
fiber
fiber composite
composite material
component
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Withdrawn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
EP12712616.7A
Other languages
German (de)
English (en)
Inventor
Heinrich Kapitza
Christian Seidel
Lutz Völker
Heinrich Zeininger
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.)
Siemens AG
Original Assignee
Siemens AG
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 Siemens AG filed Critical Siemens AG
Publication of EP2661461A1 publication Critical patent/EP2661461A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D5/00—Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
    • F01D5/12—Blades
    • F01D5/28—Selecting particular materials; Particular measures relating thereto; Measures against erosion or corrosion
    • F01D5/282—Selecting composite materials, e.g. blades with reinforcing filaments
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2220/00—Application
    • F05D2220/30—Application in turbines
    • F05D2220/31—Application in turbines in steam turbines
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2300/00—Materials; Properties thereof
    • F05D2300/60—Properties or characteristics given to material by treatment or manufacturing
    • F05D2300/603—Composites; e.g. fibre-reinforced

Definitions

  • the invention relates to resins or resin systems according to the preamble of independent claim 1, fiber composites according to the preamble of independent claim 3 and components comprising fiber composites, according to the independent claim 6, in particular turbine components.
  • Fiber composites are increasingly used for lightweight construction and lightweight constructions.
  • the fiber composites consist of individual fibers or fiber mats, which are impregnated in resin and thus form a fiber composite.
  • the fiber composite materials are characterized in comparison to metallic construction materials in that they have a much lower specific density with higher specific shear ⁇ mechanical strength.
  • fiber composites are increasingly being used in dynamically loaded components / constructions.
  • ⁇ turbine components for power generation including wind turbines
  • the resins used in the fiber composite are exposed to high hydrolytic stresses due to water vapor at high temperatures.
  • many fiber composites show significant aging effects in terms of fatigue ih ⁇ er mechanical properties. The result is a strong Re ⁇ duzierung the mechanical properties, whereby the fiber Composite materials are unsuitable for these purposes so far.
  • the resin-based fiber composites for steam turbine blades, they can be provided with a water and water vapor impermeable coating.
  • the protective layer is frequently destroyed. Subsequently, water / steam can then penetrate into the fiber composite material, reduce the fiber-matrix connection and ultimately destroy it.
  • the resin according to the invention in particular epoxy resin, vinyl ester resin, cyanate ester resin or unsaturated polyester resin or resin system is characterized in that the resin or the resin system to increase its hydrolytic stability contains a protective additive to water vapor, wherein the protective additive at least one organic nitrogen compound, in particular polycarbodiimide or 2,6 diisopropyphenylcarbodiimide.
  • the resin system is understood to mean a system consisting of several resins.
  • the Bestän ⁇ speed against water and water vapor is significantly increased temperatures at high temperature.
  • the long-term stability with respect to the modulus of elasticity (modulus of elasticity), the flexural strength and the bending elongation relative to the resin without protective additive increases significantly.
  • the protective additive improves in particular the dynamic load capacity of the resin or of the resin system.
  • the fiber composite material of the invention comprising Wenig ⁇ least a resin or resin system, and at least one fiber or fiber mat, is characterized in that the resin or resin system to increase its stability against Superheated steam containing a protective additive to water vapor, said resistant additive comprises at least one organic stick ⁇ carbon compound, in particular 2,6 or polycarbodiimide diisopropyl sopropyphenylcarbodiimid.
  • fiber material are all known fiber materials, in particular glass fiber, carbon fiber, aramid fiber and other polymeric and inorganic fibers in question.
  • a preferred embodiment of the invention provides that the proportion of the protective additive is less than 5 wt .-%, in particular less than 1 wt .- of the resin / resin system.
  • Vehicle component or component for electronic devices characterized in that the component as a whole or a part of the component, of a fiber composite material with a resin or resin system according to the invention or with a fiber composite material according to the invention with such a resin is formed.
  • it is pos ⁇ lich to train long-term stable lightweight components.
  • a particularly advantageous embodiment of the invention provides that the component is a turbine blade or a part of a turbine blade, in particular a steam turbine.
  • the resin according to the invention or the fiber composite material according to the invention is particularly suitable for the formation of turbine blades in steam turbines, as well as high temperatures ⁇ 150 ° C occur in the steam turbine in addition to very high water vapor humidities, which so far the use of fiber composite materials was excluded.
  • the resin / resin system according to the invention or the fiber composite material according to the invention with the increased resistance to water vapor, the use of fiber composite materials for steam turbines, in particular steam turbine blades, is now possible for the first time.
  • FIG. 2 shows a time comparison of the flexural strength of a normal epoxy resin versus an epoxy resin with protective additive against water vapor;
  • FIG. 3 shows a time comparison of the bending elongation between a normal epoxy resin and an epoxy resin with protective additive against water vapor;
  • - Figure 4 shows the time course of the modulus of elasticity for a fiber composite material (CFRP) with a resin without and with protective additive to water vapor
  • - Figure 5 shows the time course of the bending strength for a fiber composite material with a resin without and with protective additive to water vapor.
  • the protective additive to the resin / resin ⁇ system and to determine the fiber composite material are respectively a sample of a resin or resin system or a fiber composite material with and without protective additive, certain exposed to ambient conditions. Subsequently, the modulus of elasticity, the bending strength and the bending strain are measured at specific times and plotted against each other in diagrams. The results are shown below in the diagrams 1 to 5.
  • the resin used is a commercial epoxy resin called CY179.
  • a protective additive a polycarbodiimide was used in each case with a wt .-% share of 1%. The samples were each stored in a 80 to 150 ° C ° C hot ⁇ steam atmosphere over a period of 30 days.
  • Water vapor was chosen because the combined exposure of moisture in the form of steam and heat is particularly critical to resins.
  • the measurements of the elastic modulus, bending strength and the Bie ⁇ gedehnung were made at defined time points to the beginning of the measurement, after 10 and after 30 days.
  • Diagram 1 shows the course of the modulus of elasticity for an epoxy resin CY179 with and without protective additive against water vapor atmosphere.
  • the left part of the diagram shows the time course for the resin without protective additive. It is easy to see how the modulus of elasticity decreases significantly with increasing time. After 30 days, the elastic modulus is only about 2/3 of the original modulus of elasticity.
  • the course of the modulus of elasticity for the same epoxy resin with a Addition of 1 weight polycarbodiimide ⁇ represents Darge as a protective additive.
  • Figure 2 shows the time course for the bending strength for the same samples.
  • the sample with the epoxy resin oh ⁇ ne protective additive shows a strong decrease in bending strength with time. After 30 days, the bending strength is only about 20% of the original value.
  • the flexural strength of the epoxy resin with the polycarbodiimide as a protective additive decreases only slightly (right side). After 30 days, the flexural strength is still around 80% of the original flexural strength.
  • FIG. 3 shows the bending strain for the samples already described in FIGS. 1 and 2. It can be seen that the bending strain of the epoxy resin without protective additive decreases very much over time (left side). After 30 days, the bending strain is only about 20% of the original bending strain. The situation is different with the epoxy resin to which polycarbodiimide is added as a protective additive (right side). Here is still a bending strain of about 75% of the starting value available after 30 days. Thus, as clearly shown by all three graphs, by adding small amounts of a protective additive, the resistance of the resin to water vapor / atmosphere can be substantially improved, preferably at high temperatures.
  • the potential use of the resin can be significantly extended and it is especially a use in dynamically loaded components / structures possible.
  • Similar positive results can be achieved as a protective additive with other or ⁇ ganic nitrogen compounds.
  • favorable stabilities result for polycarbodiimide or diisopropyphenylcarbodiimide.
  • the proportion of the protective additive is preferably low, ie to choose below 5 wt .-%, in particular less than 1 wt .-% of the resin / resin system. Higher parts by weight lead to no further improved stability.
  • the positive property of the protective additive can also be seen in fiber composites having a resin with protective additive.
  • the fiber composites are a carbon fiber reinforced plastic, which is formed by means of the already described epoxy resin CY179.
  • the proportion of the protective additive to water vapor is again 1% by weight, based on the resin. Both samples were again viewed at 80 ° C, in water vapor, over a period of 30 days. The results of these measurements are shown below with reference to FIGS. 4 and 5.
  • Figure 4 shows the time course of the modulus of elasticity for a fiber composite material with and without protective additive to water vapor. On the left side, the course of the e-
  • the effect of the protective additive on the fiber composite material when viewing the flexural strength becomes clearer.
  • the time course of the bending strength for the same fiber composite material is shown in FIG. It can be seen here that the flexural strength of the fiber composite material without protective additive (left side of the diagram) drops markedly over time. After 30 days, the flexural strength of the fiber composite material is only just under 80% of the original value. In contrast, the flexural strength of the fiber composite with protective additive decreases only very slightly. After 30 days, the flexural strength is still 99% of the original flexural strength. Thus, it can also be stated here that the addition of a protective additive in fiber composites contributes to a significant increase in flexural strength.
  • the admixture of the protective additive with respect to water vapor degradation should also be less than 5% by weight, in particular less than 1% by weight, based on the resin, in the case of the fiber composite material. Higher admixtures of protective additive lead to no improvement in stability to water vapor.
  • the addition of protective additive has a similar positive effect on the stability to water vapor for all conventional fiber materials, in particular glass fiber, carbon fiber, aramid fiber and / or polymers or organic fibers.
  • the improved by means of protective additive fiber composite material is particularly suitable for components that are permanently used in humid / vaporous environment.
  • the fiber composite material according to the invention enables the formation of turbine blades or of parts of turbine blades, in particular in steam turbines.
  • high moisture contents in pure water vapor atmosphere and high temperatures (circa indication step 150 ⁇ ⁇ on.
  • These provide for a composite fiber material with an epoxy resin without a protective additive to steam in a very rapid decomposition of the fiber composite material. Therefore, the use of fiber composite materials
  • the use of fiber composite materials with a protective ad- ditive can reduce the dynamic load capacity of the components and their
  • the fiber composite according to the invention is suitable for all components which are used permanently in a moist / dam-shaped environment.
  • turbine components, vehicle components or components for electronic devices can be formed by the use of the fiber composite material according to the invention significantly more resistant to water vapor atmosphere.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

L'invention concerne une résine, de préférence une résine époxy, une résine d'ester vinylique, une résine d'ester de cyanate ou une résine de polyester insaturée ou des systèmes résine, ladite résine ou ledit système résine contenant un additif de protection pour avoir une stabilité hydrolytique accrue vis-à-vis de la vapeur d'eau. L'additif de protection permet d'augmenter la stabilité de la résine dans la vapeur d'eau. En outre, l'invention concerne un matériau composite à fibres contenant une telle résine ou un tel système résine. L'invention concerne un composant constitué en tout ou en partie d'un tel matériau composite à fibres.
EP12712616.7A 2011-03-24 2012-03-21 Résines ou systèmes résine et composites renforcés par des fibres Withdrawn EP2661461A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102011006063 2011-03-24
PCT/EP2012/054950 WO2012126927A1 (fr) 2011-03-24 2012-03-21 Résines ou systèmes résine et composites renforcés par des fibres

Publications (1)

Publication Number Publication Date
EP2661461A1 true EP2661461A1 (fr) 2013-11-13

Family

ID=45932302

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12712616.7A Withdrawn EP2661461A1 (fr) 2011-03-24 2012-03-21 Résines ou systèmes résine et composites renforcés par des fibres

Country Status (2)

Country Link
EP (1) EP2661461A1 (fr)
WO (1) WO2012126927A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104910621B (zh) * 2015-06-10 2017-10-13 苏州生益科技有限公司 热固性树脂组合物及使用其制作的半固化片及层压板

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2523690B2 (ja) * 1987-10-06 1996-08-14 株式会社東芝 原子力用タ―ビン機器の保管方法
US20070021558A1 (en) * 2005-05-12 2007-01-25 Kenichi Shinohara Polyamide resin composition
JP5164576B2 (ja) * 2005-12-02 2013-03-21 株式会社クレハ ポリグリコール酸樹脂組成物
DE102009006418A1 (de) * 2009-01-28 2010-12-09 Siemens Aktiengesellschaft Turbinenschaufel, insbesondere Laufschaufel für eine Dampfturbine, sowie Herstellungsverfahren hierfür

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2012126927A1 *

Also Published As

Publication number Publication date
WO2012126927A1 (fr) 2012-09-27

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