WO1983000159A1 - Materiau composite de resine epoxyde ayant des caracteristiques d'amortissement ameliorees - Google Patents

Materiau composite de resine epoxyde ayant des caracteristiques d'amortissement ameliorees Download PDF

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Publication number
WO1983000159A1
WO1983000159A1 PCT/US1981/000945 US8100945W WO8300159A1 WO 1983000159 A1 WO1983000159 A1 WO 1983000159A1 US 8100945 W US8100945 W US 8100945W WO 8300159 A1 WO8300159 A1 WO 8300159A1
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WO
WIPO (PCT)
Prior art keywords
epoxy
weight
damping
modulus
composite
Prior art date
Application number
PCT/US1981/000945
Other languages
English (en)
Inventor
Technologies Corporation United
Daniel A. Scola
Jr. Marvin C. Cheney
Original Assignee
United Technologies Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by United Technologies Corp filed Critical United Technologies Corp
Priority to EP19810902134 priority Critical patent/EP0083580A1/fr
Priority to PCT/US1981/000945 priority patent/WO1983000159A1/fr
Publication of WO1983000159A1 publication Critical patent/WO1983000159A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/226—Mixtures of di-epoxy 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers

Definitions

  • the field of art to which the invention pertains is mixed epoxy resin compositions and fiber containing composites made therefrom.
  • the present invention is directed to an epoxy resin, composite with high damping, high strength and high modulus of elasticity properties.
  • the resin component comprises about 12% to about 35% by weight of a high stiffness epxoy resin in admixture with about 20% to about 43% by weight of a flexible epoxy resin and about 35% to about 61% by weight of a flexibilizing curing agent.
  • a composite of such resin in admixture with about 20% to about 50% reinforcing fibers results in a high damping, high strength and high modulus composite.
  • Fig. 1 demonstrates a comparison of damping curves of conventional carbon-epoxy composites with carbon-epoxy composites of the present invention
  • Figs. 2, 3, 4 , 5, 6 and 7 compare the damping curves of composites of the present invention based on different percents of the components, with and without tip weights;
  • Fig. 8 demonstrates the relationship of damping to shear modulus and flexure modulus of composites of the present invention.
  • Fig. 9 demonstrates graphically a comparison of damping values of conventional composites and those of the present invention.
  • the main components of . the " high damping composites of the present invention are the admixture of a flexible long chain aliphatic epoxy component with a standard bisphenol-A stiff epxoy resin, and a flexible long chain amine fatty acid amide curing agent, blended in specific percentage ranges.
  • n 0, 1 or 2 (G.P.C. determined molecular weights of 340, 608 and 876 respectively).
  • the stiff epoxy component is a diglycidyl ester linoleic dimer acid such as Epon 871 with the structural
  • the curing agent is a flexible cross-linking agent which is a long chain a ine fatty acid amide such as Versamid V-40 (General Mills) .
  • the flexible epoxy (such as Epon 828) is used in a range of from about 20% to about 43% by weight and preferably about 27% by weight
  • the stiff epoxy (such as Epon 871) is used in a range of about 12% to about 35% by weight and preferably about 27% by weight
  • the flexible curing agent (such as Versamid V-40) is used in a range of about 35% to about 61% and preferably about 49% by weight.
  • Composites were formulated by dissolving the resin formulation in a solvent such as methyl ethyl ketone to make an approximately 50% by weight solution.
  • Graphite fibers were preferably used in reinforcing the composites such as HMS (Hercules) and Thornel 75 (Union Carbide) of continuous tow. Fiber loading was about 20% to about 50% by weight based on weight of fiber plus resin composition, and preferably about 42% by weight.
  • the graphite fibers were directed by a pulley through the resin bath and wound onto a 17 inch (43.18 cm) diameter, 6 inch (15.24 cm) wide drum to produce a resin impregnated tape
  • OM ' approximately 4 inches (10.16 cm) wide for testing pur ⁇ poses.
  • the particular length and thickness of the tape can be varied depending on the ultimate use.
  • the solvent was evaporated from the tape at room temperature.
  • the tape was removed and cut into four 12 inch (30.48 cm) sections and cured to a B stage in an oven at approximately 80°C for approximately 15 minutes under vacuum.
  • the tapes were removed and cut into approximately 4 by 6 inch (10.16 by 15.24 cm) sections and laid one over the other in a mold for pro ⁇ duction of a multi-layered composite.
  • fiber laying can be in any desired orientation in the composite, uni ⁇ directional laying is preferred for flexbeam uses, for example, and cross-ply laying (e.g., 0°, 45°, 90°; 0°, 30°, 60°; 0°, 90°; etc.) for other uses such as acoustical or spar uses.
  • the mold was placed in a preheated press at about 100°C and a constant pressure of approximately 200 psi .(1.33 x 10 NT/M ) for 10 minutes was imposed followed by curing under this pressure at 100°C for approximately one hour.
  • the molded composite was then post-cured for one hour at approximately 125°C.
  • Epon 828 50 40 75 75 60 60 50 50
  • the specimens were instrumented between the inner two-load points and the strain recorded on a two-axes plot.
  • the specimens were loaded to failure as indicated by complete physical separation or by large excursions and strain. Flexural tests were made for two samples of each composite and the results averaged.' The moduli were determined from the initial slope of the stress- strain curves. In some cases, particularly for the higher damping samples such as 1, 4 and 9, the curve became non ⁇ linear significantly prior to failure and thus the values of modulus given in Table III for these specimens are somewhat misleading. Nominal values of approximately 75% of those listed will be more realistic for preliminary design purposes. It should also be noted that the flexure modulus determined from four-point loading tests corre ⁇ lates well with axia tests.
  • point loading placed the specimens under shear deformation and thus, would be influenced to a greater extent by the properties (e.g. modulus) of the matrix.
  • properties e.g. modulus
  • four-point tests have produced modulus values as much as 50% higher than those from cantilevered tests. This difference, of course, is less for composites with high modulus resins. This accounts in part for the apparent inconsistencies in comparing flexure modulus of the various specimens and then comparing the corresponding torsion modulus. The percent differences in the torsional properties are generally much larger due to the above reason.
  • the shear properties were determined using a simple torsional loading fixture and manually loading cantilever specimens in torsion measuring the tip angular deflection and calculating the modulus from the formula
  • a tip weight of 76 g s was added in some cases as indicated on the Figures.
  • the tip weight clamp was securely affixed to avoid looseness but not so tight as to prevent shear deformation at the free end. Some reduction in the free end shear probably occurred which would tend to add stiffness and reduce damping; however, no estimate was made.
  • the specimen length of six inches (15.24 cm) was not maintained pre ⁇ cisely which would account for some minor differences in frequency. Variations in this dimension were less than i ⁇ .1 inch ( ⁇ 2.54 cm) for all specimens except 9 and 10. For these cases, the specimen length was approximately 7.5 inches (19.05 cm). Damping levels were calculated by comparing response amplitudes at two adjacent peaks and substituting in the equation for damping ratio:
  • Figure 9 compares the system stability of a heli ⁇ copter wind tunnel model using a high damping rotor according to the present invention (curve A) with that of a conventional or low damping rotor (curve B) . As can be seen from the tests, the blade system according to the present invention never really went unstable.
  • composites of the present invention have the following properties: flexural strength greater than 5 x 10 3 psi (3.5 x 10 7 NT M 2 ), and preferably greater than 15 x 10 3 psi (1.03 x 10 8 NT/M 2 ); flexural modulus greater than 10 x 10 psi (6.9 x 10 NT/M ) and preferably greater than 14 x 10 6 psi (9.7 x 10 10 NT/M 2 ); damping up to about 3% critical and preferably up to about
  • damping levels do not appear to be affected by the addition of a concentrated mass, response frequency, or response amplitude, however, note the test in a rotating environment discussed above.
  • the low shear modulus of these materials would allow significant reduction in flexbeam length.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Vibration Prevention Devices (AREA)

Abstract

Un matériau composite à base de résine époxy possède des propriétés améliorées d'amortissement ainsi qu'une bonne résistance et un module d'élasticité élevé. La composition comprend une résine époxyde telle qu'une résine époxyde d'éther épichlorohydrine-bisphénol-A-diglycide mélangée avec une résine époxyde flexible telle qu'une résine époxyde d'ester glycidyle d'acide dimère linoléique et un agent de réticulation flexible tel qu'une amide d'acide gras-amine à chaîne longue. La composition mélangée avec des fibres ayant un module d'élasticité élevé telles que des fibres de graphite forme des matériaux composites ayant des propriétés améliorées d'amortissement, une bonne résistance et un module d'élasticité élevé. Des utilisations caractéristiques des matériaux composites de la présente invention sont des poutres de flexions pour des rotors sans articulation et sans palier et pour des matériaux de barrière acoustique.
PCT/US1981/000945 1981-07-13 1981-07-13 Materiau composite de resine epoxyde ayant des caracteristiques d'amortissement ameliorees WO1983000159A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP19810902134 EP0083580A1 (fr) 1981-07-13 1981-07-13 Materiau composite de resine epoxyde ayant des caracteristiques d'amortissement ameliorees
PCT/US1981/000945 WO1983000159A1 (fr) 1981-07-13 1981-07-13 Materiau composite de resine epoxyde ayant des caracteristiques d'amortissement ameliorees

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1981/000945 WO1983000159A1 (fr) 1981-07-13 1981-07-13 Materiau composite de resine epoxyde ayant des caracteristiques d'amortissement ameliorees

Publications (1)

Publication Number Publication Date
WO1983000159A1 true WO1983000159A1 (fr) 1983-01-20

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1981/000945 WO1983000159A1 (fr) 1981-07-13 1981-07-13 Materiau composite de resine epoxyde ayant des caracteristiques d'amortissement ameliorees

Country Status (2)

Country Link
EP (1) EP0083580A1 (fr)
WO (1) WO1983000159A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0328411A2 (fr) * 1988-02-12 1989-08-16 Mitsui Petrochemical Industries, Ltd. Composition pour un amortisseur de vibrations, procédé pour sa préparation et amortisseur de vibration

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3445282A (en) * 1964-10-05 1969-05-20 Anaconda Wire & Cable Co Insulated electrical conductors and the method for producing the same
US3483146A (en) * 1966-07-14 1969-12-09 Schering Ag Cured and curable compositions comprising a polyglycidyl ether of a polymeric fatty alcohol
US3518221A (en) * 1967-10-30 1970-06-30 Monsanto Co Reinforcing fillers in a matrix of two thermosetting resins
US3567797A (en) * 1968-12-09 1971-03-02 Shell Oil Co Curable compositions comprising (a) a bis(1,2 - epoxyalkyl) cycloaliphatic compound,(b) a polyether polyepoxide and (c) a curing agent
US3806489A (en) * 1973-06-04 1974-04-23 Rhone Progil Composite materials having an improved resilience
US3812064A (en) * 1972-03-15 1974-05-21 Gen Electric Polyanhydrides useful as flexibilizing curing agents for epoxy resins
US3943090A (en) * 1972-06-27 1976-03-09 British Railways Board Carbon fibre composites
US3989673A (en) * 1974-12-30 1976-11-02 Hughes Aircraft Company Low temperature curing resin system
US4083735A (en) * 1977-03-29 1978-04-11 Caramanian John A Method of balancing rotors and composition therefor
US4115599A (en) * 1974-11-06 1978-09-19 Owens-Illinois, Inc. Process for producing glass article having fragment retaining and alkali resistant coating

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3445282A (en) * 1964-10-05 1969-05-20 Anaconda Wire & Cable Co Insulated electrical conductors and the method for producing the same
US3483146A (en) * 1966-07-14 1969-12-09 Schering Ag Cured and curable compositions comprising a polyglycidyl ether of a polymeric fatty alcohol
US3518221A (en) * 1967-10-30 1970-06-30 Monsanto Co Reinforcing fillers in a matrix of two thermosetting resins
US3567797A (en) * 1968-12-09 1971-03-02 Shell Oil Co Curable compositions comprising (a) a bis(1,2 - epoxyalkyl) cycloaliphatic compound,(b) a polyether polyepoxide and (c) a curing agent
US3812064A (en) * 1972-03-15 1974-05-21 Gen Electric Polyanhydrides useful as flexibilizing curing agents for epoxy resins
US3943090A (en) * 1972-06-27 1976-03-09 British Railways Board Carbon fibre composites
US3806489A (en) * 1973-06-04 1974-04-23 Rhone Progil Composite materials having an improved resilience
US4115599A (en) * 1974-11-06 1978-09-19 Owens-Illinois, Inc. Process for producing glass article having fragment retaining and alkali resistant coating
US3989673A (en) * 1974-12-30 1976-11-02 Hughes Aircraft Company Low temperature curing resin system
US4083735A (en) * 1977-03-29 1978-04-11 Caramanian John A Method of balancing rotors and composition therefor

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0328411A2 (fr) * 1988-02-12 1989-08-16 Mitsui Petrochemical Industries, Ltd. Composition pour un amortisseur de vibrations, procédé pour sa préparation et amortisseur de vibration
EP0328411A3 (fr) * 1988-02-12 1990-09-05 Mitsui Petrochemical Industries, Ltd. Composition pour un amortisseur de vibrations, procédé pour sa préparation et amortisseur de vibration

Also Published As

Publication number Publication date
EP0083580A1 (fr) 1983-07-20

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