• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to a process for the preparation of a composite material comprising graphene oxide comprising the following steps: a) dispersion of graphene oxide in an epoxy resin, b) addition to the dispersion obtained in stage a), of a hardener, c) impregnation of the reinforcing material with the hardened resin in step b), d) solidification of the product obtained in step c), wherein stage a) of dispersion does not comprise organic solvents. The present invention also relates to the composite material obtained by the process of the present invention. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2702118A1
    申请号:ES201830477
    申请日:2018-05-18
    公开日:2019-02-27
    发明作者:Gomez Gemma Sanjuan；Arias Manel Lis；De Prada Cristian López；Vela Jorge Fernandez
    申请人:Forest Next S L；
    IPC主号:
    专利说明:

    [0001] PROCEDURE FOR THE PREPARATION OF MATERIAL COMPOSED OF CARBON FIBER OR ARAMIDA WITH GRAFEN OXIDE AND REDUCED GRAFEN OXIDE
    [0002]
    [0003] Object of the invention
    [0004]
    [0005] The present invention falls within the general field of composite materials, and in particular it relates to a process for the preparation of carbon fiber or aramid composite materials with graphene oxide and reduced graphene oxide.
    [0006]
    [0007] State of the art
    [0008]
    [0009] In recent years, the use of composite materials has become widespread. The improvement of this type of material is based on the modification of the structure and composition of the material to endow it with a series of properties depending on the particular use.
    [0010]
    [0011] The aim is to achieve a material that combines a high elastic limit and a high tenacity, this is achieved by introducing nanoparticles in the composition of the material to provide a better interaction between the matrix and the reinforcement.
    [0012]
    [0013] There are different documents that describe the improvements of composite materials with different particles (Fillers), as for example in Pin-Ning Wang, et al. "Synergetic Effects of Mechanical Properties on Graphene Nanoplatelet and Multiwalled Carbon Nanotube Hybrid Reinforced Epoxy / Carbon Fiber Composites." Journal of Nanomaterials, Volume 2015 (2015), describing the synergistic effect of graphene nanoplatelets and carbon nanotubes in reinforced composite materials with carbon fiber / epoxy resin The process of preparing said reinforced compounds uses maleic anhydride to modify the particles used and a dispersion process in three steps, using acetone as a dispersant.
    [0014]
    [0015] Long-Cheng Tang et al. "The effect of graphene dispersion on the mechanical properties of graphene / epoxy composites Carbon." Vol.60, August 2013, Pages 16-27.They describe the effect of graphene dispersion on the mechanical properties of graphene / epoxy composites, using ethanol as a dispersant of the reduced graphene oxide.
    [0016]
    [0017] B.Ahmadi-Moghadam et al. "Effect of functionalization of graphene nanoplatelets on the mechanical response of graphene / epoxy composites." Materials & Design (1980-2015) Volume 66, Part A, 5 February 2015, Pages 142-149
    [0018] It uses graphene nanoplatelets (GNP) to improve the properties of composites. To disperse the GNP, it uses the "three-roll Mill" method and a dispersion in alcohol or acetone, and a solvent elimination by means of a mechanical system.
    [0019]
    [0020] Abhishek K. Pathak, et al. Improved mechanical properties of carbon fiber / graphene oxideepoxy hybrid composites. Composites Science and Technology. Volume 135, 27 October 2016, Pages 28-38
    [0021]
    [0022] They report that the mechanical properties of carbon fiber reinforced polymer composites depend on the interfacial properties of the matrix. They use graphene oxide as a filler for the preparation of carbon fiber-graphene oxide-epoxy composites. Disperse the graphene oxide in an ethanol solution before being mixed with the epoxy resin. The excess ethanol in the mixture is removed at 60 ° C.
    [0023]
    [0024] The results show that the dispersion and exfoliation of graphene is an obstacle when mixed with the polymer, giving rise to nano-defects in the laminated compounds that produce a minimum improvement in mechanical properties.
    [0025]
    [0026] Patent CN103627139, describes a method for preparing a nanocomposite of graphene oxide / functionalized epoxy resin, comprising the steps of performing an ultrasound treatment on the graphene oxide modified with silane (f-GO) and dispersion in an organic solvent ; subsequent addition of the epoxy resin and mixing; the organic solvent is finally removed by vacuum;
    [0027]
    [0028] All the procedures described above used to disperse the graphene oxide in the resin organic solvents such as acetone or ethanol, this solvent must subsequently be removed, generally by heat evaporation, or by mechanical processes that generate the crosslinking of the resins and by therefore, the loss of their properties.
    [0029]
    [0030] There is therefore a need to provide a composite material for applications with high yield strength and high stress at break, which has the properties unaltered for use in applications with high yield strength and high stress at break.
    [0031]
    [0032] BRIEF DESCRIPTION OF THE INVENTION
    [0033]
    [0034] The present invention solves the problems described in the state of the art since it provides a method of preparing a composite material with an improved fatigue resistance, better elastic limit and better resistance to breakage, compared to the original method.
    [0035]
    [0036] Thus, in a first aspect, the present invention relates to a process for the preparation of a composite comprising graphene oxide comprising the following steps:
    [0037]
    [0038] a) dispersion of graphene oxide in an epoxy resin,
    [0039]
    [0040] b) addition to the dispersion obtained in stage a), of a hardener,
    [0041]
    [0042] c) impregnation of the reinforcing material with the hardened resin in step b),
    [0043]
    [0044] d) solidification of the product obtained in step c).
    [0045]
    [0046] wherein, step a) of dispersion does not comprise organic solvents.
    [0047]
    [0048] In the present invention, composite refers to materials consisting of two components, where one of them is the matrix component and the other is the reinforcement component; where the matrix component provides the chemical properties to the composite material and the reinforcing component provides the geometric consistency and determines the mechanical properties of the composite material, such that the composite achieves the properties of the two components. In the present invention, the composite matrix is selected from epoxy and polypropylene based resins and the reinforcement is selected from among carbon fiber, polyaramide and mixture thereof.
    [0049]
    [0050] In the present invention carbon fiber refers to any fiber constituted by filaments mainly carbon.
    [0051]
    [0052] In the present invention, polyamide refers to fibrous polymers with a high degree of crystallinity, high rigidity and high chemical arrangement, which has a structure with the amide bonds in the "para" position, providing it with improved mechanical properties.
    [0053]
    [0054] In a particular embodiment, step a) consists of the following sub-stages:
    [0055]
    [0056] i) treatment of graphene oxide / graphene oxide reduced with ultrasound, with a frequency comprised between 18-20 kHz for 10-25 minutes; preferably 18 Khz for 20 minutes.
    [0057]
    [0058] ii) graphene oxide / reduced graphene oxide decomposition obtained in step i), iii) treatment of the graphene oxide obtained in step ii) with ultrasound with a frequency comprised between 18-20 Khz for 1-7 minutes; preferably 20 Khz for 5 minutes.
    [0059]
    [0060] In a particular embodiment, the graphene oxide deagglomeration of step ii) is performed by ultra centrifugation at 22,000-40,000 rpm.
    [0061]
    [0062] In a particular embodiment step ii) is repeated at least 2 times.
    [0063]
    [0064] In the present invention, epoxy resin refers to thermostable polymers with an epoxide functional group (also known as oxirane or glycidyl). In the present invention, epoxy resins are selected from phenolic glycidyl ethers, glycidyl amines. More particularly, the epoxy resin of step a) is selected from N, N, N ', N'-tetraglycidyl-4,4'-diamino diphenylmethane (TGDDM), Diglycidyl Ether of Bisphenol A (DGEBA), Biphenol epoxy (BP), Tetramethyl biphenyl epoxy (TMBP), AzomethineLinkage Epoxy Resin (AM) or mixture thereof.
    [0065]
    [0066] In another particular embodiment, the epoxy resin of step a) is at a percentage of at least 25% by weight.
    [0067]
    [0068] In another particular embodiment, the graphene oxide of step a) is in a percentage comprised between 0.01-0.35% by weight with respect to the resin.
    [0069]
    [0070] In another particular embodiment, the hardener of step b) is selected from maleic anhydride (MA), hexahydrophthalic anhydride (HHPA), methylcyclohexane-1,2-dicarboxylic anhydride (MCHDA), Polyoxypropylene diamine (D230) and sulfinyl amide (SAA).
    [0071]
    [0072] In another particular embodiment, the hardener of step b) is in a percentage comprised between 2.5-55% by weight.
    [0073]
    [0074] In another particular embodiment, the reinforcing material of step c) is selected from carbon fiber and polyaramide.
    [0075]
    [0076] In another particular embodiment, the stage d) of solidification at a temperature comprised between 12-45 ° C for 10-24 h.
    [0077]
    [0078] In another particular embodiment, the graphene oxide is reduced graphene oxide.
    [0079]
    [0080] In another aspect, the present invention relates to a composite material obtained by the process of the present invention.
    [0081] Detailed description of the invention
    [0082] EXAMPLE 1: Procedure for preparing a composite material with graphene oxide
    [0083] The test began with the dispersion of 0.3% by weight of graphene oxide in diglycidyl ether of bisphenol-A, by applying ultrasound with a frequency of 20 Khz for 20 minutes. Next, an ultra-turrax IKA T25 with a power of 30,000 rpm was performed for 5 minutes and we repeated the ultrasound application with frequency 20 Khz for 20 minutes and then ultra centrifugation, four times. To finish the process, we applied ultrasound with a frequency of 20 Khz during 5 minutes and introduced the mixture in the hardener (Polioxipropilendiamina) and we applied ultrasound during 5 minutes with a frequency of 20 Khz. Subsequently we impregnated the carbon fiber (twill of 600K) and let it solidify for 15 hours at a temperature of 20 ° C.
    [0084] With the composite material obtained, we measured the stress at break and the Young's modulus and compared it with another composite material but that did not contain graphene oxide, the results are shown in table 1. The mechanical test to determine the Young's modulus and the stress at break was carried out following the ISO527-1: 2012 standard; Each of the samples was taken from the composite made with a width of 15 +/- 2mm, and a total length of 250mm and a thickness less than or equal to 1mm. The tests were performed with a speed of 2mm / min at room temperature.
    [0085]
    [0086]
    [0087]
    [0088] Table 1
    [0089] EXAMPLE 2: Procedure for preparing a composite material with reduced graphene oxide
    [0090]
    [0091] The test began with the dispersion of 0.3% by weight of graphene oxide in diglycidyl ether of bisphenol-A, by applying ultrasound with a frequency of 18 Khz for 20 minutes. Next, an ultra-turrax IKA T25 with a power of 22,000 rpm was performed for 5 minutes and we repeated the ultrasound application with frequency 18 Khz for 20 minutes and then ultra centrifugation, four times. To finish the process, we applied ultrasound with a frequency of 20 Khz during 5 minutes and introduced the mixture in the hardener (Polioxipropilendiamina) and we applied ultrasound during 5 minutes with a frequency of 20 Khz. Subsequently we impregnated the polyamide, (twill of 300K) and let it solidify during 24 hours at a temperature of 20 ° C.
    [0092] With the composite material obtained, we measured the breaking stress and the Young's modulus and compared it with another composite material but that did not contain graphene oxide, the results are shown in table 2. As in example 1, the mechanical test to determine the Young's modulus and the stress at break was performed following the ISO527-1: 2012 standard, each of the samples taken from the composite made had a width of 15 +/- 2mm, and a total length of 250mm and a thickness less than or equal to 1mm. The tests were performed with a speed of 2mm / min at room temperature.
    [0093]
    [0094]
    权利要求:
    Claims (13)
    [1]
    Method for the preparation of a composite material comprising graphene oxide comprising the following steps:
    a) dispersion of graphene oxide in an epoxy resin,
    b) addition to the dispersion obtained in stage a), of a hardener,
    c) impregnation of the reinforcing material with the hardened resin in step b),
    d) solidification of the product obtained in step c).
    characterized in that the dispersion step a) does not comprise organic solvents.
    [2]
    The method according to claim 1, wherein step a) comprises the following sub steps:
    i) treatment of graphene oxide with ultrasound, with a frequency between 10-18khz for 10-25 minutes.
    ii) deglomeration of the graphene oxide obtained in step i),
    iii) treatment of the graphene oxide obtained in step ii) with ultrasound with a frequency comprised between 18-20 Khz for 1-7minutes.
    [3]
    3. Method according to any of the preceding claims, wherein the graphene oxide deagglomeration of step ii) is carried out by ultra centrifugation with a power comprised between 20,000-40,000 rpm.
    [4]
    4. Method according to any of the preceding claims, wherein step ii) is repeated at least 2 times.
    [5]
    Method according to any one of the preceding claims, wherein the epoxy resin of step a) is selected from N, N, N ', N'-tetraglycidyl-4,4'-diamino diphenylmethane (TGDDM), Diglycidyl Ether of Bisphenol A (DGEBA), Biphenol epoxy (BP), Tetramethyl biphenyl epoxy (TMBP), AzomethineLinkage Epoxy Resin (AM) and mixture thereof.
    [6]
    6. Process according to any of the preceding claims, wherein the epoxy resin of step a) is at a percentage of at least 25% by weight.
    [7]
    Method according to any one of the preceding claims, wherein the graphene oxide of stage a) is in a percentage comprised between 0.01-0.35 % by weight with respect to the resin.
    [8]
    8. Process according to any of the preceding claims, wherein the hardener of step b) is selected from maleic anhydride (MA), hexahydrophthalic anhydride (HHPA), methylcyclohexane-1,2-dicarboxylic anhydride (MCHDA), Polyoxypropylene diamine (D230) and sulfinyl amide (SAA).
    [9]
    9. Process according to any of the preceding claims, wherein the hardener of step b) is in a percentage comprised between 2.5-55% by weight.
    [10]
    The method according to any of the preceding claims, wherein the reinforcing material of step c) is selected from carbon fiber, polyaramide and mixture thereof.
    [11]
    11. Process according to any of the preceding claims, wherein step d) of solidification at a temperature comprised between 12-45 ° C for 10-24h.
    [12]
    12. Process according to any of the preceding claims, wherein the graphene oxide is reduced graphene oxide.
    [13]
    13. Composite material obtained by a method according to any of claims 1-12.
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    ES201830477A|ES2702118B2|2018-05-18|2018-05-18|PROCEDURE FOR THE PREPARATION OF COMPOSITE CARBON FIBER OR ARAMIDE MATERIAL WITH GRAPHENE OXIDE AND REDUCED GRAPHENE OXIDE|ES201830477A| ES2702118B2|2018-05-18|2018-05-18|PROCEDURE FOR THE PREPARATION OF COMPOSITE CARBON FIBER OR ARAMIDE MATERIAL WITH GRAPHENE OXIDE AND REDUCED GRAPHENE OXIDE|
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