• 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 provides a process for the preparation and use of a composite nanomaterial of graphene oxide – tetraethyl orthosilicate (TEOS) / silane, and belongs to the field of technologies for the protection and improvement of materials based on. cement. The process for preparing the graphene oxide – TEOS / silane composite nanomaterial provided in the present invention comprises the following steps: (1) mixing a dispersion of graphene oxide with a dispersant to obtain a first mixed ; (2) mixing silane with an emulsifying agent to obtain a second mixture; (3) mixing the first mixture with the second mixture, and adding TEOS to obtain a mixture; and (4) drying the mixture, and grinding to obtain the graphene oxide – TEOS / silane composite nanomaterial, in which there is no specific order between step (1) and step (2). Example results show that the compressive strength of a cementitious material prepared in the present invention is 45.4 to 54.1 MPa, and its flexural strength is 1.75 to 1, 96 MPa.
    公开号:FR3096983A1
    申请号:FR2005885
    申请日:2020-06-05
    公开日:2020-12-11
    发明作者:Shaochun Li；Dongshuai Hou；Yongjuan GENG；Wenjuan Zhang；Zuquan Jin；Yaguang ZHU；Youlai ZHANG
    申请人:Qingdao University of Technology；
    IPC主号:
    专利说明:

    [0001] The present invention relates to the field of technologies for the protection and improvement of cementitious materials and, in particular, to a process for the preparation and use of a composite nanomaterial of graphene oxide–tetraethyl orthosilicate (TEOS)/ silane.
    [0002] In recent years, researchers have found that after adding graphene oxide to a cementitious material, graphene oxide can be used as a matrix for cement hydration reaction due to its rich functional groups. This changes the cement hydration process, and improves the crystal structure of a cement hydration product, thereby improving the compressive strength and flexural strength of the cementitious material. Silane is a commonly used waterproof material for cementitious material. However, after silane is added in a cementitious material, due to the good waterproof performance of silane, the anti-penetrability performance of the cementitious material can be obviously improved, but the hydration of the cement is inhibited, thereby reducing the mechanical properties of the cement. SiO 2 nanoparticles with specific activity are generated during the hydrolysis of TEOS (tetraethyl orthosilicate), and are commonly used in the repair and protection of old buildings. In recent years, SiO 2 nanoparticles are also often used in a cement-based material. A secondary hydration reaction between SiO 2 nanoparticles and a cement hydration product Ca(OH) 2 can be used to improve the microstructure and mechanical properties of the cement-based material. However, the compressive strength and flexural strength of a hardened cementitious material obtained by using a reinforcing agent disposed in the above solution cannot meet the actual requirements of a cementitious material.
    [0003] Therefore, a problem which needs to be urgently solved is how to further improve the compressive strength and the flexural strength of a cementitious material, based on the improvement of the anti–penetrability performance of cement. of the cement-based material, by improving the cement-based material.
    [0004] An object of the present invention is to provide a method for preparing and using a graphene oxide–TEOS/silane composite nanomaterial. The preparation method provided in the present invention can effectively improve the waterproofing effect, the compressive strength, and the flexural strength of a cementitious material.
    [0005] To achieve the above purpose, the present invention provides the following technical solutions.
    [0006] The present invention provides a method for preparing a composite graphene oxide-tetraethyl orthosilicate (TEOS)/silane nanomaterial, comprising the following steps: (1) mixing a dispersion of graphene oxide with a dispersant to obtain a first mixture; (2) mixing silane with an emulsifying agent to obtain a second mixture; (3) mixing the first mixture with the second mixture, and adding TEOS to obtain a mixture; and (4) drying the mixture, and grinding to obtain the graphene oxide–TEOS/silane composite nanomaterial, wherein there is no specific order between step (1) and step (2).
    [0007] Preferably, the drying comprises high temperature drying or freeze-drying.
    [0008] Preferably, the milling is high energy ball milling.
    [0009] Preferably, the mixing in step (3) is carried out at a constant temperature of 50 to 80°C for 2 to 3 hours.
    [0010] Preferably, the graphene oxide–TEOS/silane composite nanomaterial contains the following components, in parts by weight: 5 to 45 parts graphene oxide dispersion, 30 to 90 parts TEOS, 30 to 80 parts silane , 1 to 5 parts emulsifying agent, and 1 to 5 parts dispersant.
    [0011] Preferably, the particle size of the graphene oxide in the graphene oxide dispersion is 3 to 8 μm, and the mass concentration of the graphene oxide dispersion is 0.5 to 5%.
    [0012] Preferably, the silane is one or more of methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, trimethoxyoctylsilane, and triethoxyoctylsilane.
    [0013] Preferably, the dispersant is one or more of sodium dodecylbenzenesulfonate, poly(vinyl alcohol), polyethylene glycol, and glycerol; and the emulsifying agent is one or more of Span 80, Peregal O, and Tween.
    [0014] Preferably, the particle size of the composite graphene oxide-TEOS/silane nanomaterial is 50 to 300 nm.
    [0015] The present invention further provides the use of the graphene oxide-TEOS/silane composite nanomaterial prepared by using the above preparation method in a cementitious material.
    [0016] The present invention provides a method for preparing a composite graphene oxide-TEOS/silane nanomaterial, comprising the following steps: (1) mixing a dispersion of graphene oxide with a dispersant to obtain a first mixture; (2) mixing silane with an emulsifying agent to obtain a second mixture; (3) mixing the first mixture with the second mixture, and adding TEOS to obtain a mixture; and (4) drying the mixture, and grinding to obtain the composite graphene oxide-TEOS/silane nanomaterial, wherein there is no specific order between step (1) and step (2). In the present invention, graphene oxide plays a matrix role in a cement hydration process because a laminar structure of graphene oxide has rich functional groups, and guides the cement hydration process. , thereby improving the structure of the cement hydration product as well as the compressive strength and flexural strength of a cementitious material. A nanogel is easily formed after a hydrolysis reaction of TEOS, so that the product in the present invention changes from a state in solution to a state of nanogel, which facilitates the subsequent preparation of nanomaterial. In addition, a secondary hydration reaction is carried out between the nano–SiO 2 formed by the hydrolysis reaction of TEOS and a cement hydration product Ca(OH) 2 , to form a C–S–H nanogel . This improves the internal microstructure of a cementitious material as well as the compressive strength and flexural strength of the cementitious material.
    [0017] In addition, in the present invention, the laminar structure of graphene oxide is used to prevent the diffusion of external moisture and erosive ions inside the cementitious material, thereby improving the anti-diffusion performance. –penetrability of the cement-based material. Due to the good waterproof performance of the silane, the silane can be used to inhibit the diffusion of moisture into the cementitious material and improve the anti-penetrability performance of the cementitious material. The secondary hydration reaction takes place between the nano–SiO 2 formed by the hydrolysis reaction of TEOS and the cement hydration product Ca(OH) 2 , to form a C–S–H nanogel. This can improve the internal microstructure and compactness of the cementitious material, and enhance the anti-penetrability performance of the cementitious material.
    [0018] Example results show that after the graphene oxide–TEOS/silane composite nanomaterial prepared in the present invention was added to a cementitious material for 28 days of curing, the compressive strength of the material cementitious is 45.4 to 54.1 MPa, and its flexural strength is 1.75 to 1.96 MPa. In Comparative Example 1, the compressive strength is 41.2 MPa, and the flexural strength is 1.68 MPa. In Comparative Example 2, the compressive strength is 41.4 MPa, and the flexural strength is 1.62 MPa. In Comparative Example 3, the compressive strength is 40.9 MPa, and the flexural strength is 1.55 MPa. This indicates that the graphene oxide–TEOS/silane composite nanomaterial provided in the present invention can visibly improve both the compressive strength and the flexural strength of the cementitious material.
    [0019] detailed description
    [0020] The present invention provides a method for preparing a graphene oxide–TEOS/silane composite nanomaterial, comprising the following steps: (1) mixing a dispersion of graphene oxide with a dispersant to obtain a first mixture; (2) mixing silane with an emulsifying agent to obtain a second mixture; (3) mixing the first mixture with the second mixture, and adding TEOS to obtain a mixture; and (4) drying the mixture, and grinding to obtain the composite graphene oxide–TEOS/silane nanomaterial.
    [0021] There is no specific order between step (1) and step (2).
    [0022] In the present invention, the graphene oxide dispersion is mixed with the dispersant to obtain the first mixture.
    [0023] In the present invention, in parts by weight, the graphene oxide dispersion is preferably 5 to 45 parts, more preferably 5 to 40 parts, and most preferably 15 to 40 parts.
    [0024] In the present invention, the particle size of the graphene oxide in the graphene oxide dispersion is preferably 3 to 8 μm and more preferably 5 μm, and the mass concentration of the graphene oxide dispersion is preferably 0.5 to 5% and more preferably 1%. In the present invention, there is no particular requirement for the source of the graphene oxide dispersion, and a commercially available product well known to those skilled in the art can be used. In the present invention, graphene oxide has a laminar structure, and can prevent external moisture and corrosive ions from entering concrete. Moreover, since there are rich functional groups such as hydroxyl and carboxyl on the surface of graphene oxide, graphene oxide is firmly adsorbed on the concrete surface by chemical reaction, forms a matrix for a secondary hydration reaction of cement, optimizes the surface structure of concrete, and improves surface compactness and surface strength, so as to improve the compressive strength and flexural strength of a base material of cement. However, when the content of graphene oxide exceeds 45 parts, the stability of the composite cementitious material suddenly changes, which affects the stability of the composite nanomaterial; and delamination will occur immediately after the reaction.
    [0025] In the present invention, in parts by weight, the dispersant is preferably 1 to 5 parts and more preferably 2 to 4 parts. In the present invention, the dispersant is preferably one or more of sodium dodecylbenzenesulfonate, poly(vinyl alcohol), polyethylene glycol, and glycerol. In the present invention, the number average molecular weight of the polyethylene glycol is preferably 2,000. In the present invention, there is no particular requirement on the source of the dispersant, and a dispersant whose source is well known to those skilled in the art.
    [0026] In the present invention, the mixing is preferably carried out at a constant temperature of preferably 40 to 70°C, and more preferably 50°C. In the present invention, the mode of mixing is preferably agitation. In the present invention, there is no particular requirement for stirring speed and time, as long as the uniformly mixed first mixture can be obtained.
    [0027] In the present invention, the silane is mixed with the emulsifying agent to obtain the second mixture.
    [0028] In the present invention, in parts by weight, the silane is preferably 30 to 80 parts, more preferably 35 to 70 parts, and most preferably 40 to 60 parts.
    [0029] In the present invention, the silane is preferably one or more of methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, trimethoxyoctylsilane, and triethoxyoctylsilane. In the present invention, there is no particular requirement regarding the source of the silane, and a silane whose source is well known to those skilled in the art can be used. In the present invention, the silane has a relatively low surface energy, and can inhibit the diffusion of water from the outside into the cement-based material and the diffusion into the cement-based material, and enhance the compressive strength, flexural strength, and anti-penetrability performance of the cementitious material.
    [0030] In the present invention, in parts by weight, the emulsifying agent is preferably 1 to 5 parts and more preferably 2 to 4 parts. In the present invention, the emulsifying agent is preferably one or more of Span 80, Peregal O, and Tween. In the present invention, there is no particular requirement regarding the source of the emulsifying agent, and an emulsifying agent whose source is well known to those skilled in the art can be used.
    [0031] In the present invention, the silane and the emulsifying agent are preferably mixed at a constant temperature of preferably 40 to 70°C, and more preferably 50°C. In the present invention, the mode of mixing is preferably agitation. In the present invention, there is no particular requirement for stirring speed and time, as long as the uniformly mixed first mixture can be obtained.
    [0032] In the present invention, there is no order requirement regarding the preparation of the first mixture and the second mixture. In the present invention, whether the first mixture is prepared first or the second mixture is prepared first has no impact on the preparation of the graphene oxide–TEOS/silane composite nanomaterial.
    [0033] In the present invention, the first mixture is mixed with the second mixture, and TEOS is added to obtain a mixture.
    [0034] In the present invention, the second mixture is preferably allowed to stand at 60°C for 24 hours for later use.
    [0035] In the present invention, a pouring method is preferably adopted, the first mixture is added dropwise to the second mixture, or the second mixture is added dropwise to the first mixture. In the present invention, the pouring rate is preferably 2 to 10 ml/min and more preferably 5 ml/min. In the present invention, pouring facilitates a complete and uniform reaction between the silane and the graphene oxide, such that a condensation reaction takes place between a hydroxyl or carboxyl group carried by the graphene oxide and an alkoxy group. in a molecular group of silane, to connect silane and graphene oxide to each other, so that heterogeneous products due to local rapid reaction are avoided.
    [0036] In the present invention, after the mixing is completed, the TEOS is preferably added dropwise to the first mixture and the second mixture which are uniformly mixed. In the present invention, the pouring rate is preferably 2 to 10 ml/min and more preferably 5 ml/min.
    [0037] In the present invention, in parts by weight, the TEOS (tetraethyl orthosilicate) is preferably 30 to 90 parts, more preferably 30 to 60 parts, and most preferably 40 to 55 parts. In the present invention, there is no particular requirement for the source of TEOS, and a commercially available product well known to those skilled in the art can be used. In the present invention, a nanogel is easily formed after a hydrolysis reaction of TEOS, so that the product in the present invention changes from a solution state to a nanogel state. A second hydration reaction can be carried out between the nano–SiO 2 formed by the hydrolysis reaction of TEOS and a cement hydration product of a cement-based material, namely Ca(OH) 2 , to form a C–S–H nanogel. This improves the microstructure of the cementitious material, and further improves the compressive strength and the flexural strength of the cementitious material, and amplifies the anti-penetrability performance of the cementitious material.
    [0038] In the present invention, the mixture is dried and ground to obtain the composite graphene oxide-TEOS/silane nanomaterial.
    [0039] In the present invention, the drying method is preferably high temperature drying or freeze-drying, and a high temperature drying condition is preferably 60 to 90°C; and a freeze-drying condition is preferably -50 to -10°C, the ice crystallization time is 0.5 to 5 hours, the pressure for sublimation under reduced pressure is 1 to 10 Pa and better of 3 Pa, the drying time for sublimation is 1 to 10 hours and even better 4 to 8 hours. In the present invention, a nanomaterial having good dispersibility can be obtained due to drying, so that incomplete reaction in a cement-based material due to relatively large agglomeration of the nanomaterial is avoided.
    [0040] In the present invention, the grinding method is preferably high energy ball milling, and the high energy ball milling is preferably carried out by means of a planetary ball mill. The parameters of high energy ball milling are as follows: the ratio of balls to powder is preferably 50 to 200/1 and more preferably 100/1, the rotation speed is preferably 300 to 800 rpm and better still from 350 to 550 rpm; and the ball milling time is preferably 0.5 to 5 hours, more preferably 1.5 to 4.5 hours, and most preferably 3 hours. In the present invention, a nanomaterial in the appropriate particle size range can be obtained by grinding, so that incomplete reaction in a later stage due to a relatively large particle size of the nanomaterial is avoided.
    [0041] In the present invention, the particle size of the composite graphene oxide-TEOS/silane nanomaterial is preferably 50 to 300 nm and more preferably 60 to 200 nm.
    [0042] The present invention further provides the use of the graphene oxide-TEOS/silane composite nanomaterial prepared by using the preparation method in the above technical solution in a cementitious material. In the present invention, there is no particular requirement regarding the implementation of the use, and an implementation well known to those skilled in the art can be used. In the present invention, the use is specifically as follows: in a method of mixing a cementitious material, the graphene oxide–TEOS/silane composite nanomaterial is added into the cementitious material, wherein the dose of the graphene oxide–TEOS/silane composite nanomaterial is 2% to 15% of the mass of the cement; a slurry is obtained after the graphene oxide–TEOS/silane composite nanomaterial and the cementitious material are mixed evenly, and it is allowed to stand for 24 hours after being added into a mold; after which the mold is removed, curing is carried out under a standard curing condition to obtain a final cementitious material.
    [0043] The preparation method and the use of the graphene oxide–TEOS/silane composite nanomaterial provided by the present invention are described in detail below with reference to examples, but these cannot be construed as limiting the scope of protection of the present invention.
    [0044] Example 1
    [0045] 25 parts of graphene oxide dispersion (having a concentration of 1% and a particle size of 5 μm) are mixed, in parts by weight, with 2 parts of polyethylene glycol 2000 with stirring at 50° C. to obtain a first mixture.
    [0046] 65 parts of isobutyltriethoxysilane, 2 parts of Span 80 and 3 parts of Peregal O are mixed with stirring at 60° C. to obtain a second mixture; the second mixture is allowed to stand at 60°C for 24 hours, and is added dropwise to the first mixture at the rate of 5 ml/min, at a constant temperature of 60°C and at a rotation speed of 3000 rpm /min; and, after stirring for 2.5 hours, 60 parts of TEOS are added dropwise to a mixture of the first mixture and the second mixture, to obtain a mixture.
    [0047] The mixture obtained is placed directly in a lyophilization oven, and it is subjected to ice crystallization at −50° C. for 2 hours; then drying is carried out by sublimation for 6 hours, and the mixture is removed and placed in an oven at 50° C. for 8 hours of drying; and placing the dried graphene oxide–TEOS/silane composite nanomaterial in a planetary ball mill to undergo ball milling at a ball to powder ratio of 100:1 and at a specified rotational speed of 400 rpm for 3 hours to finally obtain the graphene oxide–TEOS/silane composite nanomaterial.
    [0048] The prepared graphene oxide-TEOS/silane composite nanomaterial is mixed in cement, and a cement slurry is prepared according to a standard method by setting a water to cement ratio of 0.4; the cement mixture is added to a mold and kept there for 24 hours; a hardened cement-based material is obtained after removing the mould; and placing the cured cementitious material in a standard curing environment to cure for 28 days to obtain a final cementitious material. According to a test, the compressive strength of cementitious material is 47.8MPa, the flexural strength is 1.80MPa, the capillary water absorption coefficient is 210.3g •m –2 •h –1 , and the chloride ion diffusion coefficient is 10.3 x 10 – – 1 2 m –2 •s –1 .
    [0049] Example 2
    [0050] 35 parts of graphene oxide dispersion (having a concentration of 1% and a particle size of 5 μm) are mixed, in parts by weight, with 3 parts of poly(vinyl alcohol) under stirring at 50° C. to obtain a first mixed.
    [0051] 50 parts of methyltrimethoxysilane, 3 parts of Tween and 2 parts of Peregal O are mixed with stirring at 60° C. to obtain a second mixture; the second mixture is allowed to stand at 60°C for 24 hours, and is added dropwise to the first mixture at the rate of 8 ml/min, at a constant temperature of 60°C and at a rotation speed of 3000 rpm /min; and, after stirring for 2 hours, 50 parts of TEOS are added dropwise to a mixture of the first mixture and the second mixture, to obtain a mixture.
    [0052] The mixture is placed directly in a lyophilization oven, and subjected to ice crystallization at −30° C. for 5 hours; then drying is carried out by sublimation for 5 hours, and the mixture is removed and placed in an oven at 50° C. for 8 hours of drying; and placing the dried graphene oxide–TEOS/silane composite nanomaterial in a planetary ball mill to undergo ball milling at a ball to powder ratio of 100:1 and at a specified rotational speed of 500 rpm for 2.5 hours to finally obtain the composite graphene oxide–TEOS/silane nanomaterial.
    [0053] The prepared graphene oxide-TEOS/silane composite nanomaterial is mixed in cement, and a cement slurry is prepared according to a standard method by setting a water to cement ratio of 0.45; the cement mixture is added to a mold and kept there for 24 hours; a hardened cement-based material is obtained after removing the mould; and placing the cured cementitious material in a standard curing environment to cure for 28 days to obtain a final cementitious material. According to a test, the compressive strength of cementitious material is 50.3MPa, the flexural strength is 1.83MPa, the capillary water absorption coefficient is 246.6g •m –2 •h –1 , and the chloride ion diffusion coefficient is 5.5 x 10 – –11 m –2 •s –1 .
    [0054] Example 3
    [0055] 40 parts of graphene oxide dispersion (having a concentration of 2% and a particle size of 8 μm) are mixed, in parts by weight, with 2 parts of poly(vinyl alcohol) and 2 parts of polyethylene glycol under stirring at 50° C. C to obtain a first mixture.
    [0056] 60 parts of isobutyltrimethoxysilane, 2 parts of Tween and 3 parts of Span 80 are mixed with stirring at 60° C. to obtain a second mixture; the second mixture is allowed to stand at 60°C for 24 hours, and is added dropwise to the first mixture at the rate of 4 ml/min, at a constant temperature of 60°C and at a speed of rotation of 3000 rpm /min; and, after stirring for 3 hours, 40 parts of TEOS are added dropwise to a mixture of the first mixture and the second mixture, to obtain a mixture.
    [0057] The mixture is placed directly in a lyophilization oven, and subjected to ice crystallization at −30° C. for 3 hours; then drying is carried out by sublimation for 5 hours, and the mixture is removed and placed in an oven at 50° C. for 10 hours of drying; and placing the dried graphene oxide–TEOS/silane composite nanomaterial in a planetary ball mill to undergo ball milling at a ball-to-powder ratio of 150:1 and at a specified rotational speed of 500 rpm for 3 hours to finally obtain the graphene oxide–TEOS/silane composite nanomaterial.
    [0058] The prepared graphene oxide-TEOS/silane composite nanomaterial is mixed in cement, and a cement slurry is prepared according to a standard method by setting a water to cement ratio of 0.5; the cement mixture is added to a mold and kept there for 24 hours; a hardened cement-based material is obtained after removing the mould; and placing the cured cementitious material in a standard curing environment to cure for 28 days to obtain a final cementitious material. According to a test, the compressive strength of cementitious material is 52.6MPa, the flexural strength is 1.92MPa, the capillary water absorption coefficient is 216.2g •m –2 •h –1 , and the chloride ion diffusion coefficient is 11.2 x 10 – –1 2 m –2 •s –1 .
    [0059] Example 4
    [0060] 45 parts of graphene oxide dispersion (having a concentration of 0.5% and a particle size of 4 μm) are mixed, in parts by weight, with 2 parts of glycerol and 2 parts of poly(vinyl alcohol) under stirring at 50°C to obtain a first mixture.
    [0061] 30 parts of isobutyltrimethoxysilane, 20 parts of methyltriethoxysilane, 30 parts of isobutyltriethoxysilane, 2 parts of Span 80 and 2 parts of Peregal O are mixed with stirring at 60° C. to obtain a second mixture; the second mixture is allowed to stand at 60°C for 24 hours, and is added dropwise to the first mixture at the rate of 5 ml/min, at a constant temperature of 60°C and at a rotation speed of 3000 rpm /min; and, after stirring for 2.5 hours, 80 parts of TEOS are added dropwise to a mixture of the first mixture and the second mixture, to obtain a mixture.
    [0062] The mixture is placed directly in a lyophilization oven, and subjected to ice crystallization at −40° C. for 2.5 hours; then drying is carried out by sublimation for 5 hours, and the mixture is removed and placed in an oven at 50° C. for 6 hours of drying; and placing the dried graphene oxide–TEOS/silane composite nanomaterial in a planetary ball mill to undergo ball milling at a ball-to-powder ratio of 200:1 and at a specified rotational speed of 300 rpm for 5 hours to finally obtain the graphene oxide–TEOS/silane composite nanomaterial.
    [0063] The prepared graphene oxide-TEOS/silane composite nanomaterial is mixed in cement, and a cement slurry is prepared according to a standard method by setting a water to cement ratio of 0.4; the cement mixture is added to a mold and kept there for 24 hours; a hardened cement-based material is obtained after removing the mould; and placing the cured cementitious material in a standard curing environment to cure for 28 days to obtain a final cementitious material. According to a test, the compressive strength of cementitious material is 54.1MPa, the flexural strength is 1.96MPa, the capillary water absorption coefficient is 213.5g •m –2 •h –1 , and the chloride ion diffusion coefficient is 17.3 x 10 – –12 m –2 •s –1 .
    [0064] Example 5
    [0065] 20 parts of graphene oxide dispersion (having a concentration of 5% and a particle size of 6 μm) are mixed, in parts by weight, with 1 part of glycerol and 2 parts of polyethylene glycol under stirring at 50° C. to obtain a first mix.
    [0066] 15 parts of isobutyltrimethoxysilane, 20 parts of methyltriethoxysilane, 15 parts of isobutyltriethoxysilane, 1 part of Span 80 and 2 parts of Tween are mixed with stirring at 60° C. to obtain a second mixture; the second mixture is allowed to stand at 60°C for 24 hours, and is added dropwise to the first mixture at the rate of 5 ml/min, at a constant temperature of 60°C and at a rotation speed of 3000 rpm /min; and, after stirring for 2.5 hours, 30 parts of TEOS are added dropwise to a mixture of the first mixture and the second mixture, to obtain a mixture.
    [0067] The mixture is placed directly in a drying oven at high temperature for 12 hours of drying at 80° C.; and placing the dried graphene oxide–TEOS/silane composite nanomaterial in a planetary ball mill to undergo ball milling at a ball-to-powder ratio of 200:1 and at a specified rotational speed of 600 rpm for 4 hours to finally obtain the graphene oxide–TEOS/silane composite nanomaterial.
    [0068] The prepared graphene oxide-TEOS/silane composite nanomaterial is mixed in cement, and a cement slurry is prepared according to a standard method by setting a water to cement ratio of 0.4; the cement mixture is added to a mold and kept there for 24 hours; a hardened cement-based material is obtained after removing the mould; and placing the cured cementitious material in a standard curing environment to cure for 28 days to obtain a final cementitious material. According to a test, the compressive strength of cementitious material is 46.3MPa, the flexural strength is 1.75MPa, the capillary water absorption coefficient is 221.9g •m –2 •h –1 , and the chloride ion diffusion coefficient is 3.3 x 10 – –12 m –2 •s –1 .
    [0069] Example 6
    [0070] 10 parts of graphene oxide dispersion (having a concentration of 3% and a particle size of 7 μm) are mixed, in parts by weight, with 1 part of glycerol and 2 parts of polyethylene glycol under stirring at 50° C. to obtain a first mix.
    [0071] 25 parts of methyltriethoxysilane, 15 parts of methyltrimethoxysilane, 20 parts of trimethoxyoctylsilane, 3 parts of Span 80 and 2 parts of Tween are mixed with stirring at 60° C. to obtain a second mixture; the second mixture is allowed to stand at 60°C for 24 hours, and is added dropwise to the first mixture at the rate of 5 ml/min, at a constant temperature of 60°C and at a rotation speed of 3000 rpm /min; and, after stirring for 2.5 hours, 70 parts of TEOS are added dropwise to a mixture of the first mixture and the second mixture, to obtain a mixture.
    [0072] The mixture is placed directly in a drying oven at high temperature for 10 hours of drying at 80° C.; and placing the dried graphene oxide–TEOS/silane composite nanomaterial in a planetary ball mill to undergo ball milling at a ball-to-powder ratio of 250:1 and at a specified rotational speed of 600 rpm for 5 hours to finally obtain the graphene oxide–TEOS/silane composite nanomaterial.
    [0073] The prepared graphene oxide-TEOS/silane composite nanomaterial is mixed in cement, and a cement slurry is prepared according to a standard method by setting a water to cement ratio of 0.6; the cement mixture is added to a mold and kept there for 24 hours; a hardened cement-based material is obtained after removing the mould; and placing the cured cementitious material in a standard curing environment to cure for 28 days to obtain a final cementitious material. According to a test, the compressive strength of cementitious material is 45.4MPa, the flexural strength is 1.72MPa, the capillary water absorption coefficient is 222.6g •m –2 •h –1 , and the chloride ion diffusion coefficient is 18.5 x 10 – –12 m –2 •s –1 .
    [0074] Comparative example 1
    [0075] A performance test is performed on a cementitious material not doped with a graphene oxide–TEOS/silane composite nanomaterial. According to the test, after 28 days of curing the cementitious material not doped with graphene oxide–TEOS/silane composite nanomaterial, the compressive strength of the cementitious material is 41.2MPa, the flexural strength is 1.68 MPa, capillary water absorption coefficient is 288.5 g•m –2 •h – 1 , and chloride ion diffusion coefficient is 9.7 x 10 – – 11 m – 2 •s –1 .
    [0076] Comparative example 2
    [0077] 25 parts of graphene oxide dispersion (having a concentration of 1% and a particle size of 5 μm) are mixed, in parts by weight, with 2 parts of polyethylene glycol 2000 with stirring at 50° C. to obtain a first mixture.
    [0078] 65 parts of isobutyltriethoxysilane, 2 parts of Span 80 and 3 parts of Peregal O are mixed with stirring at 60° C. to obtain a second mixture; the second mixture is allowed to stand at 60°C for 24 hours, and is added dropwise to the first mixture at the rate of 5 ml/min, at a constant temperature of 60°C and at a rotation speed of 3000 rpm /min; and, after stirring for 2.5 hours, 60 parts of TEOS are added dropwise to a mixture of the first mixture and the second mixture, to obtain a composite graphene oxide-TEOS/silane nanomaterial.
    [0079] The graphene oxide–TEOS/silane composite nanomaterial is mixed in cement, and a cement slurry is prepared according to a standard method by setting a water to cement ratio of 0.4; the cement mixture is added to a mold and kept there for 24 hours; the mold is removed; and placing a prepared cured cementitious material in a standard curing environment to cure for 28 days to obtain a final cementitious material. According to a test, the compressive strength of cementitious material is 41.4MPa, the flexural strength is 1.62MPa, the capillary water absorption coefficient is 290.4g •m –2 •h –1 , and the chloride ion diffusion coefficient is 10.5 x 10 – –12 m –2 •s –1 .
    [0080] Comparative example 3
    [0081] 25 parts of graphene oxide dispersion (having a concentration of 1% and a particle size of 5 μm) are mixed, in parts by weight, with 2 parts of polyethylene glycol 2000 with stirring at 50° C. to obtain a first mixture.
    [0082] 65 parts of isobutyltriethoxysilane, 2 parts of Span 80 and 3 parts of Peregal O are mixed with stirring at 60° C. to obtain a second mixture; the second mixture is allowed to stand at 60°C for 24 hours, and is added dropwise to the first mixture at the rate of 5 ml/min, at a constant temperature of 60°C and at a rotation speed of 3000 rpm /min; and, after stirring for 2.5 hours, 60 parts of TEOS are added dropwise to a mixture of the first mixture and the second mixture, to obtain a mixture.
    [0083] The mixture obtained is placed directly in a freeze-drying oven, and it is subjected to ice crystallization at −50° C. for 3 hours; then drying by sublimation is carried out for 6 hours, and the mixture is removed and placed in an oven at 50°C for 8 hours of drying, to obtain a composite nanomaterial of graphene oxide–TEOS/silane.
    [0084] The prepared graphene oxide-TEOS/silane composite nanomaterial is mixed in cement, and a cement slurry is prepared according to a standard method by setting a water to cement ratio of 0.4; the cement mixture is added to a mold and kept there for 24 hours; the mold is removed; and placing a prepared cured cementitious material in a standard curing environment to cure for 28 days to obtain a final cementitious material. According to a test, the compressive strength of cementitious material is 40.9MPa, the flexural strength is 1.55MPa, the capillary water absorption coefficient is 293.2g •m –2 •h –1 , and the chloride ion diffusion coefficient is 10.8 x 10 – –12 m –2 •s –1 .
    [0085] From the examples and comparative examples above, it can be learned that after the graphene oxide–TEOS/silane composite nanomaterial provided in the present invention was added into a cementitious material for 28 days of hardening, the compressive strength of the cementitious material is 45.4-54.1 MPa, and its flexural strength is 1.75-1.96 MPa. In Comparative Example 1, the compressive strength is 41.2 MPa, and the flexural strength is 1.68 MPa. In Comparative Example 2, the compressive strength is 41.4 MPa, and the flexural strength is 1.62 MPa. In Comparative Example 3, the compressive strength is 40.9 MPa, and the flexural strength is 1.55 MPa. This indicates that the graphene oxide–TEOS/silane composite nanomaterial provided in the present invention can visibly improve both the compressive strength and the flexural strength of the cementitious material.
    [0086] The above descriptions are merely preferred implementations of the present invention. It should be noted that one of ordinary skill in the art can make several additional improvements and modifications without departing from the principles of the present invention, but such improvements and modifications should be considered to be within the scope. protection of the present invention.
    权利要求:
    Claims (9)
    [0001]
    A method of preparing a graphene oxide-tetraethyl orthosilicate (TEOS)/silane composite nanomaterial, comprising the following steps: (1) mixing a dispersion of graphene oxide with a dispersant to obtain a first mixture; (2) mixing silane with an emulsifying agent to obtain a second mixture; (3) mixing the first mixture with the second mixture, and adding TEOS to obtain a mixture; and (4) drying the mixture, and grinding to obtain the composite graphene oxide–TEOS/silane nanomaterial, wherein there is no specific order between step (1) and step (2).
    [0002]
    A method of preparation according to claim 1, wherein the drying comprises high temperature drying or freeze-drying.
    [0003]
    Preparation process according to claim 1, wherein the milling is high energy ball milling.
    [0004]
    Preparation process according to claim 1, wherein the mixing in step (3) is carried out at a constant temperature of 50 to 80°C for 2 to 3 hours.
    [0005]
    A process according to claim 1, wherein the starting components for preparing the composite graphene oxide-TEOS/silane nanomaterial comprise the following components, in parts by weight: 5 to 45 parts graphene oxide dispersion, 30 to 90 parts TEOS, 30 to 80 parts silane, 1 to 5 parts emulsifying agent, and 1 to 5 parts dispersant.
    [0006]
    The preparation method according to claim 1 or 5, wherein the particle size of graphene oxide in the graphene oxide dispersion is 3 to 8 µm, and the mass concentration of graphene oxide in the dispersion of graphene oxide is 0.5-5%.
    [0007]
    A method of preparation according to claim 1 or 5, wherein the silane is one or more of methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, trimethoxyoctylsilane, and triethoxyoctylsilane.
    [0008]
    A method of preparation according to claim 1 or 5, wherein the dispersant is one or more of sodium dodecylbenzenesulfonate, poly(vinyl alcohol), polyethylene glycol, and glycerol; and the emulsifying agent is one or more of Span 80, Peregal O, and Tween.
    [0009]
    Use of the graphene oxide-TEOS/silane composite nanomaterial prepared using the preparation method of any one of claims 1 to 8, in a cementitious material.
    类似技术:
    公开号 | 公开日 | 专利标题
    FR3096983A1|2020-12-11|Process for the preparation and use of graphene oxide – TEOS / silane composite nanomaterial
    CN105399091B|2017-05-10|High dispersion photosensitive graphene and preparing method thereof
    CN1315754C|2007-05-16|Method for precission shaping ceramic blank by semi-water-base injection-moulding gel process
    BE898398A|1984-03-30|Additive for concrete comprising several components containing microsilica, process for preparing it and concrete containing it.
    EP2655285A1|2013-10-30|Method for inserting carbon nanofillers into an inorganic curable system
    CN106830043B|2018-02-09|A kind of method of surface modified nano calcium carbonate
    JP4986444B2|2012-07-25|Hydrophobic inorganic powder and method for producing the same
    FR2961806A1|2011-12-30|PERMEABLE CONCRETE
    CN109650807B|2022-01-04|High-strength cement concrete prepared from modified fly ash and polymer and preparation method thereof
    JP2000026141A|2000-01-25|Carbon black for coloring cement and method for coloring cement molded article
    JP3215516B2|2001-10-09|Hydraulic composition and method for producing concrete pile using the composition
    JP2013014447A|2013-01-24|Cement hardened body, method for manufacturing the same, and cement composition
    EP1534647B1|2015-03-04|Hydraulic binder composition
    CN111392721A|2020-07-10|Graphene oxide dispersion liquid and preparation method and application thereof
    CN109809749A|2019-05-28|A kind of construction method of graphite alkenes cement-base composite material
    CN107473659B|2020-01-14|Modified cellulose nanocrystalline reinforced cement paste material and preparation method thereof
    EP3006416B1|2018-12-26|Improved method for producing an eco-friendly concrete
    JP2021516181A|2021-07-01|New composition to improve concrete performance
    FR2700162A1|1994-07-08|Composite of hydraulic binder and lignocellulosic granulate
    CN108249812A|2018-07-06|A kind of slow-release solid water-reducing agent based on haydite and preparation method thereof
    JP2887561B2|1999-04-26|Method for manufacturing high strength centrifugal concrete compact
    JP3314554B2|2002-08-12|Silicon nitride powder and silicon nitride-containing aqueous slurry
    CN111646765B|2021-11-02|Crack-resistant mortar with few pores and preparation method thereof
    CN110204242B|2021-08-10|Enhanced expansion anti-cracking agent and preparation method thereof
    KR100888826B1|2009-03-17|Coating method of silica fume for high strength conctere
    同族专利:
    公开号 | 公开日
    CN110204244B|2020-08-18|
    WO2020244506A1|2020-12-10|
    CN110204244A|2019-09-06|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    CN102275939A|2011-07-28|2011-12-14|浙江大学|Preparation method of two-dimensional porous silica nanosheet|
    KR102101749B1|2013-04-03|2020-05-12|주식회사 동진쎄미켐|Moisture transmission resistant coating composition comprising graphene oxide and silicone|
    KR20170075990A|2015-12-24|2017-07-04|김동기|A cement block method and lightweight cement method and lightweight cement high-strength containing graphene|
    US20180282214A1|2017-04-04|2018-10-04|Schlumberger Technology Corporation|Compositions and Methods for Cementing Wells|
    CN107022080A|2017-04-28|2017-08-08|青岛理工大学|A kind of preparation method of novel silicon alkanes plural gel waterproof material|
    CN107699130A|2017-11-10|2018-02-16|青岛理工大学|A kind of silane graphene waterproof composite material and preparation method thereof|
    CN108483980B|2018-04-12|2021-01-26|清华大学|Preparation method of nano carbon material-polymer-silicate composite micro-nano particle nucleating agent|
    CN108862265A|2018-07-18|2018-11-23|深圳大学|A kind of graphene oxide-nanometer silicon dioxide composite material and preparation method thereof|
    CN110183963B|2019-06-06|2020-11-20|青岛理工大学|Graphene oxide-TEOS/silane composite gel material and preparation method and application thereof|
    CN110204244B|2019-06-06|2020-08-18|青岛理工大学|Preparation method and application of graphene oxide-TEOS/silane composite nanomaterial|CN110204244B|2019-06-06|2020-08-18|青岛理工大学|Preparation method and application of graphene oxide-TEOS/silane composite nanomaterial|
    CN110183963B|2019-06-06|2020-11-20|青岛理工大学|Graphene oxide-TEOS/silane composite gel material and preparation method and application thereof|
    GB2595009A|2019-06-06|2021-11-17|Univ Qingdao Technology|Graphene oxide-TEOS/silane composite gel material, preparation method therefor and use thereof|
    法律状态:
    2021-05-17| PLFP| Fee payment|Year of fee payment: 2 |
    优先权:
    申请号 | 申请日 | 专利标题
    CN201910491260.6|2019-06-06|
    CN201910491260.6A|CN110204244B|2019-06-06|2019-06-06|Preparation method and application of graphene oxide-TEOS/silane composite nanomaterial|
    [返回顶部]