CN117509655A - Synthesis method of rice-grain-shaped nickel-iron bimetallic silicate nano aggregate and epoxy resin composite material - Google Patents
Synthesis method of rice-grain-shaped nickel-iron bimetallic silicate nano aggregate and epoxy resin composite material Download PDFInfo
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- CN117509655A CN117509655A CN202311499627.1A CN202311499627A CN117509655A CN 117509655 A CN117509655 A CN 117509655A CN 202311499627 A CN202311499627 A CN 202311499627A CN 117509655 A CN117509655 A CN 117509655A
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- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 61
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000001308 synthesis method Methods 0.000 title claims description 5
- 229910052615 phyllosilicate Inorganic materials 0.000 claims abstract description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 239000013384 organic framework Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 8
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000004593 Epoxy Substances 0.000 claims description 29
- 238000001723 curing Methods 0.000 claims description 24
- 239000000178 monomer Substances 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- CBEVWPCAHIAUOD-UHFFFAOYSA-N 4-[(4-amino-3-ethylphenyl)methyl]-2-ethylaniline Chemical group C1=C(N)C(CC)=CC(CC=2C=C(CC)C(N)=CC=2)=C1 CBEVWPCAHIAUOD-UHFFFAOYSA-N 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- 241000209094 Oryza Species 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 235000009566 rice Nutrition 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000009849 vacuum degassing Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 238000005266 casting Methods 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000005461 lubrication Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract 2
- 239000000463 material Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 14
- 238000012360 testing method Methods 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- FMQXRRZIHURSLR-UHFFFAOYSA-N dioxido(oxo)silane;nickel(2+) Chemical compound [Ni+2].[O-][Si]([O-])=O FMQXRRZIHURSLR-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- PHIQPXBZDGYJOG-UHFFFAOYSA-N sodium silicate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-][Si]([O-])=O PHIQPXBZDGYJOG-UHFFFAOYSA-N 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229940032296 ferric chloride Drugs 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
-
- 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
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/20—Two-dimensional structures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a method for synthesizing rice-shaped nickel-iron bimetallic phyllosilicate nano aggregates, which comprises the following steps: uniformly dissolving nickel chloride, ferric chloride and terephthalic acid in N, N-dimethylformamide according to a certain proportion, and obtaining a nickel-iron bimetallic organic framework precursor after hydrothermal reaction and solid-liquid separation; and uniformly dispersing the nickel-iron bimetal organic framework precursor and sodium silicate in an absolute ethyl alcohol-water solution according to a certain proportion, adding a proper amount of sodium hydroxide solution for hydrothermal reaction, and then carrying out solid-liquid separation, washing and drying to obtain the rice-shaped nickel-iron bimetal layered silicate nano aggregate. The invention also discloses a rice-shaped nickel-iron bimetallic phyllosilicate nano aggregate and an epoxy resin composite material containing the rice-shaped nickel-iron bimetallic phyllosilicate nano aggregate. The rice-shaped nickel-iron bimetallic phyllosilicate nano-aggregate can obviously reduce the lubrication coefficient of epoxy resin and improve or maintain the mechanical property of the epoxy resin, and the prepared epoxy resin composite material has the characteristics of self lubrication and high rigidity, and can be applied to precise moving parts with high requirements on lubrication and mechanical property.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a method for synthesizing rice-shaped nickel-iron bimetallic silicate nano aggregates and an epoxy resin composite material.
Background
The epoxy resin has the advantages of high strength, good chemical corrosion resistance, excellent bonding strength, simple molding process and the like, is widely applied, and is widely used in various fields of aerospace, transportation, petrochemical industry, civil buildings and the like, such as matrix materials, functional coating materials, bonding materials and the like which become high-performance composite materials. However, the lack of self-lubricating properties of epoxy resins themselves has led to great limitations in the application of epoxy resins in fields with relative motion requirements, such as mechanical moving parts. Although many researches have demonstrated that the introduction of two-dimensional layered nanomaterials into epoxy resins can effectively reduce the coefficient of friction of the material, improving its lubricity; however, in view of the characteristics of difficult dispersion and easy agglomeration of the two-dimensional layered nanomaterial, the preparation process of the material becomes particularly complex, time-consuming and labor-consuming, and the cost of the product in the manufacturing link is greatly increased. Therefore, if the dispersion capability of the two-dimensional layered nano material in the epoxy matrix is effectively enhanced, the two-dimensional layered nano material can be uniformly dispersed, so that the lubrication modification effect of the material is fully exerted as much as possible, and the epoxy resin composite material with low friction coefficient and good self-lubricating performance is very important.
Disclosure of Invention
Based on the technical problems in the background technology, the invention provides a synthesis method of a rice-shaped nickel-iron bimetallic silicate nano aggregate and an epoxy resin composite material. According to the invention, a hydrothermal method with simple and convenient process and controllable conditions is utilized to firstly prepare the nickel-iron bimetallic organic frame, so that the rice-shaped nickel-iron bimetallic silicate nano aggregate is synthesized, and finally, the rice-shaped nickel-iron bimetallic silicate nano aggregate modified epoxy resin composite material is prepared through a solution blending technology.
The invention provides a method for synthesizing rice-shaped nickel-iron bimetallic silicate nano-aggregates, which comprises the following steps:
s1, adding soluble nickel salt, soluble ferric salt and terephthalic acid into N, N-dimethylformamide according to a certain proportion, uniformly mixing, adding 4mL of absolute ethyl alcohol/water solution, transferring to a polytetrafluoroethylene reaction kettle after complete dissolution, carrying out hydrothermal reaction at 130 ℃ for 3 hours, and obtaining a product after repeated washing and centrifugation and drying, namely the nickel-iron bimetal organic framework precursor.
S2, dispersing the nickel-iron bimetal organic framework precursor and sodium silicate in 120mL of absolute ethyl alcohol/water solution in a certain proportion, fully and uniformly stirring, adding 6mL of sodium hydroxide solution, ultrasonically treating for 30min, transferring to a polytetrafluoroethylene reaction kettle, performing hydrothermal reaction at 160 ℃ for 15h, and washing and drying the obtained precipitate to obtain the rice-shaped nickel-iron bimetal layered silicate nano aggregate.
Preferably, in the step S1, the amount of the soluble nickel salt is 0.43-0.85 mmol, the amount of the soluble iron salt is 0-0.21 mmol, the amount of the terephthalic acid is 0.85mmol, and the volume ratio of the absolute ethyl alcohol to the aqueous solution is 1:1.
Preferably, in the step S2, the dosage of the nickel-iron bimetallic precursor is 0.8g, the dosage of the sodium silicate is 1.14g, the volume ratio of the absolute ethyl alcohol to the aqueous solution is 1:1, and the concentration of the sodium hydroxide solution is 1mol/L.
Preferably, the drying conditions in steps S1 and S2 are vacuum drying at 75 ℃ for at least 24 hours.
Preferably, the soluble nickel salt is at least one of nickel chloride, nickel nitrate and nickel acetate; the soluble ferric salt is at least one of ferric chloride, ferric nitrate and ferric acetate.
A rice-shaped nickel-iron bimetallic silicate nano aggregate is prepared by the preparation method.
The epoxy resin composite material comprises epoxy monomer, curing agent and rice-shaped nickel-iron bimetallic silicate nano aggregate, wherein the rice-shaped nickel-iron bimetallic silicate nano aggregate accounts for 1-10% of the total weight of the raw material.
Preferably, the epoxy resin composite material comprises the following raw materials in percentage by weight: 71-76% of epoxy monomer, 22-25% of curing agent and 1-6% of rice-shaped nickel-iron bimetallic phyllosilicate nano aggregate.
Preferably, the epoxy monomer is bisphenol A type epoxy monomer, and the epoxy value is 0.41-0.47; the curing agent is 4,4' -methylenebis (2-ethylaniline).
The preparation method of the epoxy resin composite material comprises the following steps: adding the rice-shaped nickel-iron bimetallic phyllosilicate nano aggregate into acetone to be uniformly dispersed to obtain a dispersion liquid, adding the dispersion liquid into an epoxy monomer, uniformly stirring, adding a curing agent, and carrying out vacuum degassing, casting and curing to obtain the nano-sized nickel-iron bimetallic phyllosilicate nano aggregate.
Preferably, the curing step includes: curing at 100 ℃ for 2 hours, then curing at 150 ℃ for 4 hours, and finally storing at least 72 hours at room temperature.
The beneficial effects of the invention are as follows:
the layered nickel silicate is a novel two-dimensional nano material which is very focused in research in recent years, has the characteristics of regular and ordered lamellar structure, large surface area, adjustable interlayer performance, designable morphology and the like, and has very wide application prospect in the fields of magnetism, electricity and catalysis. The synthesis method of the layered nickel silicate is more, and products with different components and morphologies can be controlled by precisely regulating and controlling the reaction conditions. However, the lamellar structure of lamellar nickel silicate of lamellar stacked structure is difficult to effectively peel, and the application field thereof is limited to a large extent. The invention designs and prepares a rice-shaped nickel-iron bimetallic phyllosilicate nano aggregate based on the structural genetics concept by taking a metal organic framework with adjustable components, structures and morphology as a precursor and utilizing a simple hydrothermal synthesis technology. The metal organic framework is used as a template and a reaction nickel source to form a large number of macroscopic aggregates of fine lamellar, and a self-hybridization structure with micro-nano trans-scale is constructed, so that on one hand, the dispersion of the nano lamellar of nickel silicate in epoxy resin is facilitated, and on the other hand, the performance of the epoxy resin composite material can be modulated by controlling the microscopic morphology and structure.
The mechanical and friction performance tests show that the rice-shaped nickel-iron bimetallic silicate nano aggregate obtained by the technology disclosed by the invention can keep the mechanical strength and the elastic modulus of the epoxy resin composite material to a certain extent or even slightly improve the mechanical strength and the elastic modulus of the epoxy resin composite material under the condition of proper addition, can also reduce the average friction coefficient by 12.6%, can obviously inhibit the running-in stage of the initial friction stage, promotes the friction process to enter the steady friction stage more quickly, and shows excellent antifriction effect.
Drawings
FIG. 1 is an x-ray diffraction pattern of a nickel-iron bimetallic organic framework precursor as described in example 1;
FIG. 2 is an x-ray diffraction pattern of the rice-shaped nickel-iron bimetallic silicate nano-aggregates described in example 1;
FIG. 3 is a scanning electron micrograph of a nickel-iron bimetallic organic framework precursor as described in example 1;
FIG. 4 is a scanning electron micrograph of the rice-shaped nickel-iron bimetallic silicate nano-aggregates described in example 1;
FIG. 5 is a transmission electron micrograph of a rice-shaped nickel-iron bimetallic silicate nano-aggregate as described in example 1;
FIG. 6 is a high resolution transmission electron micrograph of a rice-shaped nickel-iron bimetallic silicate nano-aggregate as described in example 1;
FIG. 7 is a graph showing the friction coefficient of the pure epoxy resin described in comparative example 1;
fig. 8 is a graph of the coefficient of friction of the epoxy resin composite described in example 7.
Detailed Description
In order to make the purposes, technical schemes and advantages of the embodiments of the present invention more clear, the technical schemes in the embodiments of the present invention are clearly and completely described. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
a method for synthesizing rice-shaped nickel-iron bimetallic silicate nano-aggregates comprises the following steps:
s1, dissolving 0.154g of nickel chloride hexahydrate, 0.057g of ferric chloride hexahydrate and 0.143g of terephthalic acid in 10mL of N, N-dimethylformamide at room temperature, and strongly stirring for 5min; then, 4mL of the solution was added in a volume ratio of 1:1, continuously stirring for 10min; transferring the mixture to an autoclave with a polytetrafluoroethylene substrate, performing hydrothermal reaction for 3 hours at 130 ℃, and performing repeated centrifugation, washing with deionized water and absolute ethyl alcohol, and drying overnight to obtain a rice-shaped nickel-iron bimetallic organic framework precursor;
s2, weighing 1.14g of sodium silicate nonahydrate and 0.8g of the nickel-iron bimetallic organic frame precursor prepared in the S1, and adding the precursor into 120mL of the solution with the volume ratio of 1:1, strongly stirring for 30min, adding 6mL of 1mol/L sodium hydroxide solution, performing ultrasonic treatment again for 30min, transferring to an autoclave with a polytetrafluoroethylene substrate, performing hydrothermal reaction at 160 ℃ for 15h, and performing repeated centrifugation, washing with deionized water and absolute ethyl alcohol and drying overnight to obtain the product, namely the nickel-iron bimetallic phyllosilicate nano aggregate.
Example 2
S1, dissolving 0.196g of nickel nitrate hexahydrate, 0.093g of ferric chloride hexahydrate and 0.235g of terephthalic acid in 10mL of N, N-dimethylformamide at room temperature, and strongly stirring for 5min; then adding 2mL of sodium hydroxide solution with the concentration of 0.4mol/L, and continuously stirring for 30min; transferring the mixture to an autoclave with a polytetrafluoroethylene substrate, performing hydrothermal reaction at 100 ℃ for 15 hours, and performing repeated centrifugation, washing with deionized water and absolute ethyl alcohol, and drying overnight to obtain a nickel-iron bimetal organic framework precursor;
s2, weighing 1.14g of sodium silicate nonahydrate and 0.8g of the nickel-iron bimetallic organic frame precursor prepared in the S1, and adding the precursor into 120mL of the solution with the volume ratio of 1:1, after strongly stirring for 30min, adding 6mL of sodium hydroxide solution with the concentration of 1mol/L, carrying out ultrasonic treatment again for 30min, transferring into an autoclave with a polytetrafluoroethylene substrate, carrying out hydrothermal reaction at 160 ℃ for 15h, and obtaining a powdery product after repeated centrifugation, washing with deionized water and absolute ethyl alcohol, and drying overnight.
Example 3
S1, dissolving 0.178g of nickel nitrate hexahydrate, 0.109g of ferric chloride hexahydrate and 0.185g of terephthalic acid in 12mL of N, N-dimethylformamide at room temperature, and strongly stirring for 5min; then adding 2.1mL of sodium hydroxide solution with the concentration of 0.4mol/L, and continuously stirring for 30min; transferring the mixture to an autoclave with a polytetrafluoroethylene substrate, performing hydrothermal reaction for 15h at 120 ℃, and performing repeated centrifugation, washing with deionized water and absolute ethyl alcohol, and drying overnight to obtain a nickel-iron bimetal organic framework precursor;
s2 is the same as in example 2.
Example 4
An epoxy resin composite material comprises the following raw materials in percentage by mass: 75.18 percent of epoxy monomer, 24.06 percent of curing agent and 0.76 percent of rice-shaped nickel-iron bimetallic phyllosilicate nano aggregate prepared in the example 1.
Wherein the epoxy monomer is bisphenol A type epoxy monomer, and the epoxy value is 0.41-0.47; the curing agent is 4,4' -methylenebis (2-ethylaniline).
The preparation method of the epoxy resin composite material comprises the following steps: adding 1.0g of rice-shaped nickel-iron bimetallic phyllosilicate nano aggregate into 25mL of acetone, carrying out ultrasonic oscillation for 1h, carrying out pre-dispersion uniformly to obtain a dispersion liquid, slowly dripping the dispersion liquid into 100g of epoxy monomer which is heated at 70 ℃ in advance, fully stirring for 4h, adding molten 4,4' -methylenebis (2-ethylaniline), pouring into a 60 ℃ preheated silica gel mold after uniform mixing, transferring to a vacuum oven for vacuum degassing treatment for 30min, curing for 2h at 100 ℃, and curing for 2h at 150 ℃ to obtain the epoxy resin composite material.
Example 5
An epoxy resin composite material comprises the following raw materials in percentage by mass: 74.02 percent of epoxy monomer, 23.69 percent of curing agent and 2.29 percent of rice-shaped nickel-iron bimetallic phyllosilicate nano aggregate prepared in the example 1.
Other materials and preparation methods were the same as in example 4.
Example 6
An epoxy resin composite material comprises the following raw materials in percentage by mass: 72.58% of epoxy monomer, 23.31% of curing agent and 3.83% of rice-grain nickel-iron bimetallic phyllosilicate nano aggregate prepared in example 1.
Other materials and preparation methods were the same as in example 4.
Example 7
An epoxy resin composite material comprises the following raw materials in percentage by mass: 71.67% of epoxy monomer, 22.93% of curing agent and 5.39% of rice-grain nickel-iron bimetallic phyllosilicate nano aggregate prepared in example 1.
Other materials and preparation methods were the same as in example 4.
Comparative example 1
The pure epoxy resin material comprises the following raw materials in percentage by mass: 75.76% of epoxy monomer and 24.24% of curing agent.
Wherein the epoxy monomer is bisphenol A type epoxy monomer, and the epoxy value is 0.41-0.47; the curing agent is 4,4' -methylenebis (2-ethylaniline).
The pure epoxy resin material comprises: 100g of epoxy monomer and 32g of 4,4 '-methylenebis (2-ethylaniline) were preheated at 70 ℃ and 105 ℃ respectively, then molten 4,4' -methylenebis (2-ethylaniline) was slowly dropped into the epoxy monomer and well mixed, poured into a 60 ℃ preheated silica gel mold and transferred to a vacuum oven for vacuum degassing treatment for 30min, cured at 100 ℃ for 2h, and cured at 150 ℃ for 2h, thus obtaining the epoxy resin material.
Comparative example 2
An epoxy resin composite material comprises the following raw materials in percentage by mass: 71.67% of epoxy monomer, 22.93% of curing agent and 5.39% of product prepared in example 2.
Other materials and preparation methods were the same as in example 4.
Comparative example 3
An epoxy resin composite material comprises the following raw materials in percentage by mass: 71.67% of epoxy monomer, 22.93% of curing agent and 5.39% of product prepared in example 3.
Other materials and preparation methods were the same as in example 4.
The nickel-iron bimetallic organic framework and nickel-iron bimetallic layered silicate aggregate prepared in example 1 were subjected to phase structure and microscopic morphology analysis, and the results are shown in fig. 1 to 6. As can be seen from the x-ray diffraction patterns of fig. 1 and 2, the grain-shaped nickel-iron bimetallic phyllosilicate nano-aggregate is successfully synthesized by a hydrothermal method by taking the nickel-iron bimetallic organic framework as a precursor; fig. 3 shows that the nickel-iron metal organic frame is in the shape of rice grains, the surface is smooth and flat, and fig. 4, 5 and 6 show that the prepared nickel-iron bimetallic silicate nano aggregate is in the shape of rice grains, but a large number of fine lamellar structures are formed on the surface, so that the surface becomes rough. In summary, the above analysis demonstrates that rice-shaped nickel-iron bimetallic phyllosilicate nano-aggregates can be successfully produced by the technique described in example 1.
The epoxy resin composites described in examples 4-7 and comparative examples 2-3, as well as the pure epoxy resin material described in comparative example 1, were subjected to performance testing using the following test methods: testing unidirectional tensile property according to national standard GB/T1040-2006, wherein the test sample is in a 1BA dumbbell shape, the test speed is 2mm/min, and the test process is carried out until the test sample breaks; the quasi-static compression performance test is carried out according to national standard GB/T1041-2008, and the size of the sample is 12 multiplied by 20mm 3 The compression surface is 12X 12mm 2 The experimental process is carried out until the sample is broken; according to the national standard GB/T3960-2016, the sliding dry friction performance test is carried out on the material, and the size of the sample is 6 multiplied by 7 multiplied by 30mm 3 The test was preceded by conditioning for 24 hours at a prescribed room temperature (23.+ -. 5) and relative humidity (50.+ -. 5)%, and then testing at the same temperature and humidity; the load applied during the test was 12kg, the friction pair rotational speed was 100rpm, and the test duration was 3600s.
The test results are shown in table 1:
TABLE 1 Performance test results of epoxy resin materials and epoxy resin composites
Analysis of results:
comparative example 1 pure epoxy resin material has a relativeThe mechanical property is good, the tensile strength and the compressive strength are 67.16MPa and 256.91MPa respectively, and the tensile modulus and the compressive modulus reach 1.33GPa and 402.74GPa respectively; although the pure epoxy resin has relatively good abrasion resistance, the abrasion rate is 0.46×10 -4 mm 3 Nm, but its self-lubricating ability is poor, and the average friction coefficient reaches 0.515 at the highest.
The epoxy resin composite materials prepared by adding the products described in example 2 and example 3 in comparative example 2 and comparative example 3 respectively have significantly reduced mechanical strength and elastic modulus, and simultaneously have increased average friction coefficient and greatly increased wear rate, which indicates that the products synthesized according to the methods described in comparative example 2 and comparative example 3 cannot improve the mechanical and tribological properties of the epoxy resin composite materials. The possible reasons for the above results are that the products produced according to the methods of examples 2 and 3 are not the target products, namely, the rice-shaped nickel-iron bimetallic phyllosilicate nano-aggregates, and thus the epoxy resin composites produced according to comparative examples 2 and 3 do not exhibit the desired mechanical and tribological properties.
Examples 4-7 after 0.76% -5.39% of rice-shaped nickel-iron bimetallic phyllosilicate nano-aggregate is added into epoxy resin, the tensile strength and the compressive strength of the nano-aggregate are slightly increased and then decreased; the elastic modulus change trend in the stretching state is not obvious, but the elastic modulus under the compression-resistant condition shows a gradually increasing trend; with the increase of the concentration of the nano aggregate of the rice-shaped nickel-iron bimetallic phyllosilicate, the abrasion rate of the epoxy resin composite material is slightly reduced and then gradually increased, but the average friction coefficient of the epoxy resin composite material shows a continuously reduced variation trend.
As can be seen from the performance analysis of the above examples and comparative examples, compared with the pure epoxy resin material of comparative example 1, the epoxy resin composite material prepared according to the methods of examples 4-7 has better self-lubricating property, and shows that the addition of a proper amount of the rice-shaped nickel-iron bimetallic phyllosilicate nano aggregate of the invention can maintain or even slightly improve the mechanical property of the material although the wear-resisting property of the material is reduced, and simultaneously, the epoxy resin has very excellent lubricating capability, thereby providing a feasible technical idea for designing and preparing the epoxy resin composite material with excellent self-lubricating property. For example, as can be seen from fig. 7 and 8, the friction coefficient of the pure epoxy resin is relatively high, the coefficient of friction of the pure epoxy resin rises rapidly with time in the initial stage of friction, and the friction coefficient of the pure epoxy resin gradually enters the steady-state friction stage after about 1500s of running-in period, and the average friction coefficient is relatively high; on the contrary, after less than 5.39% of rice-shaped nickel-iron bimetallic phyllosilicate nano aggregate is added, the friction behavior of the epoxy resin composite material is obviously changed, the friction coefficient of the epoxy resin composite material only slightly rises in the initial stage, the epoxy resin composite material quickly enters a steady-state friction stage after a running-in stage of about 250s, and the average friction coefficient is greatly reduced; the analysis shows that the self-lubricating performance of the epoxy resin can be obviously improved by adding a proper amount of the rice-shaped nickel-iron bimetallic phyllosilicate nano aggregate.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be able to apply equivalents and modifications to the technical solution and the inventive concept thereof within the scope of the present invention.
Claims (10)
1. The synthesis method of the rice-shaped nickel-iron bimetallic phyllosilicate nano aggregate is characterized by comprising the following steps of:
s1, adding soluble nickel salt, soluble ferric salt and terephthalic acid into N, N-dimethylformamide according to a certain proportion, uniformly mixing, adding 4mL of absolute ethyl alcohol/water solution, transferring to a polytetrafluoroethylene reaction kettle after complete dissolution, carrying out hydrothermal reaction at 130 ℃ for 3 hours, and obtaining a product after repeated washing and centrifugation and drying, namely the nickel-iron bimetal organic framework precursor.
S2, dispersing the nickel-iron bimetal organic framework precursor and sodium silicate in 120mL of absolute ethyl alcohol/water solution according to a certain proportion, fully and uniformly stirring, adding 6mL of sodium hydroxide solution, ultrasonically treating for 30min, transferring to a polytetrafluoroethylene reaction kettle, performing hydrothermal reaction at 160 ℃ for 15h, and washing and drying the obtained precipitate to obtain the rice-shaped nickel-iron bimetal layered silicate nano aggregate.
2. The method for synthesizing a nanoparticle-shaped nickel-iron bimetallic phyllosilicate nano-aggregate according to claim 1, wherein in the step S1, the amount of the soluble nickel salt is 0.43-0.85 mmol, the amount of the soluble iron salt is 0-0.21 mmol, the amount of the terephthalic acid is 0.85mmol, and the volume ratio of the absolute ethyl alcohol-water solution is 1:1.
3. The method for synthesizing a nanoparticle-shaped nickel-iron bimetallic phyllosilicate nano-aggregate according to claim 1 or 2, wherein in the step S2, the amount of the nickel-iron bimetallic organic framework precursor is 0.8g, the amount of the sodium silicate is 1.14g, the volume ratio of the absolute ethyl alcohol to the aqueous solution is 1:1, and the concentration of the sodium hydroxide solution is 1mol/L.
4. A method for synthesizing a rice grain-shaped nickel-iron bimetallic phyllosilicate nano-aggregate according to any one of claims 1-3, wherein the drying conditions in steps S1 and S2 are vacuum drying at 75 ℃ for at least 24 hours.
5. The method for synthesizing a rice-shaped nickel-iron bimetallic phyllosilicate nano-aggregate according to any one of claims 1-4, wherein the soluble nickel salt is at least one of nickel chloride, nickel nitrate, and nickel acetate; the soluble ferric salt is at least one of ferric chloride, ferric nitrate and ferric acetate.
6. A rice grain-shaped nickel-iron bimetallic phyllosilicate nano-aggregate produced by the production method according to any one of claims 1 to 5.
7. An epoxy resin composite material is characterized in that the raw materials comprise epoxy monomers, a curing agent and the rice-shaped nickel-iron bimetallic phyllosilicate nano-aggregate according to claim 6, wherein the rice-shaped nickel-iron bimetallic phyllosilicate nano-aggregate accounts for 1-10% of the total weight of the raw materials.
8. The epoxy resin composite of claim 7, comprising the following raw materials in weight percent: 71-76% of epoxy monomer, 22-25% of curing agent and 1-6% of rice-shaped nickel-iron bimetallic phyllosilicate nano aggregate.
9. The epoxy resin composite of claim 8, wherein the epoxy monomer is bisphenol a type epoxy monomer having an epoxy value of 0.41-0.47; the curing agent is 4,4' -methylenebis (2-ethylaniline).
10. A method of preparing an epoxy resin composite according to any one of claims 7 to 9, comprising: adding the rice-shaped nickel-iron bimetallic phyllosilicate nano aggregate into acetone to be uniformly dispersed to obtain a dispersion liquid, adding the dispersion liquid into an epoxy monomer, uniformly stirring, adding a curing agent, and carrying out vacuum degassing, casting and curing to obtain the nano-sized nickel-iron bimetallic phyllosilicate nano aggregate.
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