CN115703856A - Ti 3 AlC 2 -resin composite material and method for producing the same - Google Patents
Ti 3 AlC 2 -resin composite material and method for producing the same Download PDFInfo
- Publication number
- CN115703856A CN115703856A CN202110892290.5A CN202110892290A CN115703856A CN 115703856 A CN115703856 A CN 115703856A CN 202110892290 A CN202110892290 A CN 202110892290A CN 115703856 A CN115703856 A CN 115703856A
- Authority
- CN
- China
- Prior art keywords
- alc
- resin
- resin composite
- powder
- framework
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000805 composite resin Substances 0.000 title claims abstract description 75
- 239000000463 material Substances 0.000 title claims description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 239000011347 resin Substances 0.000 claims abstract description 76
- 229920005989 resin Polymers 0.000 claims abstract description 76
- 239000000843 powder Substances 0.000 claims abstract description 59
- 239000000178 monomer Substances 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 43
- 238000005245 sintering Methods 0.000 claims abstract description 34
- 238000005096 rolling process Methods 0.000 claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 230000004048 modification Effects 0.000 claims abstract description 18
- 238000012986 modification Methods 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 18
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 17
- 239000005416 organic matter Substances 0.000 claims abstract description 16
- 238000003825 pressing Methods 0.000 claims abstract description 14
- 239000011159 matrix material Substances 0.000 claims abstract description 12
- 239000011230 binding agent Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 43
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 35
- 239000000853 adhesive Substances 0.000 claims description 23
- 230000001070 adhesive effect Effects 0.000 claims description 23
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 21
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 16
- 238000001723 curing Methods 0.000 claims description 13
- 238000005470 impregnation Methods 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 13
- 238000004321 preservation Methods 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 230000001681 protective effect Effects 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- 239000002060 nanoflake Substances 0.000 claims description 5
- 241000446313 Lamella Species 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- 238000004898 kneading Methods 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 3
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 3
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 3
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 3
- 229940057995 liquid paraffin Drugs 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 25
- 238000005452 bending Methods 0.000 abstract description 10
- 238000007711 solidification Methods 0.000 abstract description 4
- 230000008023 solidification Effects 0.000 abstract description 4
- 239000000919 ceramic Substances 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 238000001816 cooling Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000000227 grinding Methods 0.000 description 7
- 238000007731 hot pressing Methods 0.000 description 7
- 239000002135 nanosheet Substances 0.000 description 7
- 239000012300 argon atmosphere Substances 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- 229960000583 acetic acid Drugs 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000013001 point bending Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241001085205 Prenanthella exigua Species 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000002064 nanoplatelet Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- -1 polydimethylsiloxane Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009777 vacuum freeze-drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Landscapes
- Powder Metallurgy (AREA)
Abstract
The invention relates to a Ti 3 AlC 2 -a method for preparing a resin composite comprising the steps of: mixing Ti 3 AlC 2 Mixing the powder with a binder to obtain Ti 3 AlC 2 Bonding the powder together to obtain Ti 3 AlC 2 Mud; ti 3 AlC 2 The diameter of the powder is 200nm-2 μm, and the thickness is 20-200nm; for Ti 3 AlC 2 The mud is subjected to stack rolling treatment to obtain Ti 3 AlC 2 Ti in mud 3 AlC 2 The powder is arranged in an orientation way to obtain Ti with an oriented arrangement structure 3 AlC 2 Thin blanks; a plurality of directionally arranged structural Ti 3 AlC 2 Stacking the thin blanks together and pressing to obtain Ti 3 AlC 2 A green body; for Ti 3 AlC 2 The green body is subjected to organic matter removal treatment and sintering treatment to obtain Ti 3 AlC 2 A framework; for Ti 3 AlC 2 Carrying out surface modification on the framework; impregnating the surface-modified Ti with a resin monomer solution 3 AlC 2 A framework, and obtaining Ti after the polymerization and solidification of the resin monomer solution 3 AlC 2 -a resin composite. The invention is mainly used for preparing Ti by a simple process 3 AlC 2 Ti oriented in resin matrix 3 AlC 2 -a resin composite; the composite material has excellent bending strength, fracture toughness, conductivity and wear resistance.
Description
Technical Field
The invention relates to the technical field of MAX phase ceramic-resin composite materials, in particular to Ti 3 AlC 2 -resin composite material and process for its preparation.
Background
Ceramics have the advantages of high strength, high hardness, high modulus, corrosion resistance, wear resistance, low density and the like, and thus, the ceramics become one of the most promising candidates for hot-end high-temperature components in aerospace, armor protection, rail transit and the like. Wherein, the MAX phase ceramics (such as Ti) 3 AlC 2 、Ti 3 SiC 2 ) Has special nano-layered crystal structure characteristics, so that the ceramic material has the excellent mechanical properties of ceramics and also has the electric conductivity and heat conductivity of metal. This property of MAX phase ceramics has attracted considerable attention from researchers. However, like the conventional oxide or nitride ceramics, the MAX phase ceramics have high brittleness and poor fracture toughness due to strong covalent bonds, and are often catastrophically failed under severe stress conditions, which seriously affects the application range of the MAX phase ceramics. Therefore, it is an urgent problem to improve the fracture toughness of MAX phase ceramics as much as possible without reducing the strength.
Currently, the conventional technology is to add second phase particles, whiskers or fibers to a MAX phase ceramic matrix to improve its performance; although these methods can improve the fracture toughness to some extent, the introduction of the second phase may cause problems of weak bonding force of the two-phase interface, mismatch of thermal expansion, and the like.
It is well known that resins generally have good toughness and that the resins are incorporated into MAX phase ceramics to form MAX phase ceramic-resin composites with a certain structure. In the composite material, MAX phase ceramic is used as a strengthening phase, resin is used as a toughening phase, and the deflection and bridging of cracks are induced through the specific structure of the composite material, so that the crack propagation resistance is increased, and the material is favorable for realizing the optimized mechanical property along a specific direction.
One of the prior art proposes Ti 3 AlC 2 The preparation method of the epoxy resin conductive composite material comprises the following specific scheme: making particulate Ti by blending 3 AlC 2 Communicate with each other and are uniformly dispersed in the epoxy resin matrix. However, ti 3 AlC 2 The particle size is about 18 μm, but a larger particle size results in a coarse microstructure, and Ti 3 AlC 2 The particles are not completely communicated, obvious defects exist, the volume fraction is not more than 50%, the mechanical properties of the composite material are limited to a great extent, and the effect of excellent comprehensive mechanical properties cannot be achieved. In addition, the composite material adopts granular Ti 3 AlC 2 The orientation of the microstructure cannot be realized, and the optimization of the mechanical property cannot be realized.
The other prior art provides a layered alumina-epoxy resin composite material containing whiskers which are directionally arranged perpendicular to a layer interface and a preparation method thereof, aiming at simulating a 'mineral bridge' structure of a shell pearl layer, forming a 'whisker bridge' structure with a structure similar to the 'mineral bridge' in the layered ceramic, and preparing the layered alumina-epoxy resin composite ceramic containing the whiskers which are directionally arranged in a direction perpendicular to the layer interface (silicon carbide whiskers are directionally arranged as the mineral bridges along the interface which is perpendicular to the alumina ceramic layer and the epoxy resin layer) so as to further improve the strong and toughness properties of the layered alumina-epoxy resin composite material. However, in the ceramic matrix laminate composite, the ceramic layer has a thickness of 3 to 10 μm and the resin layer has a thickness of 10 to 80 μm, in contrast to the thinner ceramic layer which severely limits the strength and hardness of the composite. In addition, one end of a metal rod is inserted into the prepared suspension, the other end of the metal rod is immersed into the refrigerant, and the suspension is frozen from top to bottom by utilizing the heat transfer of the metal rod to realize orientation.
In conclusion, the MAX phase ceramics are directionally arranged in the MAX phase ceramic-resin composite material, and the mechanical property of the MAX phase ceramic-resin composite material can be improved. However, the inventors of the present invention found that: the ceramic powder selected in the preparation of ceramic-resin composite materials at present is generally micron-sized, which easily causes the coarse microstructure, and the granular powder can not realize the microstructure orientation; in addition, the existing method for realizing the oriented arrangement has a plurality of limitations (for example, only a lamellar structure can be obtained, the orientation of a ceramic phase can not be realized between single-sheet layers; for example, the sampling is difficult after the orientation is finished, and the existing orientation effect is easy to damage) when the ceramic-resin composite material with the oriented lamellar structure is prepared; in addition, the existing methods for realizing the directional arrangement are only limited to the preparation of small-size samples, the preparation steps of materials are more, the process is more complex, and the industrial production is difficult to realize.
Disclosure of Invention
In view of the above, the present invention provides a Ti 3 AlC 2 A resin composite material and a preparation method thereof, mainly aiming at preparing Ti by a simple process 3 AlC 2 Ti oriented in resin matrix 3 AlC 2 -a resin composite.
In order to achieve the purpose, the invention mainly provides the following technical scheme:
in one aspect, embodiments of the present invention provide a Ti 3 AlC 2 -a method for preparing a resin composite, comprising the steps of:
bonding: mixing Ti 3 AlC 2 Mixing the powder with a binder to obtain Ti 3 AlC 2 Bonding the powder together to obtain Ti 3 AlC 2 Mud (doughy mixture); wherein the Ti is 3 AlC 2 The powder is selected from nanometer sheet Ti with diameter of 200nm-2 μm and thickness of 20-200nm 3 AlC 2 Powder;
and (3) rolling and pressing: to the Ti 3 AlC 2 The mud is rolledRegulating and making Ti 3 AlC 2 Ti in mud 3 AlC 2 The powder is arranged in a directional way to obtain Ti with a directional arrangement structure 3 AlC 2 Thin blanks; a plurality of directionally arranged structural Ti 3 AlC 2 Stacking the thin blanks together and pressing to obtain Ti 3 AlC 2 A blank body;
organic matter removal and sintering steps: to the Ti 3 AlC 2 Removing organic matters from the blank, and sintering to obtain Ti 3 AlC 2 A framework;
resin monomer impregnation, polymerization and curing: to the Ti 3 AlC 2 Carrying out surface modification on the framework; impregnating the surface-modified Ti with a resin monomer solution 3 AlC 2 A framework, and Ti is obtained after the polymerization and solidification of the resin monomer solution 3 AlC 2 -a resin composite.
Preferably, in the bonding step: the adhesive is one or more of polyvinyl alcohol adhesive, hydroxypropyl methyl cellulose adhesive, polyethylene glycol adhesive, sucrose adhesive, liquid paraffin adhesive and glycerol adhesive; preferably, the polyvinyl alcohol binder includes low viscosity polyvinyl alcohol and water; more preferably, the mass fraction of the low-viscosity polyvinyl alcohol in the polyvinyl alcohol adhesive is 2 to 15%.
Preferably, ti is added 3 AlC 2 Mixing the powder and the adhesive to form a mixture, kneading the mixture until Ti is formed 3 AlC 2 The powder is completely bonded together to obtain Ti 3 AlC 2 And (4) mud.
Preferably, the step of pack rolling treatment includes: making the Ti 3 AlC 2 Rolling the mud between two rollers of a roller mill to form a thin blank, folding the thin blank, rolling again, and repeating the operations of folding and rolling for multiple times to obtain Ti with a directional arrangement structure 3 AlC 2 Thin blanks; preferably, the distance between the two rolls of the rolling mill is constant during a plurality of rolling operations.
Preferably, in the step of press-treating: the temperature of the pressing treatment is 30-120 ℃, the pressure is 2-20MPa, and the time is 0.5-3h.
Preferably, the step of press treating includes: ti of the alignment structure 3 AlC 2 Cutting thin blank into Ti with a plurality of directionally arranged structures with same size 3 AlC 2 After the thin blanks are stacked together and pressed.
Preferably, the step of removing organic matter includes: subjecting the Ti to vacuum in a protective atmosphere (first, and then, introducing a protective gas such as hydrogen, argon, or nitrogen) 3 AlC 2 Keeping the temperature of the blank at the heat preservation temperature for a first set time; preferably, the heat preservation temperature is 300-700 ℃, and the first set time is 3-8h; preferably, the Ti is added under a protective atmosphere 3 AlC 2 Heating the blank to a heat preservation temperature, and preserving heat for a first set time at the heat preservation temperature; more preferably, the Ti is added 3 AlC 2 And in the process of heating the blank to the heat preservation temperature, the heating rate is 1-8 ℃/min.
Preferably, the sintering treatment step includes: under the protection atmosphere (firstly vacuuming and then protective gas, such as hydrogen, argon and nitrogen), removing organic matters, and then treating the Ti 3 AlC 2 Sintering the blank at a sintering temperature to obtain Ti 3 AlC 2 A framework; wherein the sintering temperature is 700-1300 ℃, and the sintering time is 1-5h; preferably, under the protective atmosphere, ti after organic matter removal treatment is firstly adopted 3 AlC 2 And heating the blank to the sintering temperature, wherein the heating rate is 2-10 ℃/min.
Preferably, the Ti is 3 AlC 2 The porosity of the framework is 10-70%.
Preferably, in the resin monomer impregnation, polymerization curing step:
to the Ti 3 AlC 2 The step of surface modification of the backbone, comprising: adding the Ti 3 AlC 2 Immersing the skeleton in a modifying liquid containing silane coupling agent to treat Ti 3 AlC 2 Surface modification of the skeletonAfter the modification is finished, taking out the Ti with the modified surface 3 AlC 2 Framework and drying; preferably, the mass percent of the silane coupling agent in the modification liquid is 5-25%; preferably, the solvent in the modified solution is a mixed solution of methanol and water, the pH value of which is adjusted to 4-7 by acetic acid; more preferably, the mixed solution of methanol and water has a methanol mass fraction of 70 to 90%.
Preferably, in the resin monomer impregnation, polymerization curing step: impregnating the surface-modified Ti with a resin monomer solution 3 AlC 2 Skeleton (amount of resin monomer and Ti) 3 AlC 2 The size of the skeleton is related, only Ti is required 3 AlC 2 The skeleton is completely immersed in the resin monomer solution), and after the resin monomer is polymerized, the resin is cured by heat treatment to obtain Ti 3 AlC 2 -a resin composite; preferably, the resin monomer solution comprises methyl methacrylate and an initiator; further preferably, in the resin monomer solution, the mass fraction of the initiator is 0.2-1%; preferably, the temperature of the heat treatment is 40-90 ℃; preferably, the polymerization time of the resin monomer is 4 to 10 days; preferably, the resin monomer solution is added dropwise to the impregnation vessel, immersed in the sample, and vacuum assisted (due to Ti) 3 AlC 2 The skeleton contains many pores, and the vacuum assistance is to fill the Ti with resin monomer solution 3 AlC 2 In the pores of the framework), continuously dripping the resin monomer solution until the sample is submerged, standing in the atmospheric environment, and waiting for the polymerization of the resin monomer; further preferably, the vacuum-assisted time is 20-40min.
In another aspect, embodiments of the present invention provide a Ti 3 AlC 2 -a resin composite material, wherein the Ti 3 AlC 2 The resin composite material is made of two-dimensional nano-flaky Ti 3 AlC 2 And a resin, wherein, in volume percent, the Ti is 3 AlC 2 The content of (A) is 30-90%, and the rest is resin; in the microstructure, the Ti 3 AlC 2 -nano-flake Ti in resin composite 3 AlC 2 The materials are arranged in a preferred orientation in a resin matrix to form a two-phase continuous structure; preferably, in the two-phase continuous structure, the Ti 3 AlC 2 The thickness of the lamella is 20-200nm, and the space between the lamellae is 0.1-1 μm; preferably, the resin is polymethyl methacrylate; preferably, the Ti is 3 AlC 2 -the resin composite is Ti as defined in any of the above 3 AlC 2 -a method of preparing a resin composite; preferably, the Ti 3 AlC 2 -nano-platelet Ti in resin composite 3 AlC 2 In the resin matrix, the orientation is preferred along the direction of rotation of the rolls.
Compared with the prior art, the Ti of the invention 3 AlC 2 The resin composite material and the preparation method thereof have at least the following beneficial effects:
the embodiment of the invention provides Ti 3 AlC 2 -resin composite material and method for preparing the same by forming nano-flaky Ti 3 AlC 2 The powder is used as raw material (with thickness of 20-200 nm), and then mixed with binder to obtain Ti 3 AlC 2 After the mud is removed, the mud is subjected to multiple times of stack rolling treatment (rolling-folding-rolling) operation by a roller machine, so that Ti is realized 3 AlC 2 The powder is directionally arranged, and then the Ti is prepared by the steps of pressing, removing organic matters, sintering, impregnating resin monomers, polymerizing and curing 3 AlC 2 -a resin composite; in the above preparation process, nano-flaky Ti 3 AlC 2 Selection and pack rolling process of powder to realize Ti 3 AlC 2 The powder is oriented, so that the composite material has excellent strength. The Ti 3 AlC 2 Resin composite material compared to Ti 3 AlC 2 The fracture toughness of the ceramic is obviously improved, and the ceramic has dynamic energy consumption characteristics, so that the ceramic has excellent comprehensive mechanical properties and has considerable application prospects when used as a structural material.
It should be noted that: the preparation process of the invention realizes the nano flaky Ti 3 AlC 2 The powder orientation method only requires sheet Ti 3 AlC 2 The powder has larger length-diameter ratio without adding any additiveThe plasticizer has the advantages of simple operation, short process period, high efficiency and low cost, and the prepared material has no size limitation and is easy to realize industrialization; in addition, the lamellar structure formed in the repeated rolling and folding process can reduce the thermal stress in the sintering process and is easy to form.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to make the technical solutions of the present invention practical in accordance with the contents of the specification, the following detailed description is given of preferred embodiments of the present invention with reference to the accompanying drawings.
Drawings
FIG. 1 is a schematic representation of example 1 for the preparation of Ti 3 AlC 2 -a process flow diagram of a resin composite;
FIG. 2 shows Ti obtained after sintering treatment in the embodiment of example 1 3 AlC 2 A macro map (fig. 2 (a)) and a micro-structure map (fig. 2 (b));
FIG. 3 shows Ti prepared in example 1 3 AlC 2 -a macroscopic view (a) in fig. 3) and a microscopic view (b) of the resin composite; wherein the bright white area in the figure is Ti 3 AlC 2 The dark black area is resin.
FIG. 4 shows Ti prepared in example 1 3 AlC 2 Resin composite along perpendicular, parallel Ti 3 AlC 2 Room temperature three-point bending stress-strain curve in the lamellar direction (wherein the graph (a) in FIG. 4 is perpendicular Ti) 3 AlC 2 The room-temperature three-point bending stress-strain curve in the lamellar direction, and the graph (b) in FIG. 4 is parallel Ti 3 AlC 2 Room temperature three point bending stress-strain curve in the sheet direction).
Detailed Description
To further explain the technical means and effects of the present invention adopted to achieve the predetermined object, the following detailed description of the embodiments, structures, features and effects according to the present invention will be made with reference to the accompanying drawings and preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
The embodiment of the invention provides Ti 3 AlC 2 A resin composite material and a preparation method thereof, wherein the specific scheme is as follows:
Ti 3 AlC 2 the resin composite material is made of two-dimensional nano flaky Ti 3 AlC 2 And a resin, wherein, in volume percent, the Ti is 3 AlC 2 The content of (B) is 30-90%, and the rest is resin; in the microstructure, ti 3 AlC 2 -nano-flake Ti in resin composite 3 AlC 2 Preferentially arranging in a resin matrix (preferentially arranging along the rotation direction of the roller) to form a two-phase continuous structure; preferably, in the two-phase continuous structure, the Ti 3 AlC 2 The thickness of the lamella is 20-200nm, and the space between the lamellae is 0.1-1 μm. Preferably, the resin is polymethyl methacrylate.
Wherein, ti 3 AlC 2 -a method for preparing a resin composite comprising the steps of:
and (3) bonding: mixing Ti 3 AlC 2 Mixing the powder and the adhesive to form a mixture, kneading the mixture until Ti is formed 3 AlC 2 The powder is completely bonded together to obtain Ti 3 AlC 2 And (4) mud. Wherein, ti 3 AlC 2 The powder is selected from nanometer sheet Ti with diameter of 200nm-2 μm and thickness of 20-200nm 3 AlC 2 And (3) powder.
Wherein the adhesive is one or more of polyvinyl alcohol, hydroxypropyl methylcellulose, polyethylene glycol, sucrose, liquid paraffin and glycerol.
Preferably, the adhesive is a low-viscosity polyvinyl alcohol solution, and the mass fraction of the low-viscosity polyvinyl alcohol in the low-viscosity polyvinyl alcohol solution is 2-15, preferably 7-15%. Preferably, the low viscosity polyvinyl alcohol is type 1788.
And (3) rolling and pressing: for Ti 3 AlC 2 Subjecting the mud to a pack rolling treatment to obtain Ti 3 AlC 2 Ti in mud 3 AlC 2 Powder bodyDirectionally arranging to obtain Ti with directionally arranged structure 3 AlC 2 Thin blanks; a plurality of directionally arranged structural Ti 3 AlC 2 Stacking the thin blanks together and pressing to obtain Ti 3 AlC 2 A green body.
Wherein, the process of the pack rolling treatment comprises the following steps: using a roller mill to make Ti 3 AlC 2 The mud passes through two rollers to form a thin blank, the thin blank is folded and rolled again, and the step is repeated (the thickness of the roller is doubled in the folding process, the distance between the two rollers of the roller is unchanged, and the rolling is carried out again to promote the nano flaky Ti to be rolled again 3 AlC 2 Powder orientation), rolling-folding-rolling Ti 3 AlC 2 Mud ", repeat operation). In the continuous pack rolling process, the roller is applied to the nano flaky Ti 3 AlC 2 Shear force on the powder promotes Ti 3 AlC 2 The powder is preferentially arranged along the rotation direction of the roller to generate the orientation effect.
The pressing process comprises the following steps: cutting the green body slices into the same size, stacking together, and pressing at 30-120 deg.C under 2-20MPa for 0.5-3h.
Organic matter removal and sintering steps: for Ti 3 AlC 2 The green body is subjected to organic matter removal treatment and sintering treatment to obtain Ti 3 AlC 2 And (3) a framework.
The method comprises the following steps: for Ti 3 AlC 2 And heating and preserving the blank in an argon atmosphere, wherein the heat preservation temperature is 300-700 ℃, the heat preservation time is 3-8h, and the heating rate is 1-8 ℃/min (for removing organic matters). To the Ti 3 AlC 2 The sintering atmosphere of the green body is argon or nitrogen or vacuum atmosphere, the sintering temperature is 700-1300 ℃, the sintering time is 1-5h, and the heating rate is 2-10 ℃/min.
Ti 3 AlC 2 The porosity of the framework is 10-70%.
The sintering temperature affects the porosity, the higher the sintering temperature, the lower the porosity.
Resin monomer impregnation, polymerization and curing:to the Ti 3 AlC 2 Carrying out surface modification on the framework; impregnating the surface-modified Ti with a resin monomer solution 3 AlC 2 Skeleton until the resin monomer solution is polymerized and cured to obtain Ti 3 AlC 2 -a resin composite.
Wherein, for Ti 3 AlC 2 The surface modification of the skeleton comprises the following specific steps: preparing a mixed solution of methanol and water, wherein the mass percent of the methanol is 70-90%; adjusting the pH of the mixed solution to 4-7 by adding acetic acid to the mixed solution of methanol and water; adding 5-25% of silane coupling agent (preferably gamma-methacryloxypropyltrimethoxysilane) by mass percent into the mixed solution and stirring to obtain modified solution; mixing Ti 3 AlC 2 And immersing the framework into the modification liquid, standing, taking out and drying after the modification is finished.
Resin monomer impregnated Ti 3 AlC 2 The specific steps of framework, polymerization and curing are as follows: preparing a resin monomer solution comprising methyl methacrylate and an initiator, wherein the mass of the initiator accounts for 0.2-1% of the mass of the resin monomer solution; dripping the resin monomer solution into an impregnation container, and slowly immersing Ti 3 AlC 2 Carrying out skeleton vacuum assistance for 20-40min; continuously dropwise adding the methyl methacrylate solution until the Ti is submerged 3 AlC 2 The framework is kept stand in the atmospheric environment until methyl methacrylate is polymerized; after the polymerization is completed, ti 3 AlC 2 The backbone is heat treated at 40-90 c to ensure adequate curing of the polymerized methyl methacrylate.
(A) The components of the composite material are nano flaky Ti 3 AlC 2 Powder and resin, flaky Ti 3 AlC 2 The reinforcing phase realizes powder orientation in the process of multiple times of rolling, and the reinforcing effect of the reinforcing phase is fully exerted in the composite material, so that the composite material has excellent strength.
(B) The composite material of the present invention is comparable to Ti 3 AlC 2 The fracture toughness of the ceramic is obviously improved, and the ceramic has dynamic energy consumption characteristics, so that the ceramic has excellent comprehensive mechanical properties and can be used as a structural materialConsiderable application prospect
(C) The composite material of the invention realizes nano-sheet Ti 3 AlC 2 The powder orientation method only requires sheet Ti 3 AlC 2 The powder has a larger length-diameter ratio, no plasticizer is required to be added, the operation is simple, the process period is short, the efficiency is high, the cost is low, and the prepared material has no size limitation and is easy to realize industrialization; in addition, the lamellar structure formed in the repeated rolling and folding process can reduce the thermal stress in the sintering process and is easy to form.
The invention is further illustrated below by means of specific examples:
example 1
This example prepares mainly a Ti 3 AlC 2 -a resin composite. Wherein the raw material mainly comprises nano-sheet Ti 3 AlC 2 Powder (diameter of 500 + -50 nm and thickness of 50 + -10 nm), low viscosity polyvinyl alcohol (type 1788), deionized water, methanol solution, acetic acid solution, gamma-methacryloxypropyltrimethoxysilane, and methyl methacrylate; the specific preparation process is shown in figure 1.
Bonding: adding 10g of low-viscosity polyvinyl alcohol into 100mL of deionized water, and continuously and mechanically stirring at the temperature of 100 ℃ until the polyvinyl alcohol is completely dissolved to obtain the liquid polyvinyl alcohol adhesive with the mass fraction of 10%. Weighing 30g of nano flaky Ti by using an electronic balance with the precision of 0.0001 3 AlC 2 Pouring the powder into a watch glass, then dripping 15mL of the liquid polyvinyl alcohol adhesive into the watch glass, and continuously and mechanically stirring to obtain Ti 3 AlC 2 Repeatedly kneading the mixture of powder and liquid polyvinyl alcohol binder to obtain nanometer sheet Ti 3 AlC 2 The powder is completely bonded together to form Ti 3 AlC 2 Mud (i.e., a dough-like mixture).
And (3) rolling and pressing: rolling of Ti with a roller 3 AlC 2 Mud, ti obtained by first rolling under the premise of ensuring the distance between two rollers to be unchanged 3 AlC 2 Rolling after the thin blank is folded, repeating for 30 times to obtain the nano-sheetForm Ti 3 AlC 2 The powder is preferentially arranged in an oriented way along the rotation direction of the roller under the action of the shearing force applied by the roller, and finally Ti with an oriented arrangement structure is obtained 3 AlC 2 Thin blanks; mixing Ti 3 AlC 2 Cutting the thin blank into 3 × 3cm, stacking the thin blank in a steel mold, compressing the blank in a direction perpendicular to the sheet by using a thermal press at 100 deg.C under 6MPa for 1h, cooling, releasing the pressure, and cooling to obtain Ti 3 AlC 2 The green body is removed from the mold and dried.
Organic matter removal and sintering steps: mixing Ti 3 AlC 2 And placing the blank body in a tubular furnace, heating the blank body from room temperature to 600 ℃ at the heating rate of 2 ℃/min under the argon atmosphere condition, preserving the heat for 5 hours, and then cooling the blank body to the room temperature at the heating rate of 2 ℃/min to remove organic matters. Ti to be freed of organic matter 3 AlC 2 Placing the blank in a hot pressing furnace, vacuumizing the hot pressing furnace, introducing argon, heating from room temperature to 900 ℃ at a heating rate of 10 ℃/min under the argon atmosphere, preserving the heat for 1h, and then cooling to room temperature at a cooling rate of 10 ℃/min to obtain the porous Ti with the micro-oriented structure 3 AlC 2 Skeleton, as shown in FIG. 2, of Ti 3 AlC 2 The porosity of the framework is about 62%.
Resin monomer impregnation, polymerization and curing: the configuration mass ratio is 9:1 of methanol and deionized water, 200g, adding glacial acetic acid dropwise into the mixed solution under the stirring condition to adjust the pH of the mixed solution to 4, then adding 50g of gamma-methacryloxypropyl trimethoxy silane, and stirring by using a magnetic stirrer to obtain a silane coupling agent solution. Mixing Ti 3 AlC 2 Slowly immersing the skeleton into a silane coupling agent solution, standing for 24 hours at room temperature in the atmospheric environment, and drying to obtain Ti with modified surface 3 AlC 2 And (3) a framework. 1g of azobisisobutyronitrile initiator was added to 200g of methyl methacrylate monomer, and stirred with a magnetic stirrer until completely dissolved, to obtain a resin monomer solution. Surface-modified Ti under vacuum condition of 1Pa 3 AlC 2 The skeleton is slowly immersed in the resin monomer solution, sealed and then placed in an atmosphereThen, after the resin monomer is slowly polymerized, the resin monomer is heated for 2 hours at 80 ℃ to be completely solidified to obtain Ti 3 AlC 2 -a resin composite.
Ti prepared in this example 3 AlC 2 -a resin composite material having a microstructure as shown in figure 3. As can be seen from fig. 3: bright white nano flaky Ti with volume fraction of 38% 3 AlC 2 The powder is arranged in a preferred orientation in a dark black resin matrix, and two phases present a bicontinuous structure. Wherein, ti 3 AlC 2 The thickness of the lamella is 100 +/-10 nm, ti 3 AlC 2 The spacing of the lamellae was 100. + -.10 nm.
By testing, ti prepared in this example 3 AlC 2 -resin composite parallel to Ti 3 AlC 2 The hardness in the lamellar direction was 0.79GPa, perpendicular to Ti 3 AlC 2 The hardness in the lamellar direction is 1.03GPa; bending strength in the direction perpendicular to the sheet layer is about 160MPa, parallel to Ti 3 AlC 2 The bending strength in the lamellar direction is about 68MPa, and accordingly, the three-point bending stress-strain curve is shown in FIG. 4; at right angles to Ti 3 AlC 2 Fracture toughness in lamellar direction of 2.34MPa m 0.5 In parallel with Ti 3 AlC 2 Fracture toughness in lamellar direction of 2.04MPa m 0.5 . In addition, ti prepared in this example 3 AlC 2 -resin composite with Si 3 N 4 The friction coefficient during the opposite grinding is 0.48, and the conductivity is 26S.m -1 。
Example 2
This example prepares mainly a Ti 3 AlC 2 -a resin composite. The starting materials used were the same as in example 1.
The preparation process of the present example is different from that of example 1 in that: removing organic matters and sintering. The organic matter removal and sintering steps in this embodiment are: mixing Ti 3 AlC 2 And placing the blank body in a tubular furnace, heating the blank body from room temperature to 600 ℃ at the heating rate of 2 ℃/min under the argon atmosphere condition, preserving the heat for 5 hours, and then cooling the blank body to the room temperature at the heating rate of 2 ℃/min to remove organic matters. To remove organic matterTi 3 AlC 2 Placing the blank in a hot pressing furnace, vacuumizing the hot pressing furnace, introducing argon, heating from room temperature to 800 ℃ at a heating rate of 2 ℃/min under the argon atmosphere, preserving heat for 1h, and cooling to room temperature at a cooling rate of 10 ℃/min to obtain the porous Ti with the micro-oriented structure 3 AlC 2 Skeleton, as shown in FIG. 2, of Ti 3 AlC 2 The porosity of the framework is about 69%.
The other steps are consistent.
By testing, ti prepared in this example 3 AlC 2 Resin composite material, parallel to Ti 3 AlC 2 The hardness in the lamellar direction was 0.63GPa, perpendicular to Ti 3 AlC 2 The hardness in the lamellar direction was 0.94GPa; at right angles to Ti 3 AlC 2 Flexural strength in the lamellar direction of about 150MPa, parallel to Ti 3 AlC 2 The bending strength in the sheet direction is about 65MPa; the fracture toughness in the direction perpendicular to the sheet layer is 3.03MPa m 0.5 In a direction parallel to Ti 3 AlC 2 Fracture toughness in lamellar direction of 2.83MPa m 0.5 (ii) a In addition, ti prepared in this example 3 AlC 2 -resin composite with Si 3 N 4 The friction coefficient during the opposite grinding is 0.36, and the electric conductivity is 20.2S.m -1 。
Example 3
This example mainly prepares a Ti 3 AlC 2 -a resin composite. The starting materials used were the same as in example 1.
The preparation process of this example differs from that of example 1 in that: removing organic matters and sintering. The organic matter removal and sintering steps in this embodiment are: mixing Ti 3 AlC 2 And placing the blank body in a tubular furnace, heating the blank body from room temperature to 600 ℃ at the heating rate of 2 ℃/min under the argon atmosphere condition, preserving the heat for 5 hours, and then cooling the blank body to the room temperature at the heating rate of 2 ℃/min to remove organic matters. Ti to be freed of organic matter 3 AlC 2 Placing the blank in a hot pressing furnace, vacuumizing the hot pressing furnace, introducing argon, and heating from room temperature at a heating rate of 2 ℃/min in an argon atmosphereKeeping the temperature for 1h to 1200 ℃, and then cooling to room temperature at a cooling rate of 10 ℃/min to obtain porous Ti with a micro-oriented structure 3 AlC 2 Skeleton, as shown in FIG. 2, of Ti 3 AlC 2 The porosity of the framework is about 44%.
The other steps are consistent.
By testing, ti prepared in this example 3 AlC 2 Resin composite material, parallel to Ti 3 AlC 2 The hardness in the lamellar direction was 1.01GPa, perpendicular to Ti 3 AlC 2 The hardness in the lamellar direction was 1.30GPa; at right angles to Ti 3 AlC 2 The flexural strength in the lamellar direction is about 201MPa, parallel to Ti 3 AlC 2 The bending strength in the sheet direction is about 94MPa; at right angles to Ti 3 AlC 2 Fracture toughness in the lamellar direction of 1.94MPa m 0.5 In a direction parallel to Ti 3 AlC 2 Fracture toughness in lamellar direction of 1.51MPa m 0.5 (ii) a In addition, the composite material is mixed with Si 3 N 4 The friction coefficient during the opposite grinding is 0.56, and the conductivity is 32S.m -1 。
As can be seen from the above examples of the present invention, nano-sheet Ti is realized 3 AlC 2 The orientation of the powder can improve the mechanical properties, especially the strength, of the composite material. The embodiment of the invention adopts a composite design of composition in strong and hard Ti 3 AlC 2 Introducing tough resin to make nano sheet Ti in the composite material 3 AlC 2 The powder is arranged in the resin matrix in an oriented way and shows a bicontinuous structure. The embodiment of the invention prepares the Ti which not only has excellent bending strength and fracture toughness, but also has excellent conductivity and wear resistance by a simple process 3 AlC 2 -a resin composite.
Comparative example 1
This comparative example mainly prepares a Ti 3 AlC 2 -a resin composite. Wherein the raw material is nano-sheet Ti 3 AlC 2 Powder (diameter of 500 + -50 nm, thickness of 50 + -10 nm). The specific preparation process comprises the following steps:
preparing a framework: by usingAn electronic balance with the precision of 0.0001 weighs 100g of nano flaky Ti 3 AlC 2 Pouring the powder into a graphite crucible with the diameter of 50mm, placing the graphite crucible into a hot-pressing furnace, heating the powder from room temperature to 900 ℃ at the heating rate of 10 ℃/min under the condition of argon protective atmosphere, preserving the heat for 1h, and then cooling the powder to the room temperature at the heating rate of 10 ℃/min to obtain the porous Ti without the micro-oriented structure 3 AlC 2 A scaffold, the scaffold having a porosity of about 73%.
Resin monomer impregnation, polymerization and curing: the configuration mass ratio is 9: 1g of methanol and deionized mixed solution, dropwise adding glacial acetic acid into the mixed solution under the stirring condition to adjust the pH value of the mixed solution to be 4, then adding 100g of gamma-methacryloxypropyltrimethoxysilane, and stirring by using a magnetic stirrer to obtain the modified solution. Mixing Ti 3 AlC 2 Slowly immersing the framework into the modification liquid, standing for 24 hours at room temperature in the atmospheric environment, and drying to obtain Ti with modified surface 3 AlC 2 And (3) a framework. 2g of azobisisobutyronitrile initiator was added to 400g of methyl methacrylate monomer, and stirred with a magnetic stirrer until completely dissolved to obtain a resin monomer solution. Surface-modified Ti under vacuum condition of 1Pa 3 AlC 2 Slowly immersing the skeleton in the resin monomer solution, sealing, standing in atmospheric environment, slowly polymerizing the resin monomer, and heat treating at 80 deg.C for 2 hr to completely cure to obtain Ti 3 AlC 2 -a resin composite.
The Ti prepared in the comparative example was tested 3 AlC 2 Resin composite material, parallel to Ti 3 AlC 2 The hardness in the lamellar direction was 0.51GPa, perpendicular to Ti 3 AlC 2 The hardness in the lamellar direction was 0.84GPa; in a direction perpendicular to Ti 3 AlC 2 Flexural strength in the lamellar direction of about 105MPa, parallel to Ti 3 AlC 2 The flexural strength in the lamellar direction is about 43MPa; fracture toughness in the direction perpendicular to the sheet layer was 1.79Pa m 0.5 In parallel with Ti 3 AlC 2 Fracture toughness in lamellar direction of 1.32MPa m 0.5 (ii) a In addition, ti prepared in this example 3 AlC 2 -resin compositeMaterial and Si 3 N 4 The friction coefficient during the counter-grinding is 0.24, and the conductivity is 19.6S.m -1 。
Comparative example 1 Ti preparation directly by blending 3 AlC 2 Resin composite material, without nano-flake Ti 3 AlC 2 And (5) orienting the powder. By comparing the data of comparative example 1 and the above examples, it can be seen that Ti prepared in comparative example 1 3 AlC 2 The resin composite material is poor in hardness, bending strength, fracture toughness, friction coefficient and electrical conductivity.
Comparative example 2
This comparative example mainly prepares a Ti 3 AlC 2 -a resin composite. Wherein the raw material is micron sheet Ti 3 AlC 2 Powder (diameter of 16 + -1 μm and thickness of 500 + -50 nm).
The other steps were in accordance with comparative example 1.
By testing, ti prepared in this comparative example 3 AlC 2 Resin composite material, parallel to Ti 3 AlC 2 The hardness in the lamellar direction was 0.57GPa, perpendicular to Ti 3 AlC 2 The hardness in the lamellar direction was 0.92GPa; at right angles to Ti 3 AlC 2 Flexural strength in the lamellar direction of about 83MPa, parallel to Ti 3 AlC 2 The bending strength in the lamellar direction is about 32MPa; the fracture toughness in the direction perpendicular to the sheet layer is 1.91MPa m 0.5 In a direction parallel to Ti 3 AlC 2 Fracture toughness in lamellar direction of 1.47MPa m 0.5 (ii) a In addition, ti prepared in this example 3 AlC 2 -resin composite with Si 3 N 4 The friction coefficient during the counter-grinding is 0.31, and the conductivity is 19.2S.m -1 。
Comparative example 2 comparative example 1, nano-flaky Ti 3 AlC 2 The powder is replaced by micron-sized powder. By comparing the data of comparative example 2 and the above examples, it can be seen that Ti prepared in comparative example 2 3 AlC 2 The resin composite material is poor in hardness, bending strength, fracture toughness, friction coefficient and electrical conductivity.
Comparative example 3
This comparative example mainly prepares a Ti 3 AlC 2 -a resin composite. Wherein the raw materials used were the same as in comparative example 1. The method comprises the following specific steps:
disposing Ti 3 AlC 2 Slurry preparation: 65g of deionized water was dropped into a 250ml plastic jar, and 35g of nanoplatelet Ti was weighed with an electronic balance having an accuracy of 0.0001 3 AlC 2 Pouring the powder into a wide-mouth bottle and continuously mechanically stirring until the powder is Ti 3 AlC 2 The powder is uniformly dispersed in water. The jar was placed in a water bath at 70 ℃ for 30min and then 0.325g of propylene hydroxymethyl cellulose powder was added and mechanical agitation continued until completely dispersed in the slurry. The slurry was taken out, cooled, and then 0.35g of Darvan CN dispersant was added to the slurry and stirred until uniformly dispersed. Finally, 5 zirconia grinding balls with the diameters of 3mm and 6mm are added respectively, and the mixture is sealed and then placed on a roller ball mill with the rotating speed of 300rpm for ball milling for 24 hours.
Freeze casting and vacuum freeze drying: pouring the ball-milled slurry into a rectangular polymethyl methacrylate mould with the size of 20mm multiplied by 20mm, sealing the lower end of the mould by a polydimethylsiloxane base with the inclination angle of 25 degrees, placing the mould on a copper plate, connecting the other side of the copper plate with a copper rod with one end immersed in liquid nitrogen, cooling the copper plate to enable the water in the slurry to be directionally solidified from bottom to top, and using ice crystals growing along the solidification direction to enable nano flaky Ti to be subjected to directional solidification 3 AlC 2 The powder is squeezed between the ice crystals to achieve the directional arrangement of the powder. Taking out the slurry from the mold after the slurry is completely solidified, and standing in a freeze drier with a cold trap temperature of-60 deg.C and a vacuum degree of 1Pa for 72 hr to remove water, to obtain Ti with directional porous structure and composed of sheets 3 AlC 2 And (3) a framework.
Organic matter removal, sintering, resin monomer impregnation, polymerization and curing steps are the same as in comparative example 1.
The Ti prepared in the comparative example was tested 3 AlC 2 Resin composite material, parallel to Ti 3 AlC 2 The hardness in the lamellar direction was 0.87GPa and in the perpendicular directionIn the presence of Ti 3 AlC 2 The hardness in the lamellar direction is 1.05GPa; at right angles to Ti 3 AlC 2 Flexural strength in the lamellar direction of about 151MPa, parallel to Ti 3 AlC 2 The bending strength in the lamellar direction is about 59MPa; in a direction perpendicular to Ti 3 AlC 2 Fracture toughness in lamellar direction of 1.52MPa m 0.5 In parallel with Ti 3 AlC 2 Fracture toughness in lamellar direction of 1.09MPa m 0.5 (ii) a In addition, the composite material is mixed with Si 3 N 4 The friction coefficient during the counter-grinding is 0.49, and the conductivity is 25S.m -1 。
Comparative example 3 is Ti prepared by an orientation method using an ice template 3 AlC 2 -a resin composite; the composite material has good hardness and strength, but poor toughness and friction coefficient; although the ice template orientation method can orient to form a lamellar structure, the nanosheets in each lamellar structure cannot be oriented, but the pack rolling orientation method provided by the embodiment of the invention can not only orient to form the lamellar structure, but also orient the nanosheets in each lamellar structure, so that crack deflection can be induced, and the toughness of the composite material is improved.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.
Claims (10)
1. Ti 3 AlC 2 -a method for preparing a resin composite, characterized in that it comprises the following steps:
bonding: mixing Ti 3 AlC 2 Mixing the powder with a binder to obtain Ti 3 AlC 2 Bonding the powder together to obtain Ti 3 AlC 2 Mud; wherein, the Ti 3 AlC 2 The powder is selected from nanometer sheet Ti with diameter of 200nm-2 μm and thickness of 20-200nm 3 AlC 2 Powder;
and (3) rolling and pressing: to the Ti 3 AlC 2 Subjecting the mud to a pack rolling treatment to obtain Ti 3 AlC 2 Ti in mud 3 AlC 2 The powder is arranged in an orientation way to obtain Ti with an oriented arrangement structure 3 AlC 2 Thin blank; a plurality of directionally arranged structural Ti 3 AlC 2 Stacking the thin blanks together and pressing to obtain Ti 3 AlC 2 A green body;
organic matter removal and sintering steps: to the Ti 3 AlC 2 Removing organic matters from the blank, and sintering to obtain Ti 3 AlC 2 A framework;
resin monomer impregnation, polymerization and curing: to the Ti 3 AlC 2 Carrying out surface modification on the framework; impregnating the surface-modified Ti with a resin monomer solution 3 AlC 2 A framework, and Ti is obtained after the resin monomer solution is polymerized and solidified 3 AlC 2 -a resin composite.
2. The Ti of claim 1 3 AlC 2 -a method for preparing a resin composite, characterized in that, in the bonding step:
the adhesive is one or more of polyvinyl alcohol adhesive, hydroxypropyl methyl cellulose adhesive, polyethylene glycol adhesive, sucrose adhesive, liquid paraffin adhesive and glycerol adhesive; preferably, the polyvinyl alcohol binder includes a low viscosity polyvinyl alcohol and water; more preferably, the mass fraction of the low-viscosity polyvinyl alcohol in the polyvinyl alcohol adhesive is 2-15%; and/or
Mixing Ti 3 AlC 2 Mixing the powder and the adhesive to form a mixture, kneading the mixture until Ti is formed 3 AlC 2 The powder is completely bonded together to obtain Ti 3 AlC 2 And (4) mud.
3. The Ti of claim 1 or 2 3 AlC 2 -a method for manufacturing a resin composite material, characterized in that the step of pack rolling treatment comprises:
making the Ti 3 AlC 2 Mud passing throughRolling between two rollers of a roller mill to form a thin blank, folding the thin blank, rolling again, and repeating the operations of folding and rolling for multiple times to obtain Ti with a directional arrangement structure 3 AlC 2 Thin blanks;
preferably, the distance between the two rolls of the rolling mill is constant during a plurality of rolling operations.
4. The Ti of any of claims 1-3 3 AlC 2 -a method for preparing a resin composite, characterized in that, in the step of pressing treatment: the temperature of the pressing treatment is 30-120 ℃, the pressure is 2-20MPa, and the time is 0.5-3h; and/or
The step of press treatment includes: ti of the alignment structure 3 AlC 2 Cutting thin blank into Ti with a plurality of directionally arranged structures with same size 3 AlC 2 After the thin blanks are stacked together and pressed.
5. The Ti of any of claims 1-4 3 AlC 2 -a method for preparing a resin composite, characterized in that said step of organic matter removal treatment comprises:
under a protective atmosphere, the Ti 3 AlC 2 Keeping the temperature of the blank at the heat preservation temperature for a first set time;
preferably, the heat preservation temperature is 300-700 ℃, and the first set time is 3-8h;
preferably, the Ti is added under a protective atmosphere 3 AlC 2 Heating the blank to a heat preservation temperature, and preserving heat for a first set time at the heat preservation temperature; more preferably, the Ti is added 3 AlC 2 And in the process of heating the blank to the heat preservation temperature, the heating rate is 1-8 ℃/min.
6. The Ti of any of claims 1-5 3 AlC 2 -a method for the preparation of a resin composite material, characterized in that said step of sintering treatment comprises:
under the protective atmosphere, ti after organic matter removal treatment 3 AlC 2 Sintering the blank at a sintering temperature to obtain Ti 3 AlC 2 A framework; wherein the sintering temperature is 700-1300 ℃, and the sintering time is 1-5h;
preferably, under the protective atmosphere, ti after organic matter removal treatment is firstly adopted 3 AlC 2 And heating the green body to the sintering temperature, wherein the heating rate is 2-10 ℃/min.
7. The Ti of any of claims 1-6 3 AlC 2 -method for preparing a resin composite, characterized in that said Ti 3 AlC 2 The porosity of the framework is 10-70%.
8. The Ti of any of claims 1-7 3 AlC 2 -a method for preparing a resin composite material, characterized in that in the resin monomer impregnation, polymerization curing step:
to the Ti 3 AlC 2 The step of surface modification of the backbone, comprising: adding the Ti 3 AlC 2 Immersing the skeleton in a modifying liquid containing silane coupling agent to treat Ti 3 AlC 2 Carrying out surface modification on the framework, and taking out the Ti after surface modification after the surface modification 3 AlC 2 Framework and drying;
preferably, in the modifying solution: the mass percent of the silane coupling agent is 5-25%;
preferably, in the modifying solution: the solvent is a mixed solution of methanol and water with the pH value adjusted to 4-7 by acetic acid; more preferably, the mixed solution of methanol and water has a methanol mass fraction of 70 to 90%.
9. The Ti of claim 8 3 AlC 2 -a method for preparing a resin composite material, characterized in that, in the resin monomer impregnation, polymerization curing step:
impregnating the surface-modified Ti with a resin monomer solution 3 AlC 2 A skeleton, after the resin monomer solution is polymerized, performing heat treatment to solidify the resin to obtain Ti 3 AlC 2 -a resin composite;
preferably, the resin monomer solution comprises methyl methacrylate and an initiator; further preferably, in the resin monomer solution, the mass fraction of the initiator is 0.2-1%;
preferably, the temperature of the heat treatment is 40-90 ℃;
preferably, the polymerization time of the resin monomer is 4 to 10 days;
preferably, the resin monomer solution is dripped into the impregnation container, immersed into the sample, vacuum-assisted, and continuously dripped until the sample is submerged, and the solution is kept standing in the atmospheric environment until the resin monomer solution is polymerized; further preferably, the vacuum-assisted time is 20-40min.
10. Ti 3 AlC 2 -a resin composite material, characterized in that said Ti 3 AlC 2 The resin composite material is made of two-dimensional nano-flaky Ti 3 AlC 2 And a resin, wherein, in volume percent, the Ti is 3 AlC 2 The content of (B) is 30-90%, and the rest is resin;
in the microstructure, the Ti 3 AlC 2 -nano-flake Ti in resin composite 3 AlC 2 The materials are arranged in a resin matrix in a preferred orientation mode to form a two-phase continuous structure; preferably, in the two-phase continuous structure, the Ti 3 AlC 2 The thickness of the lamella is 20-200nm, and the space between the lamellae is 0.1-1 μm;
preferably, the resin is polymethyl methacrylate;
preferably, the Ti is 3 AlC 2 -the resin composite is Ti according to any one of claims 1 to 9 3 AlC 2 -a method of preparing a resin composite;
preferably, the Ti is 3 AlC 2 -nano-flake Ti in resin composite 3 AlC 2 In the resin matrix, the orientation is preferred along the direction of rotation of the rolls.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110892290.5A CN115703856B (en) | 2021-08-04 | 2021-08-04 | Ti (titanium) 3 AlC 2 -resin composite material and method for preparing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110892290.5A CN115703856B (en) | 2021-08-04 | 2021-08-04 | Ti (titanium) 3 AlC 2 -resin composite material and method for preparing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115703856A true CN115703856A (en) | 2023-02-17 |
| CN115703856B CN115703856B (en) | 2023-11-03 |
Family
ID=85179872
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110892290.5A Active CN115703856B (en) | 2021-08-04 | 2021-08-04 | Ti (titanium) 3 AlC 2 -resin composite material and method for preparing the same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115703856B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116716022A (en) * | 2023-05-04 | 2023-09-08 | 湖北工业大学 | High-permeability concrete protective material imitating shell structure vinyl resin and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090025941A (en) * | 2007-09-07 | 2009-03-11 | 한국기계연구원 | A manufacturing method of phosphorus dioxidized copper sheet using three-layer stack accumulative roll-bonding process |
| CN102424920A (en) * | 2011-09-14 | 2012-04-25 | 上海交通大学 | In-situ preparation method of micro nano laminated metal-based composite material |
| CN108752821A (en) * | 2018-06-14 | 2018-11-06 | 中国科学院金属研究所 | Silicon carbide with microcosmic oriented structure/resin bionic composite material and preparation method thereof |
-
2021
- 2021-08-04 CN CN202110892290.5A patent/CN115703856B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090025941A (en) * | 2007-09-07 | 2009-03-11 | 한국기계연구원 | A manufacturing method of phosphorus dioxidized copper sheet using three-layer stack accumulative roll-bonding process |
| CN102424920A (en) * | 2011-09-14 | 2012-04-25 | 上海交通大学 | In-situ preparation method of micro nano laminated metal-based composite material |
| CN108752821A (en) * | 2018-06-14 | 2018-11-06 | 中国科学院金属研究所 | Silicon carbide with microcosmic oriented structure/resin bionic composite material and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116716022A (en) * | 2023-05-04 | 2023-09-08 | 湖北工业大学 | High-permeability concrete protective material imitating shell structure vinyl resin and preparation method thereof |
| CN116716022B (en) * | 2023-05-04 | 2024-06-07 | 湖北工业大学 | High-permeability concrete protective material imitating shell structure vinyl resin and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115703856B (en) | 2023-11-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108752821B (en) | Silicon carbide/resin bionic composite material with micro-oriented structure and preparation method thereof | |
| CN111644615B (en) | Preparation method for realizing high strength and toughness of TC4 titanium alloy by co-strengthening method | |
| CN107021785B (en) | A kind of ultra-toughness layered polymer-ceramic composite and preparation method thereof | |
| CN111423698B (en) | High-filling-amount hexagonal boron nitride nanosheet/fiber/polymer blocky composite material and preparation method thereof | |
| CN109320276A (en) | Silicon nitride crystal whisker and beta-silicon nitride nanowire enhancing nitridation silicon substrate wave transparent ceramic preparation | |
| CN109482882B (en) | Foam metal with micro-oriented pore structure and preparation method thereof | |
| CN112707736B (en) | Graphene modified ceramic composite material, preparation method and product | |
| CN111876622A (en) | Preparation method of graphene reinforced aluminum alloy tensile heat-conducting composite material | |
| CN109880290A (en) | A kind of preparation method of epoxy resin/MXene composite material | |
| CN113912410B (en) | Preparation method of bionic multifunctional cement-hydrogel composite material | |
| CN115703856B (en) | Ti (titanium) 3 AlC 2 -resin composite material and method for preparing the same | |
| CN112011151A (en) | Preparation method of honeycomb-shaped resin material | |
| CN112592188A (en) | Preparation method of graphene composite silicon carbide ceramic material | |
| CN115677364A (en) | Multilayer zirconium carbide reinforced carbon-based composite material and preparation method and application thereof | |
| CN114716258B (en) | Preparation method of carbon fiber reinforced boron carbide composite material | |
| CN113800837B (en) | Continuous carbon fiber reinforced phosphate group geopolymer composite material and preparation method thereof | |
| CN109402532B (en) | Preparation method of high-strength whisker precast block with whiskers distributed in plane | |
| CN109180186B (en) | Preparation method of bionic pearl layer MAX phase carbide ceramic matrix composite material | |
| CN111995413A (en) | Silicon carbide whisker toughened aluminum oxide composite ceramic material for bulletproof armor and preparation method thereof | |
| CN113831101A (en) | Chopped carbon fiber reinforced phosphate group geopolymer composite material and preparation method thereof | |
| Liu et al. | Additive manufacturing of continuous carbon fiber–reinforced silicon carbide ceramic composites | |
| CN115259859B (en) | Boron carbide bulletproof ceramic material and preparation method thereof | |
| CN111020264A (en) | Three-dimensional accumulation body reinforced titanium-based composite material and preparation method thereof | |
| CN116396089A (en) | Three-dimensional silicon carbide/molybdenum carbide ceramic skeleton reinforced carbon-based composite material and preparation method and application thereof | |
| CN110452415A (en) | A kind of preparation method of high dispersive graphene enhancing bismaleimide resin based composites |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |