CN110172603B - Preparation method of modified carbon nanotube reinforced titanium-based composite material - Google Patents
Preparation method of modified carbon nanotube reinforced titanium-based composite material Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 149
- 239000010936 titanium Substances 0.000 title claims abstract description 149
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- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 133
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 156
- 239000000843 powder Substances 0.000 claims abstract description 101
- 238000005096 rolling process Methods 0.000 claims abstract description 62
- 239000000243 solution Substances 0.000 claims abstract description 60
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 37
- 238000005245 sintering Methods 0.000 claims abstract description 36
- 238000002156 mixing Methods 0.000 claims abstract description 27
- 239000012190 activator Substances 0.000 claims abstract description 18
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 150000002815 nickel Chemical class 0.000 claims abstract description 16
- 239000012266 salt solution Substances 0.000 claims abstract description 14
- RYYXDZDBXNUPOG-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1,3-benzothiazole-2,6-diamine;dihydrochloride Chemical compound Cl.Cl.C1C(N)CCC2=C1SC(N)=N2 RYYXDZDBXNUPOG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005520 cutting process Methods 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 238000005406 washing Methods 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000011268 mixed slurry Substances 0.000 claims description 15
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 14
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 14
- 238000002604 ultrasonography Methods 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
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- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- BHATUINFZWUDIX-UHFFFAOYSA-N Zwittergent 3-14 Chemical compound CCCCCCCCCCCCCC[N+](C)(C)CCCS([O-])(=O)=O BHATUINFZWUDIX-UHFFFAOYSA-N 0.000 claims description 7
- 230000009471 action Effects 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
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- 239000000203 mixture Substances 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 31
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 17
- 239000002245 particle Substances 0.000 abstract description 12
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
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- 238000011065 in-situ storage Methods 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 229910009871 Ti5Si3 Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 3
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- 238000003917 TEM image Methods 0.000 description 2
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- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- -1 3-sulfopropyl tetradecyl dimethyl ammonium ethanol Chemical compound 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 238000007731 hot pressing Methods 0.000 description 1
- KHYBPSFKEHXSLX-UHFFFAOYSA-N iminotitanium Chemical class [Ti]=N KHYBPSFKEHXSLX-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229910001000 nickel titanium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
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- B22—CASTING; POWDER METALLURGY
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
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- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
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Abstract
The invention discloses a preparation method of a novel modified carbon nanotube reinforced titanium-based composite material, which comprises the following steps: firstly, preparing an organic activator solution; secondly, dispersing the carbon nano tube into an organic activator solution to obtain a mixed solution; thirdly, adjusting the pH value of the mixed solution, and then adding a nickel salt solution and thiourea dioxide to react to obtain Ni @ CNTs composite powder; mixing the Ni @ CNTs composite powder with titanium powder or titanium alloy powder to obtain Ni @ CNTs titanium-based composite powder; and fifthly, adopting a rapid plasma discharge sintering method to perform pressure sintering on the Ni @ CNTs titanium-based composite powder, and sequentially performing rolling and linear cutting to obtain the Ni @ CNTs reinforced titanium-based composite material. According to the invention, Ni particles are uniformly coated on the surface of the carbon nano tube for modification, the formation of TiC is prevented, the integrity of the carbon material and the titanium matrix is ensured, the reinforcement effect is enhanced, and the Ni @ CNTs/TC4 reinforced titanium matrix composite material with the synergistically improved strong plasticity is obtained.
Description
Technical Field
The invention belongs to the technical field of composite material preparation, and particularly relates to a preparation method of a modified carbon nanotube reinforced titanium-based composite material.
Background
The titanium and the titanium alloy have wide application prospects in the fields of aerospace, automobile manufacturing, biomedical use and the like. The application in the related field requires not only high specific strength, high specific modulus, good biocompatibility and other properties, but also excellent high temperature performance.
For example, L i and the like adopt a powder metallurgy process to prepare 0-0.4 wt% of CNTs/Ti-based composite material, and when 0.4 wt% of CNTs is added, the titanium-based composite material obtains the optimal mechanical property, the yield strength and the tensile strength are respectively improved by 40.4% and 11.4%.
However, according to the Ti-C binary phase diagram, Ti atoms and C atoms are easy to react at a high temperature of more than 900 ℃ to generate stable TiC hard particles, so that the structural integrity of the carbon material and the matrix is seriously damaged, and the reinforcing effect of the CNTs is greatly weakened. The reported data show that the CNTs are added into the matrix titanium alloy, and TiC particles with different degrees are generated. How to exert the unique intrinsic characteristics of the CNTs and the matrix titanium alloy and synergistically improve the strong plasticity of the matrix is a problem to be solved at present.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a method for preparing a modified carbon nanotube reinforced titanium matrix composite material, aiming at the defects of the prior art. According to the method, the carbon nanotube is modified, so that the Ni particles uniformly coated on the surface of the carbon nanotube isolate Ti in a titanium base from C in the carbon nanotube, the reaction interface energy of Ti-C is reduced, and the formation of TiC is prevented, thus the damage of TiC hard particles generated by Ti and C to the structural integrity of the carbon material and the titanium base is avoided, the reinforcing effect of CNTs is enhanced, the plasticity of the Ni @ CNTs/TC4 reinforced titanium base composite material is improved, and the Ni @ CNTs/TC4 reinforced titanium base composite material with the synergistically improved strong plasticity is obtained.
In order to solve the technical problems, the invention adopts the technical scheme that: a preparation method of a modified carbon nanotube reinforced titanium-based composite material is characterized by comprising the following steps:
step one, dispersing 3-sulfopropyl tetradecyl dimethyl ammonium in an ethanol solution, and performing ultrasonic dispersion for 30-60 min to obtain an organic activator solution; the volume concentration of the ethanol solution is 5-20%;
dispersing the carbon nano tube into the organic activator solution obtained in the step one under the action of ultrasound to obtain a mixed solution; the power of the ultrasound is less than 20kW, and the time is not more than 60 min;
step three, adjusting the pH value of the mixed solution obtained in the step two to 8-10 by adopting ammonia water, then adding a soluble nickel salt solution, uniformly stirring, adding thiourea dioxide for reaction, centrifugally washing to obtain Ni @ CNTs mixed slurry, and carrying out low-temperature heat treatment on the Ni @ CNTs mixed slurry at the temperature of 100-300 ℃ to obtain Ni @ CNTs composite powder;
step four, placing the Ni @ CNTs composite powder obtained in the step three and titanium-based powder in a planetary powder mixer to be uniformly mixed to obtain Ni @ CNTs titanium-based composite powder; the titanium-based powder is titanium powder or titanium alloy powder;
putting the Ni @ CNTs titanium-based composite powder obtained in the fourth step into a die, performing pressure sintering by adopting a rapid plasma discharge sintering method to obtain a Ni @ CNTs reinforced titanium-based composite material blank, then performing medium-temperature and high-temperature multi-pass rolling in sequence, and performing warp cutting to obtain a Ni @ CNTs reinforced titanium-based composite material; the temperature of the medium-temperature multi-pass rolling is 400-600 ℃, the temperature of the high-temperature multi-pass rolling is 800-1000 ℃, the total deformation amount of the medium-temperature and high-temperature multi-pass rolling is 50-90%, the pressing amount of each pass of rolling is 1mm, and the heat preservation time of each pass of rolling is 10-30 min.
Dispersing Carbon Nano Tubes (CNTs) into an organic activator solution, adjusting the pH value, adding a soluble nickel salt solution and thiourea dioxide to perform one-step chemical co-reduction reaction to obtain Ni @ CNTs mixed slurry, performing low-temperature heat treatment to obtain Ni @ CNTs composite powder, performing dry-method powder mixing on the Ni @ CNTs composite powder and titanium powder or titanium alloy powder, performing pressure sintering by adopting a rapid plasma discharge sintering method, performing medium-temperature and high-temperature multi-pass rolling, and performing warp cutting to obtain Ni @ CNTs/TC4 composite material. The invention firstly utilizes 3-sulfopropyl tetradecyl dimethyl ammonium ethanol as an activator to improve the dispersibility of CNTs, further improves the uniform mixing degree of the CNTs, nickel sulfate and thiourea dioxide, then leads Ni particles to be uniformly coated on the surface of the CNTs after one-step chemical co-reduction reaction to obtain Ni @ CNTs composite powder, and in the process of pressure sintering after the Ni @ CNTs composite powder is mixed with titanium powder or titanium alloy powder, Ni in the Ni @ CNTs composite powder reacts with the titanium powder or the titanium alloy powder in situ to generate Ni2Ni in Ti, Ni @ CNTs composite powder2Ti isolates Ti in titanium powder or titanium alloy powder and C in CNTs, the Ti-C reaction interface energy is reduced, and the formation of TiC is prevented, so that the damage of TiC hard particles generated by Ti and C to the structural integrity of a carbon material and a titanium matrix is avoided, the reinforcing effect of CNTs is enhanced, the plasticity of the Ni @ CNTs/TC4 reinforced titanium matrix composite material is improved, and the Ni @ CNTs/TC4 reinforced titanium matrix composite material with the synergistically improved strong plasticity is obtained; meanwhile, Ni in the Ni @ CNTs composite powder2Ti improves the interfacial wettability of CNTs and titanium powder or titanium alloy powder matrix, improves the interfacial bonding strength and further improves the strong plasticity of the Ni @ CNTs/TC4 reinforced titanium-based composite material.
The preparation method of the modified carbon nanotube reinforced titanium-based composite material is characterized in that the volume concentration of ammonia water in the third step is 35%, the mass ratio of soluble nickel salt to carbon nanotubes in thiourea dioxide and soluble nickel salt solution is (0.1-1): 1-15): 2-50, and the reaction time is 10-60 min.
The preparation method of the modified carbon nanotube reinforced titanium-based composite material is characterized in that the soluble nickel salt solution is a mixed nickel salt solution formed by a nickel sulfate solution and a nickel chloride solution, or a nickel sulfate solution, the molar concentration ratio of the nickel sulfate solution to the nickel chloride solution in the mixed nickel salt solution is 1:2, and the concentration of the nickel sulfate solution in the mixed nickel salt solution is 0.1 mol/L-1.0 mol/L.
The preparation method of the modified carbon nanotube reinforced titanium-based composite material is characterized in that the washing liquid adopted in the centrifugal washing in the third step is formed by mixing ethanol and deionized water according to the volume ratio of 2: 1. By adopting the washing liquid, redundant impurities can be removed, and a better washing effect can be obtained.
The preparation method of the modified carbon nanotube reinforced titanium-based composite material is characterized in that the mass of the Ni @ CNTs composite powder in the Ni @ CNTs titanium-based composite powder is not more than 10%. The Ni @ CNTs titanium-based composite powder with the mass ratio is preferably adopted, so that the agglomeration of the Ni @ CNTs composite powder can be effectively prevented, the Ni @ CNTs composite powder is uniformly dispersed in titanium powder or titanium alloy powder, and the Ni @ CNTs titanium-based composite powder which is more uniformly mixed is obtained.
The preparation method of the modified carbon nanotube reinforced titanium-based composite material is characterized in that in the step four, the rotating speed of the planetary powder mixer in the mixing process is 100 to 300rmp, the ball-material ratio is (3 to 5) to 1, and the mixing time is 1 to 5 hours. The adoption of the mixing process parameters is beneficial to realizing good dispersion and full mixing between the Ni @ CNTs composite powder and the titanium powder or the titanium alloy powder, so that the Ni @ CNTs titanium-based composite powder with uniform components is obtained, and meanwhile, the Ni @ CNTs composite powder is partially alloyed with the titanium powder or the titanium alloy powder, so that the subsequent sintering is facilitated.
The preparation method of the modified carbon nanotube reinforced titanium-based composite material is characterized in that the mold is a graphite mold with the diameter of 60 mm.
The preparation method of the modified carbon nanotube reinforced titanium-based composite material is characterized in that the pressure of the pressure sintering is 30MPa to 45MPa, the heating rate is 50 ℃/min to 100 ℃/min, the temperature is 1000 ℃ to 1200 ℃, and the time is 5min to 10 min. The technological parameters of the pressure sintering are beneficial to the sintering of the Ni @ CNTs titanium-based composite powder in a two-phase region, the formation of a sintering neck is promoted, and the density of the Ni @ CNTs reinforced titanium-based composite material is improved.
The preparation method of the modified carbon nanotube reinforced titanium-based composite material is characterized in that the Ni @ CNTs reinforced titanium-based composite material blank is subjected to landfill cooling and then medium-temperature and high-temperature multi-pass rolling. The embedding and cooling are adopted, so that the oxidation of the Ni @ CNTs reinforced titanium-based composite material blank and the formation of nano-crystals by the titanium matrix in the Ni @ CNTs reinforced titanium-based composite material blank are effectively avoided, and the further dispersion of the CNTs in the titanium matrix is promoted.
Compared with the prior art, the invention has the following advantages:
1. the invention adopts a one-step chemical co-reduction method to ensure that Ni particles are uniformly coated on the surface of the carbon nano tube to modify the carbon nano tube, and then combines a rapid plasma discharge sintering method to ensure that the Ni particles generate Ni in situ2Ti isolates Ti in titanium powder or titanium alloy powder and C in CNTs, reduces the reaction interface energy of Ti-C and prevents the formation of TiC, thereby avoiding the damage of TiC hard particles generated by Ti and C to the structural integrity of carbon materials and titanium matrixes, enhancing the strengthening effect of CNTs, improving the plasticity of the Ni @ CNTs strengthened titanium matrix composite material and obtaining the Ni @ CNTs strengthened titanium matrix composite material with the synergetic improvement of the strong plasticity.
2. The invention makes Ni particles evenly coated on the surface of the carbon nano tube to modify the carbon nano tube, Ni is used as β stable element, and Ni is generated in situ on the surface of the carbon nano tube2Ti improves the interfacial wettability of CNTs and titanium powder or titanium alloy powder matrix, improves the interfacial bonding strength and further improves the strong plasticity of the Ni @ CNTs/TC4 reinforced titanium-based composite material.
3. The invention has simple operation process, low cost, no need of intermediate in-situ synthesis process precursor, wide application range, suitability for titanium alloy powder and aluminum alloy powder of various brands and industrial production.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Drawings
FIG. 1 is an SEM photograph of a Ni @ CNTs/TC4 reinforced titanium matrix composite prepared according to example 1 of the present invention.
FIG. 2a is a TEM image of Ni @ CNTs/TC4 reinforced titanium matrix composite prepared by the method of example 1.
FIG. 2b is a TEM spectrum of the Ni @ CNTs/TC4 reinforced titanium matrix composite prepared in example 1 of the present invention.
FIG. 3 is an SEM photograph of the CNTs/TC4 reinforced titanium matrix composite prepared by comparative example 1 of the present invention.
FIG. 4 is a graph of tensile stress vs. strain for Ni @ CNTs/TC4 reinforced titanium matrix composites prepared in example 1 of the present invention and CNTs/TC4 reinforced titanium matrix composites prepared in comparative example 1.
Detailed Description
Example 1
The preparation method of this example includes the following steps:
step one, 3g of 3-sulfopropyltetradecyldimethylammonium is dispersed in a 200m L volume concentration 5% ethanol solution for ultrasonic dispersion for 45min to obtain an organic activator solution;
step two, dispersing 1.0g of carbon nano tube into the organic activator solution obtained in the step one under the action of ultrasound to obtain a mixed solution; the power of the ultrasound is 18kW, and the time is 30 min;
step three, adjusting the pH value of the mixed solution obtained in the step two to 9 by adopting 35% ammonia water, then adding 5m L nickel sulfate solution with the concentration of 0.5 mol/L and 2m L nickel chloride solution with the concentration of 1.0 mol/L, uniformly stirring, then adding 0.05g thiourea dioxide, reacting for 10min at 25 ℃, performing centrifugal washing to obtain Ni @ CNTs mixed slurry, and performing low-temperature heat treatment on the Ni @ CNTs mixed slurry at 0.1MPa and 100 ℃ for 24h to remove redundant organic activating solution to obtain Ni @ CNTs composite powder, wherein the washing solution adopted in the centrifugal washing is formed by mixing ethanol and deionized water according to the volume ratio of 2: 1;
step four, putting 0.5g of Ni @ CNTs composite powder obtained in the step three and 199.5g of spherical TC4 powder into a planetary powder mixer to be uniformly mixed to obtain Ni @ CNTs/TC4 titanium-based composite powder; the rotating speed of the planetary powder mixer in the mixing process is 200rmp, the ball-material ratio is 4:1, and the mixing time is 3 hours;
putting the Ni @ CNTs/TC4 titanium-based composite powder obtained in the fourth step into a graphite die with the diameter of 60mm, performing pressure sintering by adopting a rapid plasma discharge sintering method to obtain a Ni @ CNTs/TC4 reinforced titanium-based composite material blank, burying and cooling the Ni @ CNTs/TC4 reinforced titanium-based composite material blank, sequentially performing medium-temperature 2-pass rolling and high-temperature 2-pass rolling, and performing warp cutting to obtain a Ni @ CNTs/TC4 reinforced titanium-based composite material; the pressure of the pressure sintering is 40MPa, the heating rate is 80 ℃/min, the temperature is 1100 ℃, and the time is 8 min; the temperature of the medium-temperature 2-pass rolling is 400 ℃; the temperature of the high-temperature 2-pass rolling is 800 ℃, the total deformation of the medium-temperature 2-pass rolling and the high-temperature 2-pass rolling is 66.7%, the rolling reduction of each pass is 1mm, and the heat preservation time of each pass is 20 min.
The titanium-based powder in this embodiment may also be titanium powder.
FIG. 1 is an SEM photograph of the Ni @ CNTs/TC4 reinforced titanium matrix composite prepared in this example, and it can be seen from FIG. 1 that almost no interfacial products are formed in the Ni @ CNTs/TC4 reinforced titanium matrix composite prepared in this example.
FIG. 2a is a TEM image of the Ni @ CNTs/TC4 reinforced titanium matrix composite prepared in this example, and it can be seen from FIG. 2a that no carbide is generated at the interface of the Ni @ CNTs/TC4 reinforced titanium matrix composite prepared in this example.
FIG. 2b is a TEM spectrum of the Ni @ CNTs/TC4 reinforced Ti-based composite material prepared in this example, and it can be seen from FIG. 2b that the Ni and Ti elements at the interface of the Ni @ CNTs/TC4 reinforced Ti-based composite material have opposite trend, which shows that Ni-Ti compounds are generated in the Ni @ CNTs/TC4 reinforced Ti-based composite material, and mainly Ni2Ti, NiTi and the like can be used as a bridge to connect the interfaces, and the interface bonding strength is obviously improved.
The mechanical properties of the Ni @ CNTs/TC4 reinforced titanium-based composite material prepared in the example are compared with those of the reinforced titanium-based composite material reported in the prior art, and the results are shown in the following table 1.
TABLE 1 mechanical properties of the Ni @ CNTs/TC4 reinforced titanium matrix composites prepared in example 1 and those of the prior art
5 vol% in the column of materials in Table 1 (TiB)w+TiCP) The term,/Ti 64, is described In L JTiBw+TiCP)/Ti6Al4V composites with a network reinforcement distribution”,MaterialScience and Engineering A 527(2010)6723-6727；4vol％Ti5Si3And 4 vol% Ti5Si3+0.5vol％TiBwSee literature: jiano "Effects of first-scale TiBW on second-scale Ti5Si3characteristics and mechanical properties of in-situ(Ti5Si3+TiBw)/Ti6Al4V composites”,Journal of Alloys and Compounds 704(2017)269-281；5vol％TiBwThe term/TC 4 is described In L Jw/Ti6Al4V composites with novelreinforcement architecture fabricated by reaction hot pressing”,ScriptaMaterialia(2009)996-999。
As can be seen from Table 1, the tensile strength and the yield strength of the Ni @ CNTs/TC4 reinforced titanium-based composite material prepared in the embodiment are equivalent to those of the reinforced titanium-based composite material in the existing report, but the elongation of the Ni @ CNTs/TC4 reinforced titanium-based composite material prepared in the embodiment is greatly improved compared with that of several reinforced titanium-based composite materials in the existing report, which indicates that the Ni particles are uniformly coated on the surface of the carbon nanotube to modify the carbon nanotube, the formation of TiC is prevented, the damage to the structural integrity of the carbon material and the titanium matrix is avoided, the plasticity of the Ni @ CNTs/TC4 reinforced titanium-based composite material is improved, and the Ni @ CNTs/TC4 reinforced titanium-based composite material with the synergistically improved strong plasticity is obtained.
Comparative example 1
The preparation method of this comparative example comprises the following steps:
step one, 0.5g of carbon nano tube and 199.5g of spherical TC4 powder are placed in a planetary powder mixer to be uniformly mixed to obtain CNTs/TC4 titanium-based composite powder; the rotating speed of the planetary powder mixer in the mixing process is 200rmp, the ball-material ratio is 4:1, and the mixing time is 3 hours;
putting the CNTs/TC4 titanium-based composite powder obtained in the step one into a graphite die with the diameter of 60mm, performing pressure sintering by adopting a rapid plasma discharge sintering method to obtain a CNTs/TC4 reinforced titanium-based composite material blank, burying and cooling the CNTs/TC4 reinforced titanium-based composite material blank, sequentially performing medium-temperature 2-pass rolling and high-temperature 2-pass rolling, and performing warp cutting to obtain the Ni @ CNTs/TC4 reinforced titanium-based composite material; the pressure of the pressure sintering is 40MPa, the heating rate is 80 ℃/min, the temperature is 1100 ℃, and the time is 8 min; the temperature of the medium-temperature 2-pass rolling is 400 ℃; the temperature of the high-temperature 2-pass rolling is 800 ℃, the total deformation of the medium-temperature 2-pass rolling and the high-temperature 2-pass rolling is 66.7%, the rolling reduction of each pass is 1mm, and the heat preservation time of each pass is 20 min.
FIG. 3 is an SEM photograph of the CNTs/TC4 reinforced Ti-based composite material prepared by the present comparative example, and it can be seen from FIG. 3 that a great amount of interface carbide products are generated at the grain boundary of the CNTs/TC4 reinforced Ti-based composite material prepared by directly sintering carbon nanotubes and TC4 powder in the prior art.
As can be seen by comparing FIG. 1 with FIG. 3, the Ni @ CNTs/TC4 reinforced titanium matrix composite material of the present invention effectively prevents Ti and C from reacting to form carbide at high temperature, thereby maintaining the structural integrity of TC4 matrix and CNTs.
FIG. 4 is a tensile stress-strain diagram of the Ni @ CNTs/TC4 reinforced titanium-based composite material prepared in example 1 of the present invention and the CNTs/TC4 reinforced titanium-based composite material prepared in comparative example 1, and it can be seen from FIG. 4 that the tensile stress-strain of the Ni @ CNTs/TC4 reinforced titanium-based composite material prepared in example 1 is greatly improved compared with the tensile stress-strain of the CNTs/TC4 reinforced titanium-based composite material prepared in comparative example 1, which shows that the present invention adopts Ni to uniformly coat the surface of the carbon nanotube for modification and then sintering, which greatly improves the interfacial properties of the TC4 matrix, and greatly synergistically improves the strength and plasticity of the Ni @ CNTs/TC4 reinforced titanium-based composite material.
Example 2
The preparation method of this example includes the following steps:
step one, dispersing 1g of 3-sulfopropyltetradecyldimethylammonium into an ethanol solution with the volume concentration of 100m L of 8% for ultrasonic dispersion for 30min to obtain an organic activator solution;
step two, dispersing 0.5g of carbon nano tube into the organic activator solution obtained in the step one under the action of ultrasound to obtain a mixed solution; the power of the ultrasound is 18kW, and the time is 30 min;
step three, adjusting the pH value of the mixed solution obtained in the step two to 8 by adopting 35% ammonia water, then adding 0.1 mol/L nickel sulfate solution with the volume concentration of 4m L and 0.2 mol/L nickel chloride solution with the volume concentration of 1.5m L, uniformly stirring, then adding 0.01g of thiourea dioxide, reacting for 10min at 25 ℃, performing centrifugal washing to obtain Ni @ CNTs mixed slurry, performing low-temperature heat treatment on the Ni @ CNTs mixed slurry at 1MPa and 300 ℃ for 12h to remove redundant organic activating solution, and obtaining Ni @ CNTs composite powder, wherein the washing solution adopted in the centrifugal washing is formed by mixing ethanol and deionized water according to the volume ratio of 2: 1;
step four, putting 0.2g of Ni @ CNTs composite powder 2 obtained in the step three and 199.8g of spherical TC4 powder into a planetary powder mixer to be uniformly mixed to obtain Ni @ CNTs/TC4 titanium-based composite powder; the rotating speed of the planetary powder mixer in the mixing process is 100rmp, the ball-material ratio is 5:1, and the mixing time is 2 hours;
putting the Ni @ CNTs/TC4 titanium-based composite powder obtained in the fourth step into a graphite die with the diameter of 60mm, performing pressure sintering by adopting a rapid plasma discharge sintering method to obtain a Ni @ CNTs/TC4 reinforced titanium-based composite material blank, burying and cooling the Ni @ CNTs/TC4 reinforced titanium-based composite material blank, sequentially performing medium-temperature 2-pass rolling and high-temperature 2-pass rolling, and performing warp cutting to obtain a Ni @ CNTs/TC4 reinforced titanium-based composite material; the pressure of the pressure sintering is 45MPa, the heating rate is 100 ℃/min, the temperature is 1000 ℃, and the time is 10 min; the temperature of the medium-temperature 2-pass rolling is 550 ℃; the temperature of the high-temperature 2-pass rolling is 900 ℃, the total deformation of the medium-temperature 2-pass rolling and the high-temperature 2-pass rolling is 50%, the pressing amount of each pass of rolling is 1mm, and the heat preservation time of each pass of rolling is 10 min.
The titanium-based powder in this embodiment may also be titanium powder.
Example 3
The preparation method of this example includes the following steps:
step one, dispersing 4g of 3-sulfopropyltetradecyldimethylammonium into 500m L volume concentration 12% ethanol solution, and performing ultrasonic dispersion for 60min to obtain organic activator solution;
step two, dispersing 2.5g of carbon nano tubes into the organic activator solution obtained in the step one under the action of ultrasound to obtain a mixed solution; the power of the ultrasound is 18kW, and the time is 60 min;
step three, adjusting the pH value of the mixed solution obtained in the step two to 10 by adopting 35% ammonia water, then adding 1.0 mol/L nickel sulfate solution with the volume concentration of 3.2m L and 2 mol/L nickel chloride solution with the volume concentration of 1m L, uniformly stirring, then adding 0.05g of thiourea dioxide, reacting for 30min at 25 ℃, performing centrifugal washing to obtain Ni @ CNTs mixed slurry, performing low-temperature heat treatment on the Ni @ CNTs mixed slurry at 0.1MPa and 200 ℃ for 15h to remove redundant organic activating solution, and obtaining Ni @ CNTs composite powder, wherein the washing solution adopted in the centrifugal washing is formed by mixing ethanol and deionized water according to the volume ratio of 2: 1;
step four, putting 1g of the Ni @ CNTs composite powder obtained in the step three and 199g of spherical TC4 powder into a planetary powder mixer to be uniformly mixed to obtain Ni @ CNTs/TC4 titanium-based composite powder; the rotating speed of the planetary powder mixer in the mixing process is 300rmp, the ball-material ratio is 3:1, and the mixing time is 5 hours;
putting the Ni @ CNTs/TC4 titanium-based composite powder obtained in the fourth step into a graphite die with the diameter of 60mm, performing pressure sintering by adopting a rapid plasma discharge sintering method to obtain a Ni @ CNTs/TC4 reinforced titanium-based composite material blank, burying and cooling the Ni @ CNTs/TC4 reinforced titanium-based composite material blank, sequentially performing medium-temperature 2-pass rolling and high-temperature 2-pass rolling, and performing warp cutting to obtain a Ni @ CNTs/TC4 reinforced titanium-based composite material; the pressure of the pressure sintering is 30MPa, the heating rate is 50 ℃/min, the temperature is 1200 ℃, and the time is 5 min; the temperature of the medium-temperature 2-pass rolling is 500 ℃; the temperature of the high-temperature 2-pass rolling is 850 ℃, the total deformation of the medium-temperature 2-pass rolling and the high-temperature 2-pass rolling is 80%, the pressing amount of each pass of rolling is 1mm, and the heat preservation time of each pass of rolling is 30 min.
The titanium-based powder in this embodiment may also be titanium powder.
Example 4
The preparation method of this example includes the following steps:
step one, dispersing 10g of 3-sulfopropyltetradecyldimethylammonium into a 100m L volume concentration 20% ethanol solution, and performing ultrasonic dispersion for 30min to obtain an organic activator solution;
step two, dispersing 20g of carbon nano tubes into the organic activator solution obtained in the step one under the action of ultrasound to obtain a mixed solution; the power of the ultrasound is 18kW, and the time is 30 min;
step three, adjusting the pH value of the mixed solution obtained in the step two to 8 by adopting 35% ammonia water, then adding 31m L of 1.0 mol/L nickel sulfate solution and 40m L of 1.0 mol/L nickel chloride solution, uniformly stirring, then adding 1g thiourea dioxide, reacting for 60min at 25 ℃, obtaining Ni @ CNTs mixed slurry through centrifugal washing, and carrying out low-temperature heat treatment on the Ni @ CNTs mixed slurry at 1MPa and 300 ℃ for 10h to remove redundant organic activating solution, thus obtaining Ni @ CNTs composite powder, wherein the washing solution adopted in the centrifugal washing is formed by mixing ethanol and deionized water according to the volume ratio of 2: 1;
step four, putting 20g of the Ni @ CNTs composite powder obtained in the step three and 180g of spherical TC4 powder into a planetary powder mixer to be uniformly mixed to obtain Ni @ CNTs/TC4 titanium-based composite powder; the rotating speed of the planetary powder mixer in the mixing process is 300rmp, the ball-material ratio is 3:1, and the mixing time is 1 h;
putting the Ni @ CNTs/TC4 titanium-based composite powder obtained in the fourth step into a graphite die with the diameter of 60mm, performing pressure sintering by adopting a rapid plasma discharge sintering method to obtain a Ni @ CNTs/TC4 reinforced titanium-based composite material blank, burying and cooling the Ni @ CNTs/TC4 reinforced titanium-based composite material blank, sequentially performing medium-temperature 2-pass rolling and high-temperature 2-pass rolling, and performing warp cutting to obtain a Ni @ CNTs/TC4 reinforced titanium-based composite material; the pressure of the pressure sintering is 45MPa, the heating rate is 100 ℃/min, the temperature is 1150 ℃, and the time is 8 min; the temperature of the medium-temperature 2-pass rolling is 600 ℃; the temperature of the high-temperature 2-pass rolling is 1000 ℃, the total deformation of the medium-temperature 2-pass rolling and the high-temperature 2-pass rolling is 90%, the pressing amount of each pass of rolling is 1mm, and the heat preservation time of each pass of rolling is 10 min.
The titanium-based powder in this embodiment may also be titanium powder.
Example 5
The preparation method of this example includes the following steps:
step one, dispersing 5g of 3-sulfopropyltetradecyldimethylammonium into a 100m L volume concentration 20% ethanol solution, and performing ultrasonic dispersion for 30min to obtain an organic activator solution;
step two, dispersing 20g of carbon nano tubes into the organic activator solution obtained in the step one under the action of ultrasound to obtain a mixed solution; the power of the ultrasound is 18kW, and the time is 30 min;
step three, adjusting the pH value of the mixed solution obtained in the step two to 8 by adopting 35% ammonia water, adding 129m L nickel sulfate solution with the concentration of 0.5 mol/L, adding 0.8g thiourea dioxide, reacting for 60min at 25 ℃, performing centrifugal washing to obtain Ni @ CNTs mixed slurry, performing low-temperature heat treatment on the Ni @ CNTs mixed slurry at 1MPa and 300 ℃ for 10h to remove redundant organic activating solution, and obtaining Ni @ CNTs composite powder, wherein the washing solution adopted in the centrifugal washing is formed by mixing ethanol and deionized water according to the volume ratio of 2: 1;
step four, putting 10g of the Ni @ CNTs composite powder obtained in the step three and 90g of spherical TC4 powder into a planetary powder mixer to be uniformly mixed to obtain Ni @ CNTs/TC4 titanium-based composite powder; the rotating speed of the planetary powder mixer in the mixing process is 300rmp, the ball-material ratio is 3:1, and the mixing time is 1 h;
putting the Ni @ CNTs/TC4 titanium-based composite powder obtained in the fourth step into a graphite die with the diameter of 60mm, performing pressure sintering by adopting a rapid plasma discharge sintering method to obtain a Ni @ CNTs/TC4 reinforced titanium-based composite material blank, burying and cooling the Ni @ CNTs/TC4 reinforced titanium-based composite material blank, sequentially performing medium-temperature 2-pass rolling and high-temperature 2-pass rolling, and performing warp cutting to obtain a Ni @ CNTs/TC4 reinforced titanium-based composite material; the pressure of the pressure sintering is 45MPa, the heating rate is 100 ℃/min, the temperature is 1150 ℃, and the time is 8 min; the temperature of the medium-temperature 2-pass rolling is 600 ℃; the temperature of the high-temperature 2-pass rolling is 900 ℃, the total deformation of the medium-temperature 2-pass rolling and the high-temperature 2-pass rolling is 70%, the pressing amount of each pass of rolling is 1mm, and the heat preservation time of each pass of rolling is 30 min.
The titanium-based powder in this embodiment may also be titanium powder.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (9)
1. A preparation method of a modified carbon nanotube reinforced titanium-based composite material is characterized by comprising the following steps:
step one, dispersing 3-sulfopropyl tetradecyl dimethyl ammonium in an ethanol solution, and performing ultrasonic dispersion for 30-60 min to obtain an organic activator solution; the volume concentration of the ethanol solution is 5-20%;
dispersing the carbon nano tube into the organic activator solution obtained in the step one under the action of ultrasound to obtain a mixed solution; the power of the ultrasound is less than 20kW, and the time is not more than 60 min;
step three, adjusting the pH value of the mixed solution obtained in the step two to 8-10 by adopting ammonia water, then adding a soluble nickel salt solution, uniformly stirring, adding thiourea dioxide for reaction, centrifugally washing to obtain Ni @ CNTs mixed slurry, and carrying out low-temperature heat treatment on the Ni @ CNTs mixed slurry at the temperature of 100-300 ℃ to obtain Ni @ CNTs composite powder;
step four, placing the Ni @ CNTs composite powder obtained in the step three and titanium-based powder in a planetary powder mixer to be uniformly mixed to obtain Ni @ CNTs titanium-based composite powder; the titanium-based powder is titanium powder or titanium alloy powder;
putting the Ni @ CNTs titanium-based composite powder obtained in the fourth step into a die, performing pressure sintering by adopting a rapid plasma discharge sintering method to obtain a Ni @ CNTs reinforced titanium-based composite material blank, then performing medium-temperature and high-temperature multi-pass rolling in sequence, and performing warp cutting to obtain a Ni @ CNTs reinforced titanium-based composite material; the temperature of the medium-temperature multi-pass rolling is 400-600 ℃, the temperature of the high-temperature multi-pass rolling is 800-1000 ℃, the total deformation amount of the medium-temperature and high-temperature multi-pass rolling is 50-90%, the pressing amount of each pass of rolling is 1mm, and the heat preservation time of each pass of rolling is 10-30 min.
2. The method for preparing the modified carbon nanotube reinforced titanium-based composite material as claimed in claim 1, wherein the volume concentration of the ammonia water in the step three is 35%, the mass ratio of the soluble nickel salt to the carbon nanotube in the thiourea dioxide and soluble nickel salt solution is (0.1-1): 1-15): 2-50, and the reaction time is 10-60 min.
3. The method for preparing the modified carbon nanotube reinforced titanium-based composite material of claim 1, wherein the soluble nickel salt solution is a mixed nickel salt solution formed by a nickel sulfate solution and a nickel chloride solution, or a nickel sulfate solution, the molar concentration ratio of the nickel sulfate solution to the nickel chloride solution in the mixed nickel salt solution is 1:2, and the concentration of the nickel sulfate solution in the mixed nickel salt solution is 0.1 mol/L-1.0 mol/L.
4. The method for preparing the modified carbon nanotube reinforced titanium-based composite material as claimed in claim 1, wherein the washing solution used in the centrifugal washing in the third step is a mixture of ethanol and deionized water in a volume ratio of 2: 1.
5. The method for preparing the modified carbon nanotube reinforced titanium-based composite material of claim 1, wherein the mass of the Ni @ CNTs composite powder in the Ni @ CNTs titanium-based composite powder in the step four is not more than 10%.
6. The method for preparing the modified carbon nanotube reinforced titanium-based composite material as claimed in claim 1, wherein the planetary powder mixer in the mixing process in the step four has a rotation speed of 100 to 300rmp, a ball-to-material ratio of (3 to 5) to 1, and a mixing time of 1 to 5 hours.
7. The method of claim 1, wherein the mold is a graphite mold with a diameter of 60 mm.
8. The method for preparing the modified carbon nanotube reinforced titanium-based composite material of claim 1, wherein the pressure sintering is performed at a pressure of 30MPa to 45MPa, a temperature rise rate of 50 ℃/min to 100 ℃/min, a temperature of 1000 ℃ to 1200 ℃, and a time of 5min to 10 min.
9. The method for preparing the modified carbon nanotube reinforced titanium-based composite material as claimed in claim 1, wherein the Ni @ CNTs reinforced titanium-based composite material blank is subjected to medium-temperature and high-temperature multi-pass rolling after being buried and cooled.
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