CN103526136B - Preparation method for reinforced titanium matrix composite of three-dimensional network-shaped carbon nanotube - Google Patents
Preparation method for reinforced titanium matrix composite of three-dimensional network-shaped carbon nanotube Download PDFInfo
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- CN103526136B CN103526136B CN201310453576.9A CN201310453576A CN103526136B CN 103526136 B CN103526136 B CN 103526136B CN 201310453576 A CN201310453576 A CN 201310453576A CN 103526136 B CN103526136 B CN 103526136B
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Abstract
The invention discloses a preparation method for a reinforced titanium matrix composite of a three-dimensional network-shaped carbon nanotube. The method comprises the processes as follows: sodium chloride powder and pure titanium powder are mixed into a blank, and sintering and dissolution are performed, so that porous titanium is obtained; and the porous titanium is immersed into a catalyst solution prepared through cobalt nitrate or nickel nitrate and yttrium nitrate, and the porous titanium loaded with catalyst salt is subjected to calcination, hydrogen gas reduction and catalytic cracking, so that the reinforced titanium matrix composite of the three-dimensional network-shaped carbon nanotube is obtained. The preparation method has the advantages as follows: on one hand, a catalyst, a growth technology and the like are adjusted, so that the carbon nanotube with homo-disperse and an integral structure can directly grow on the porous titanium; and on the other hand, the porous titanium can be directly taken as a composite material matrix, so that a subsequent high-temperature sintering process is avoided, an integral structure of the matrix and a reinforced phase is guaranteed, and the preparation process of the method is simple, and the implementation and the promotion are facilitated.
Description
Technical field
The present invention relates to the preparation method that a kind of three-dimensional network shape carbon nanotube strengthens titanium matrix composite, belong to the technology of preparing of matrix material.
Background technology
Carbon nanotube (CNTs) has enjoyed investigator to pay close attention to owing to having the performance of unique structure and excellence since being found by Japanese Scientists Iijima from 1991.In carbon nanotube, carbon atom adopts sp
2hydridization, compares sp
3hydridization, sp
2in hydridization, S orbital composition is larger, makes carbon nanotube have high-modulus and high strength.Owing to having low density (1.3g/cm
3) and high Young's modulus (973GPa) carbon nanotube become the desirable wild phase preparing matrix material.Research in the past shows that CNTs strengthens the feature of metal-base composites, and mainly some Industrial Metals, as aluminium, magnesium, nickel, copper and alloy thereof.CNTs is the dispersiveness of CNTs and the associativity with interface as the subject matter of wild phase.When preparing metal-base composites, the feed postition of carbon nanotube can be divided into two classes: a class is outer addition, namely utilizes high speed machine ball milling or organic solvent ultrasonic disperse, makes CNTs reach good dispersion effect in the base.But this method can destroy the structural integrity of CNTs, affect the raising of composite property; Another kind of is in-situ synthesis, namely adopts deposition-precipitation method or pickling process at surface of metal particles deposited catalyst salt, forms granules of catalyst, introduce gas or solid carbon source at a certain temperature, growth in situ CNTs after certain temperature calcining, reduction.In matrix material prepared by the method, CNTs can be dispersed in metal powder surface more uniformly, and the composite property prepared through powder metallurgic method improves more obvious.
Titanium and titanium alloys is owing to having high specific tenacity, specific rigidity and Young's modulus, be widely used in the field such as automobile, aviation, therefore the attractive matrix of the one preparing metal-base composites is also become, and owing to having high erosion resistance, the application of titanium and titanium alloys in chemistry and petrochemical complex etc. is also very excellent.Take titanium as matrix material prepared by matrix, become the candidate material of ultrahigh frequency speed aerospace vehicle and advanced aero engine of future generation due to its high specific tenacity, specific rigidity, high tenacity and high temperature resistance characteristic.Titanium matrix composite can be divided into two large classes by the difference of reinforcement: discontinuous particle reinforce and continuous fiber reinforcing titanium matrix composite.Conventional enhanced granule has TiB, TiB
2, TiC, SiC, B
4c, GrB, Ti
5si
3deng, conventional fortifying fibre has carbon fiber, boron fibre, silicon carbide fiber etc.
A major issue in matrix material research is the interface cohesion problem of wild phase and matrix, and adopt matrix material prepared by the method for in-situ authigenic wild phase, its performance obtains better improvement.At present, the method for In Situ Synthesized Titanium Matrix Composites has: powder metallurgic method (P/M), mechanical alloying (MA), Self-propagating High-temperature Synthesis Process (SHS), heat release diffusion process (XDTM), flash set technology (RSP) and various melting and casting technology.Kondoh etc. are with zwitterionics to CNTs process, and make its surface with hydrophilic and hydrophobic functional group, such CNTs can reach good dispersion, obtain CNTs/Ti composite powder after then dripping titanium valve drying.Composite powder is used graphite jig compression moulding, after 873K and 1073K cremate plasma body Fast Sintering, obtain CNTs/Ti matrix material respectively, finally under 1273K, hot extrusion is carried out to obtained matrix material.The tensile strength of the titanium matrix composite prepared in this way and the purer titanium of yielding stress improve 157MPa and 169MPs respectively, but its unit elongation decreases 34-38%.University Of Tianjin Wang Ying etc. utilizes the CNTs that chemical Vapor deposition process (CVD) is evenly distributed on titanium valve surface, pattern is good.The general CNTs for preparing strengthens in the method for titanium matrix composite, it is all the composite powder first obtaining CNTs and titanium, then titanium matrix composite is prepared through powder metallurgy, the problem wherein existed is that titanium and CNTs are easy to react under high temperature (general more than 900 DEG C), generate titanium carbide granule, thus destroy the satisfactory texture of CNTs, and the titanium carbide generated is a kind of hard phase, can reduce the performance of matrix material when content exceedes certain value.
Summary of the invention
A kind of three-dimensional network shape carbon nanotube is the object of the present invention is to provide to strengthen the preparation method of titanium matrix composite.In titanium matrix composite obtained in this way, three-dimensional network CNTs is uniformly distributed, and structural integrity, its preparation process is simple.
The present invention is realized by the following technical programs, and a kind of three-dimensional network shape carbon nanotube strengthens the preparation method of titanium matrix composite, it is characterized in that comprising following process:
1) POROUS TITANIUM is prepared
Be 300 ~ 500 revs/min by sodium-chlor with rotational speed of ball-mill, ratio of grinding media to material is (10 ~ 20): 1, Ball-milling Time is that the parameter ball milling of 40 ~ 60min becomes particle diameter to be 30 ~ 60um, by the sodium-chlor after ball milling and 400 order titanium valves with volume ratio 3:2 mixer batch mixing 2 ~ 3h, and then compressing tablet; Compressing tablet is placed in tube furnace, under argon shield with heat-up rate be 10 DEG C/min be warming up to 790 DEG C calcining 2 hours, then continue to be warming up to 1100 DEG C of calcinings 2 hours with 10 DEG C/min, cool to room temperature with the furnace, compressing tablet block after sintering is placed in 80 ~ 100 DEG C of heat recirculated water 8 ~ 10h and removes sodium-chlor, obtain POROUS TITANIUM;
2) vacuum impregnation catalyzer
POROUS TITANIUM step 1) obtained is placed in filter flask, under vacuum tightness is 0.001 ~ 0.01MPa, vacuumize 20 ~ 30min, then in filter flask, add the cobalt nitrate hexahydrate solution submergence POROUS TITANIUM of 0.001 ~ 0.05mol/L concentration, or in filter flask, add amount of substance than the six water nickelous nitrates and the six water Yttrium trinitrate mixing solutionss that are 1:1, mixed liquid concentration is the solution submergence POROUS TITANIUM of 0.001 ~ 0.05mol/L, continue to vacuumize 20 ~ 30min, through vacuum-drying 8 ~ 10h at 60 ~ 100 DEG C of temperature, obtain the POROUS TITANIUM that load has catalyzer salt;
3) chemical Vapor deposition process prepares three-dimensional network shape carbon nanotube enhancing titanium matrix composite
By step 2) obtained load has the POROUS TITANIUM of catalyzer salt to be placed in quartz tube furnace, under the protection of argon gas, is warming up to 400 ~ 450 DEG C, calcining at constant temperature 1h with the heat-up rate of 10 DEG C/min.Then continue to be warming up to 450 ~ 500 DEG C with 10 DEG C/min, closing argon gas, is that 150 ~ 250ml/min passes into H in stove with flow velocity
2reduction 1h, continue to be warming up to 500 DEG C ~ 700 DEG C with 10 DEG C/min, be the gas mixture that 310 ~ 340mL/min passes into acetylene and argon gas in stove with flow velocity, the volume ratio of acetylene and argon gas is 1:(15 ~ 30), carry out the catalytic cracking reaction of 20 ~ 60min, then be cooled to room temperature under an argon atmosphere, obtain three-dimensional network shape carbon nanotube and strengthen titanium matrix composite.
The present invention has the following advantages: solve carbon nanotube on the one hand and be easy to difficult problem of disperseing of reuniting in the composite, in gained titanium matrix composite of the present invention, carbon nanotube dispersed is even, and carbon nanotube structure is complete, purity is high, the performance of matrix material can be made to be improved significantly, meanwhile, by the control of the experiment parameter such as growth temperature, carrier gas ratio, the productive rate of carbon nanotube, pattern and distribution etc. can be regulated.On the other hand, the present invention for CNTs growing substrate, avoids the high-temperature sintering process of follow-up powder metallurgy with POROUS TITANIUM block materials, effectively can avoid the reaction between carbon nanotube and titanium, ensure that body material and wild phase are not destroyed, composite property is improved significantly.
Accompanying drawing explanation
Fig. 1 is the SEM photo of the POROUS TITANIUM sample that the embodiment of the present invention 1 obtains.
Fig. 2 is the SEM photo of the CNTs obtained after the embodiment of the present invention 1 catalytic pyrolysis carbon-source gas.
Fig. 3 obtains the SEM photo that three-dimensional network shape CNTs strengthens titanium matrix composite after the embodiment of the present invention 1 catalytic pyrolysis carbon-source gas.
Fig. 4 obtains the SEM photo that three-dimensional network shape CNTs strengthens titanium matrix composite after the embodiment of the present invention 2 catalytic pyrolysis carbon-source gas.
Fig. 5 obtains the SEM photo that three-dimensional network shape CNTs strengthens titanium matrix composite after the embodiment of the present invention 5 catalytic pyrolysis carbon-source gas.
Embodiment
Embodiment 1
By 10g sodium-chlor and 200g agate ball, be 500rpm at rotating speed, ball milling 40min, obtains the sodium chloride powder that median size is 30 μm.The sodium-chlor got after the 400 order titanium valves of 10g and 7.08g ball milling puts into drum mixer batch mixing 2h.Then get mixed powder Φ 10 mould compressing tablet on powder compressing machine of 0.6g ball milling sodium-chlor and titanium valve, pressure is 8MPa, dwell time 2min.Be placed in tube furnace by compressing tablet gained block, pass into the Ar gas of 300ml/min for protection gas, be warming up to 790 DEG C of insulation 2h with the heat-up rate of 10 DEG C/min, rear continuation is warming up to 1100 DEG C of insulation 2h with the speed of 10 DEG C/min, then cools to room temperature with the furnace.Block after sintering is placed in the heat recirculated water 8h removing sodium-chlor wherein of 80 DEG C, ultrasonic 30min removes impurity, and 80 DEG C of vacuum-drying 5h, obtain porous titanium material.
The POROUS TITANIUM of preparation be placed in dry filter flask, Erlenmeyer flask connect cone point funnel, close phragmocone and divide funnel switch, filter flask connects with circulating water type vacuum pump, continues to vacuumize 30min after being evacuated to 0.001MPa.Take 0.2908g six water nickelous nitrate and 0.1264g six water Yttrium trinitrate respectively, dissolve in 100ml deionized water, be mixed with the solution of 0.01mol/L, join in cone point funnel, open cone point funnel switch, allow solution flow into submergence POROUS TITANIUM in filter flask, closing switch, continues to vacuumize 30min.Then the POROUS TITANIUM of catalyzer salts solution load is had to take out, to be placed at vacuum drying oven 80 DEG C after vacuum-drying 8h, put it in quartzy Noah's ark, be placed in the flat-temperature zone, middle part of silica tube Reaktionsofen, pass into Ar gas shielded, temperature 400 DEG C is risen to the heat-up rate of 10 DEG C/min, calcining at constant temperature 1h, then 450 DEG C are warming up to the heat-up rate of 10 DEG C/min, pass into hydrogen with flow velocity 200ml/min to silica tube and carry out reduction 1h, then hydrogen is closed, pass into argon gas, 550 DEG C are warming up to equally with the speed of 10 DEG C/min, pass into the mixed gas of argon gas and acetylene with flow velocity 310ml/min after temperature-stable, wherein the volume ratio of argon gas acetylene is 30:1, scission reaction 30min, then room temperature is cooled to stove under an ar atmosphere, obtain the network-like CNTs of growing three-dimensional in POROUS TITANIUM and strengthen titanium matrix composite.
Embodiment 2
Concrete grammar and step are with embodiment 1, different conditions is: change 0.2908g six water nickelous nitrate and 0.1264g six water Yttrium trinitrate into 0.02908g six water nickelous nitrate and 0.01264g six water Yttrium trinitrate, due to the minimizing of catalytic amount, the amount obtaining CNTs after catalytic cracking reaction reduces, and distribution is in the base also uneven.
Embodiment 3
Concrete grammar and step are with embodiment 1, different conditions is: change 0.2908g six water nickelous nitrate and 0.1264g six water Yttrium trinitrate into 0.2910g cobalt nitrate hexahydrate, the pattern obtaining CNTs after catalytic cracking reaction is good, and can form homodisperse one deck at POROUS TITANIUM particle surface.
Embodiment 4
Concrete grammar and step are with embodiment 1, different conditions is: change 0.2908g six water nickelous nitrate and 0.1264g six water Yttrium trinitrate into 1.4550g cobalt nitrate hexahydrate, because catalyst content increases, reunion may be there is in the granules of catalyst after calcining reduction, after catalytic pyrolysis carbon-source gas, the CNTs major part of growth can dispersed POROUS TITANIUM surface, but has occurred CNTs agglomeration in some positions.
Embodiment 5
Concrete grammar and step are with embodiment 1, different conditions is: the temperature of catalytic pyrolysis carbon-source gas is brought up to 600 DEG C, granules of catalyst after reduction may have occurred reunion at the temperature of 600 DEG C, the activity of catalyzer is also had a certain impact, makes the pattern of CNTs different from the situation obtaining CNTs at 550 DEG C with dispersiveness.
Claims (1)
1. three-dimensional network shape carbon nanotube strengthens a preparation method for titanium matrix composite, it is characterized in that comprising following process:
1) POROUS TITANIUM is prepared
Be 300 ~ 500 revs/min by sodium-chlor with rotational speed of ball-mill, ratio of grinding media to material is (10 ~ 20): 1, and Ball-milling Time is that the parameter ball milling of 40 ~ 60min becomes particle diameter to be 30 ~ 60
μm, by the sodium-chlor after ball milling and 400 order titanium valves with volume ratio 3:2 mixer batch mixing 2 ~ 3h, then compressing tablet; Compressing tablet is placed in tube furnace, under argon shield with heat-up rate be 10 DEG C/min be warming up to 790 DEG C calcining 2 hours, then continue to be warming up to 1100 DEG C of calcinings 2 hours with 10 DEG C/min, cool to room temperature with the furnace, compressing tablet block after sintering is placed in 80 ~ 100 DEG C of heat recirculated water 8 ~ 10h and removes sodium-chlor, ultrasonic 30min removes impurity, and 80 DEG C of vacuum-drying 5h, obtain POROUS TITANIUM;
2) vacuum impregnation catalyzer
POROUS TITANIUM step 1) obtained is placed in filter flask, under vacuum tightness is 0.001 ~ 0.01MPa, vacuumize 20 ~ 30min, then in filter flask, add the cobalt nitrate hexahydrate solution submergence POROUS TITANIUM of 0.001 ~ 0.05mol/L concentration, or in filter flask, add amount of substance than the six water nickelous nitrates and the six water Yttrium trinitrate mixing solutionss that are 1:1, mixed liquid concentration is the solution submergence POROUS TITANIUM of 0.001 ~ 0.05mol/L, continue to vacuumize 20 ~ 30min, through vacuum-drying 8 ~ 10h at 60 ~ 100 DEG C of temperature, obtain the POROUS TITANIUM that load has catalyzer salt;
3) chemical Vapor deposition process prepares three-dimensional network shape carbon nanotube enhancing titanium matrix composite
By step 2) obtained load has the POROUS TITANIUM of catalyzer salt to be placed in quartz tube furnace; under the protection of argon gas; 400 ~ 450 DEG C are warming up to the heat-up rate of 10 DEG C/min; calcining at constant temperature 1h; then continue to be warming up to 450 ~ 500 DEG C with 10 DEG C/min; closing argon gas, is that 150 ~ 250ml/min passes into H in stove with flow velocity
2reduction 1h, continue to be warming up to 500 DEG C ~ 700 DEG C with 10 DEG C/min, be the gas mixture that 310 ~ 340mL/min passes into acetylene and argon gas in stove with flow velocity, the volume ratio of acetylene and argon gas is 1:(15 ~ 30), carry out the catalytic cracking reaction of 20 ~ 60min, then be cooled to room temperature under an argon atmosphere, obtain three-dimensional network shape carbon nanotube and strengthen titanium matrix composite.
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| CN102477502A (en) * | 2010-11-30 | 2012-05-30 | 西安赛特金属材料开发有限公司 | Medical high-strength titanium alloy wire and preparation method thereof |
| CN102513479A (en) * | 2011-11-18 | 2012-06-27 | 宝鸡市金盛伟业稀有金属有限公司 | Production process for large-diameter fine isometric crystal tissue titanium alloy bar |
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| CN102477502A (en) * | 2010-11-30 | 2012-05-30 | 西安赛特金属材料开发有限公司 | Medical high-strength titanium alloy wire and preparation method thereof |
| CN102513479A (en) * | 2011-11-18 | 2012-06-27 | 宝鸡市金盛伟业稀有金属有限公司 | Production process for large-diameter fine isometric crystal tissue titanium alloy bar |
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