CN108396173A - A kind of fire-retardant graphene titanium matrix composite and preparation method - Google Patents
A kind of fire-retardant graphene titanium matrix composite and preparation method Download PDFInfo
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- CN108396173A CN108396173A CN201810164736.0A CN201810164736A CN108396173A CN 108396173 A CN108396173 A CN 108396173A CN 201810164736 A CN201810164736 A CN 201810164736A CN 108396173 A CN108396173 A CN 108396173A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/045—Alloys based on refractory metals
- C22C1/0458—Alloys based on titanium, zirconium or hafnium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C14/00—Alloys based on titanium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
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Abstract
The present invention is difficult evenly dispersed to provide a kind of fire-retardant graphene titanium matrix composite and preparation method to solve the problems, such as graphene in titanium alloy material.The composite material, which includes group by mass percentage, to be become：The graphene oxide and titanium copper series alloy of 0.01~1wt%.Preparation method is as follows：First by chemical method in deionized water by uniform load copper on the surface of stannic oxide/graphene nano piece, then supported copper graphene oxide powder is uniformly mixed in absolute ethyl alcohol using mechanical agitation methods with titanium copper series alloy powder, the excellent composite material of structure property is obtained through process combinations such as jacket vacuumize process, hot isostatic pressings after drying.The present invention is new material concept, and preparation method is simple, reliable, has a extensive future.
Description
Technical field
The invention belongs to titanium materials technology field, it is related to a kind of titanium matrix composite and preparation method, especially relates to
And a kind of fire-retardant graphene titanium matrix composite and preparation method.
Background technology
With the spanning development of the advanced aviation power equipment of a new generation, function and structure-integrated titanium alloy material are carried
Active demand is gone out.Currently, the performance of conventional titanium alloy material already close to or reached theoretical limit, research and development synthesis
The better new titanium alloy material of performance has caused the great attention of countries in the world.
Graphene rapidly becomes and structure-integrated material because having the function of excellent mechanical performance and physical and chemical performance
The ideal reinforcement of material is rapidly developed in metal alloy compositions fields such as enhancing aluminium, nickel and copper, and is achieved larger at present
Progress, this widely applies in titanium alloy material for graphene and provides referential technological approaches.
However, compared with other metal materials, titanium has that chemism is high, burning point is less than characteristics such as fusing points, graphene with
Titanium alloy can chemically react at quite low temperatures, and the nature differences such as density between the two are larger, lead to graphite
Alkene difficulty evenly dispersed in titanium alloy substrate is very big.Processes such as current existing " ball millings+sintering " can not achieve stone
Black alkene it is evenly dispersed, therefore how to prepare graphene uniform dispersion titanium matrix composite be that bottleneck urgently to be resolved hurrily is asked
Topic.
Invention content
The present invention is difficult evenly dispersed problem in titanium alloy substrate for graphene and designs and propose a kind of fire-retardant stone
Black alkene titanium matrix composite and preparation method.First by chemical method by surface of graphene oxide uniform load copper, so
The mixed-powder for preparing graphene oxide and titanium copper series alloy by mechanical agitation technique afterwards is most vacuumized through jacket, heat afterwards
The processing such as isostatic pressed obtain the excellent composite material of structure property.
The technical scheme is that
A kind of fire-retardant graphene titanium matrix composite, including following compositions by mass percentage：Graphene oxide is
0.01~1wt%, remaining is titanium copper series alloy.
The ingredient of the titanium copper series alloy is Cu by mass percentage：8~20wt%, Al：0~10wt%, V：0~
10wt%, Mo：0~6wt%, Sn：0~6wt%, Zr：0~6wt%, Cr：0~5wt%, Nb：0~5wt%, Ta：0~
2wt%, Si：0~1wt%, O：0~0.3wt%, remaining is Ti.
Preferably, a kind of fire-retardant graphene titanium matrix composite, including following compositions by mass percentage：Aoxidize stone
Black alkene：0.1~0.5wt%, Cu：13~18wt%, Al：1~5wt%, Mo：0~4wt%, Zr：0~4wt%, O：0~
0.1wt%, remaining is Ti.
A method of fire-retardant graphene titanium matrix composite of the present invention is prepared, is included the following steps：
(1) the stannic oxide/graphene nano piece of 0.01~1wt% of titanium copper series alloy powder quality is added to deionized water
In, 60~120min of decentralized processing then is carried out using ultrasonic cell disrupte machine, working frequency is vibration 2s, gap 3s, is prepared
Go out the graphene oxide solution of a concentration of 0.1~3.5g/L；
(2) by the CuCl of a concentration of 0.015mol/L2The graphene oxide solution of solution and step (1) is according to 2:1 body
It after product is than mixing, is placed on blender and is stirred, mixing speed is 100~1500r/min, and whipping temp is 50~80
DEG C, stir and the NaOH solution of a concentration of 0.1mol/L be added dropwise using titration pump after 30~120min, be added dropwise NaOH solution with
CuCl2The volume ratio of solution is 3:10, continue the ascorbic acid that a concentration of 0.2mol/L is added dropwise after 30~120min of stirring
Ascorbic acid solution and CuCl is added dropwise in solution2The volume ratio of solution is 1:2, continue to be added dropwise after 60~120min of stirring dense
Degree is 1/2 NaBH of 0.01mol/L4NaBH is added dropwise in solution4Solution and CuCl2The volume ratio of solution is 1:2, it then proceedes to stir
60~120min is mixed, graphene oxide reaction solution is prepared；
(3) the graphene oxide reaction solution of step (2) is transferred in the centrifuge tube of centrifuge and is detached, centrifuge
Rotating speed is 2000~6000r/min, when the liquid for centrifuging after 2~5min to centrifuge tube upper end is transparent, is outwelled in centrifuge tube point
Then the transparency liquid separated out is added deionized water and tests the pH value of graphene oxide reaction solution with pH meter；
(4) repeat step (3) continue that graphene oxide reaction solution is centrifuged, until pH value of solution be 6.8~
7.2, supported copper graphene oxide solution is obtained, then supported copper graphene oxide solution is transferred in drying box and is dried
Dry, heating temperature is 60~80 DEG C, and soaking time is 12~36h, prepares supported copper graphene oxide powder；
(5) the supported copper graphene oxide powder of step (4) and titanium copper series alloy powder are put into absolute ethyl alcohol, then
It is stirred on mechanical stirring device, mixing speed is 500~2000r/min, and mixing time is 30~180min, is stirred
It mixes temperature and is no more than 80 DEG C, prepare supported copper graphene oxide and titanium copper system mixed powder for alloy slurry；
(6) the supported copper graphene oxide of step (5) and titanium copper system mixed powder for alloy slurry are transferred in drying box
It is dried, heating temperature is 50~80 DEG C, and soaking time is 5~20h, obtains supported copper graphene oxide and titanium copper series alloy
Mixed-powder；
(7) the supported copper graphene oxide of step (6) and titanium copper system mixed powder for alloy are fitted into stainless steel capsule, so
Vacuumize process is carried out to jacket afterwards, until vacuum degree is less than 5 × 10-38~16h is kept the temperature when Pa, then by jacket welded seal；
(8) the sealing jacket of step (7) is subjected to hot isostatic pressing, heating temperature is 900~1300 DEG C, and heat preservation pressure is
100~150MPa, soaking time are 2~4h, prepare fire-retardant graphene titanium matrix composite.
The blender is substituted by magnetic stirring apparatus.
The titanium copper series alloy powder is spherical or subsphaeroidal, and oxygen content is less than 1000ppm, and grain size is 30~150 μm.
The hot isostatic pressing can be by one in hot isostatic pressing and extruding, hot isostatic pressing and forging, hot isostatic pressing and rolling
Kind substitutes.
The present invention has the following advantages and high-lighting effect：
(1) it is added in titanium alloy instead of common graphite alkene using supported copper graphene oxide, makes the close of graphene oxide
The density close to titanium alloy powder is spent, is avoided since density difference is caused greatly between graphene oxide and titanium alloy powder
Evenly dispersed degree of the graphene oxide in titanium alloy powder greatly improved in the lamination of mixed-powder.(2) it is obtaining
Supported copper graphene oxide in, the coverage rate of copper reaches 90% or more on the surface of stannic oxide/graphene nano piece, and point
Cloth is relatively uniform, not only avoids the reunion of graphene oxide itself, and has been effectively isolated the direct of graphene oxide and titanium
Contact, reduces interfacial reaction degree, in combination with vacuumize process, graphene oxide is made substantially to be decomposed to form graphene,
The very good mechanical properties and physical and chemical performance of graphene are played.(3) supported copper is aoxidized by stone using churned mechanically mode
Black alkene is added in titanium alloy powder, improves the apparent density of mixed-powder, is improved the mouldability of follow-up powder metallurgy, is obtained
The fire-retardant graphene titanium matrix composite densification degree higher obtained.(4) the fire-retardant graphene titanium matrix composite prepared is fire-retardant
It has excellent performance, the common high-temperature titanium alloy than same heatproof rank is high by 50% or more, and heat resistance is more preferable；The machinery of composite material
Performance is significantly improved, such as compared with alloy substrate, in the case where plasticity does not reduce substantially, room temperature tensile intensity and
Testing Tensile Strength at Elevated Temperature improves 10% or more.(5) present invention is new material concept, and preparation method is simple, reliable, and application prospect is wide
It is wealthy.
Specific implementation mode
The fire-retardant graphene titanium matrix composite of the present invention includes following compositions by mass percentage：Graphite oxide
Alkene：0.1~0.5wt%, Cu：8~20wt%, Al：0~10wt%, V：0~10wt%, Mo：0~6wt%, Sn：0~
6wt%, Zr：0~6wt%, Cr：0~5wt%, Nb：0~5wt%, Ta：0~2wt%, Si：0~1wt%, O：0~
0.3wt%, remaining is Ti.
The preparation method of above-mentioned fire-retardant graphene titanium matrix composite is obtained by following steps.
(1) 50~150mg graphene oxides are put into 100mL deionized waters, are divided using ultrasonic cell disrupte machine
Processing is dissipated, the ultrasonic cell disrupte machine working time is 60~120min, and working frequency is vibration 2s, gap 3s, prepares oxidation
Graphene solution；
(2) by the CuCl of 511mg2·2H2O is put into 200mL deionized waters, is stirred to and is completely dissolved, and 200mL is prepared
The CuCl of a concentration of 0.015mol/L2Solution；
(3) by 3522mg ascorbic acid (C6H8O6) be put into 100mL deionized waters, it is stirred to and is completely dissolved, prepare
The ascorbic acid solution of a concentration of 0.2mol/L of 100mL；
(4) by the NaBH of 37.8mg4It is put into 100mL deionized waters, is stirred to and is completely dissolved, prepare 100mL concentration
For the NaBH of 0.01mol/L4Solution；
(5) by the CuCl of a concentration of 0.015mol/L of 200mL of step (2)2Solution and the graphene oxide of step (1) are molten
After liquid mixing, it is placed on blender and is stirred, mixing speed is 100~1500r/min, and whipping temp is 50~80 DEG C,
The NaOH solution of a concentration of 0.1mol/L of 60mL is added dropwise after stirring 30min using titration pump, rate of addition is 2~5mL/
Min, continue stir 30min after be added dropwise step (3) a concentration of 0.2mol/L of 100mL ascorbic acid solution, be added dropwise speed
Degree be 5~10mL/min, continue stir 60min after be added dropwise step (4) a concentration of 0.01mol/L of 100mL NaBH4
Solution, rate of addition are 5~10mL/min, then proceed to stirring 60min, prepare graphene oxide reaction solution；
(6) the graphene oxide reaction solution of step (5) is transferred in the centrifuge tube of centrifuge and is detached, centrifuge
Rotating speed is 2000~6000r/min, when the liquid for centrifuging after 2~5min to centrifuge tube upper end is transparent, is outwelled in centrifuge tube point
Then the transparency liquid separated out is added deionized water and tests the pH value of graphene oxide reaction solution with pH meter；
(7) repeat step (6) continue that graphene oxide reaction solution is centrifuged, until pH value of solution be 6.8~
7.2, obtain supported copper graphene oxide solution；
(8) the supported copper graphene oxide solution of step (7) is transferred in drying box and is dried, heating temperature 60
~80 DEG C, soaking time is 12~36h, supported copper graphene oxide powder is prepared, according to the graphene oxide quality of addition
And CuCl2The quality of cupric in solution, the composition for obtaining supported copper graphene oxide powder are in mass ratio：Graphene oxide：
34.5wt%, Cu：65.5wt%；
(9) quality of the quality and titanium copper series alloy powder of the supported copper graphene oxide powder of step (8) needed for calculating,
Detailed process is as follows：If desired it is M to prepare fire-retardant graphene titanium matrix composite quality, then graphene oxide in composite material
Quality is that (0.1~0.5wt%) M, Cu is (8~20wt%) M, then needs the quality of supported copper graphene oxide powder to beThe quality of wherein copper isThe quality for then obtaining titanium copper series alloy powder isThe quality of wherein copper is
(10) supported copper graphene oxide powder and titanium copper series alloy powder that step (9) calculates are put into absolute ethyl alcohol
In, be then stirred on mechanical stirring device, mixing speed be 500~2000r/min, mixing time be 30~
180min, whipping temp are no more than 80 DEG C, prepare supported copper graphene oxide and titanium copper system mixed powder for alloy slurry；
(11) the supported copper graphene oxide of step (10) and titanium copper system mixed powder for alloy slurry are transferred to drying box
In dried, heating temperature is 50~80 DEG C, and soaking time is 5~20h, obtains supported copper graphene oxide and titanium copper system and closes
Golden mixed-powder；
(12) the supported copper graphene oxide of step (11) and titanium copper system mixed powder for alloy are fitted into stainless steel capsule,
Then vacuumize process is carried out to jacket, until vacuum degree is less than 5 × 10-38~16h is kept the temperature when Pa, then by jacket welded seal；
(13) the sealing jacket of step (12) is subjected to hot isostatic pressing, heating temperature is 900~1300 DEG C, and heat preservation pressure is
100~150MPa, soaking time are 2~4h, prepare fire-retardant graphene titanium matrix composite.
The present invention is further explained in the light of specific embodiments, but the present invention is not limited to following embodiments.
Embodiment 1
The fire-retardant graphene titanium matrix composites of 1#, including following compositions by mass percentage：Graphene oxide is
0.2wt%, Cu 13wt%, Al 4wt%, Mo 4wt%, Zr 2wt%, remaining is Ti.Preparation method is as follows：
(1) 400mg graphene oxides are put into 400mL deionized waters, are carried out at dispersion using ultrasonic cell disrupte machine
Reason, ultrasonic cell disrupte machine working time are 60~120min, and working frequency is vibration 2s, gap 3s, prepares graphite oxide
Alkene solution；
(2) by the CuCl of 2044mg2·2H2O is put into 800mL deionized waters, is stirred to and is completely dissolved, and 800mL is prepared
The CuCl of a concentration of 0.015mol/L2Solution；
(3) by 14088mg ascorbic acid (C6H8O6) be put into 400mL deionized waters, it is stirred to and is completely dissolved, prepare
The ascorbic acid solution of a concentration of 0.2mol/L of 400mL；
(4) by the NaBH of 151.2mg4It is put into 400mL deionized waters, is stirred to and is completely dissolved, prepare 400mL concentration
For the NaBH of 0.01mol/L4Solution；
(5) CuCl for a concentration of 0.015mol/L of 800mL for preparing step (2)2The graphite oxide of solution and step (1)
It after the mixing of alkene solution, is placed into constant temperature blender with magnetic force and is stirred, whipping temp is 50~80 DEG C, stirs profit after 30min
The NaOH solution of a concentration of 0.1mol/L of 240mL is added dropwise with titration pump, rate of addition 12mL/min continues to stir
Ascorbic acid solution (the C of a concentration of 0.2mol/L of 400mL of step (3) preparation is added dropwise after 30min6H8O6), rate of addition
For 20mL/min, continue to stir the NaBH for a concentration of 0.01mol/L of 400mL that step (4) preparation is added dropwise after 60min4It is molten
Liquid, rate of addition 20mL/min then proceed to stirring 60min, prepare graphene oxide reaction solution；
(6) the graphene oxide reaction solution of step (5) is transferred in the centrifuge tube of supercentrifuge and is detached, from
Scheming rotating speed is 3000r/min, when the liquid for centrifuging after 3min to centrifuge tube upper end is transparent, outwells and is isolated in centrifuge tube
Then transparency liquid is added deionized water and tests the pH value of graphene oxide reaction solution with pH meter；
(7) it repeats step (6) to continue that graphene oxide reaction solution is centrifuged, until pH value of solution is 7, prepare
Go out supported copper graphene oxide solution；
(8) the supported copper graphene oxide solution of step (7) is dry in vacuum drying chamber, drying temperature is 70 DEG C,
Drying time is that for 24 hours, vacuum degree is less than 100Pa, supported copper graphene oxide powder is prepared, according to the graphene oxide of addition
Quality and CuCl2Contain copper mass in solution, it is to aoxidize stone in mass ratio that supported copper graphene oxide powder composition is prepared in calculating
Black alkene：34.5%, Cu：65.5%；
(9) quality of the quality and titanium copper series alloy powder of the supported copper graphene oxide powder of step (8) needed for calculating,
Detailed process is as follows：It needs to prepare the fire-retardant graphene titanium matrix composite quality of 1# to be 100g, then graphite oxide in composite material
The quality of alkene is 0.2g, Cu 13g, then it is 0.58g to need the quality of supported copper graphene oxide powder, and the quality of wherein copper is
0.38g, the then quality for obtaining titanium copper series alloy powder are 99.42g, and wherein the quality of copper is 12.62g；
(10) the 0.58g supported coppers graphene oxide powder of step (9) and 99.42g titanium copper series alloy powders are put into nothing
It in water-ethanol, is then stirred on mechanical stirring device, mixing speed is 500~1000r/min, and mixing time is
60~120min, whipping temp are no more than 80 DEG C, prepare supported copper graphene oxide and titanium copper system mixed powder for alloy slurry；
(11) the supported copper graphene oxide of step (10) and titanium copper system mixed powder for alloy slurry are transferred to drying box
In dried, heating temperature be 70 DEG C, soaking time be 5~20h, vacuum degree be less than 100Pa, obtain supported copper graphite oxide
Alkene and titanium copper system mixed powder for alloy；
(12) the supported copper graphene oxide of step (11) and titanium copper system mixed powder for alloy are fitted into stainless steel capsule,
Then vacuumize process is carried out to jacket, until vacuum degree is 1 × 10-38~16h is kept the temperature when Pa, then by jacket welded seal；
(13) the sealing jacket of step (12) is subjected to hot isostatic pressing, heating temperature is 900~1200 DEG C, and heat preservation pressure is
120~140MPa, soaking time 2h prepare the fire-retardant graphene titanium matrix composites of 1#.
Embodiment 2
The fire-retardant graphene titanium matrix composites of 2#, including following compositions by mass percentage：Graphene oxide is
1wt%, Cu 18wt%, Al 2wt%, Mo 2wt%, remaining is Ti.Preparation method is as follows：
(1) 1000mg graphene oxides are put into 1000mL deionized waters, are disperseed using ultrasonic cell disrupte machine
Processing, ultrasonic cell disrupte machine working time are 60~120min, and working frequency is vibration 2s, gap 3s, prepares oxidation stone
Black alkene solution；
(2) by the CuCl of 5110mg2·2H2O is put into 2000mL deionized waters, is stirred to and is completely dissolved, and is prepared
The CuCl of a concentration of 0.015mol/L of 2000mL2Solution；
(3) by 35220mg ascorbic acid (C6H8O6) be put into 1000mL deionized waters, it is stirred to and is completely dissolved, prepare
The ascorbic acid solution of a concentration of 0.2mol/L of 1000mL；
(4) by the NaBH of 378mg4It is put into 1000mL deionized waters, is stirred to and is completely dissolved, prepare 1000mL concentration
For the NaBH of 0.01mol/L4Solution；
(5) CuCl for a concentration of 0.015mol/L of 2000mL for preparing step (2)2The oxidation stone of solution and step (1)
It after black alkene solution mixing, is placed into constant temperature blender with magnetic force and is stirred, whipping temp is 50~80 DEG C, after stirring 30min
The NaOH solution of a concentration of 0.1mol/L of 600mL is added dropwise using titration pump, rate of addition 20mL/min continues to stir
Ascorbic acid solution (the C of a concentration of 0.2mol/L of 1000mL of step (3) preparation is added dropwise after 30min6H8O6), speed is added dropwise
Degree is 50mL/min, continues to stir the 1000mL a concentration of 0.01mol/L that step (4) preparation is added dropwise after 60min
NaBH4Solution, rate of addition 50mL/min then proceed to stirring 60min, prepare graphene oxide reaction solution；
(6) the graphene oxide reaction solution of step (5) is transferred in the centrifuge tube of supercentrifuge and is detached, from
Scheming rotating speed is 4000r/min, when the liquid for centrifuging after 5min to centrifuge tube upper end is transparent, outwells and is isolated in centrifuge tube
Then transparency liquid is added deionized water and tests the pH value of graphene oxide reaction solution with pH meter；
(7) it repeats step (6) to continue that graphene oxide reaction solution is centrifuged, until pH value of solution is 7, prepare
Go out supported copper graphene oxide solution；
(8) the supported copper graphene oxide solution of step (7) is dry in vacuum drying chamber, drying temperature is 80 DEG C,
Drying time is 30h, and vacuum degree is less than 100Pa, supported copper graphene oxide powder is prepared, according to the graphene oxide of addition
Quality and CuCl2Contain copper mass in solution, it is to aoxidize stone in mass ratio that supported copper graphene oxide powder composition is prepared in calculating
Black alkene：34.5%, Cu：65.5%；
(9) step (1)~(8) are repeated, supported copper graphene oxide powder is repeatedly prepared；
(10) matter of the quality and titanium copper series alloy powder of the supported copper graphene oxide powder of step (9) needed for calculating
Amount, detailed process are as follows：It needs to prepare the fire-retardant graphene titanium matrix composite quality of 2# to be 1000g, is then aoxidized in composite material
The quality of graphene is 10g, Cu 180g, then it is 29g to need the quality of supported copper graphene oxide powder, and the quality of wherein copper is
19g, the then quality for obtaining titanium copper series alloy powder are 971g, and wherein the quality of copper is 161g；
(11) the 29g supported coppers graphene oxide powder of step (10) and 971g titanium copper series alloy powders are put into anhydrous second
In alcohol, be then stirred on mechanical stirring device, mixing speed be 500~1000r/min, mixing time be 60~
120min, whipping temp are no more than 80 DEG C, prepare supported copper graphene oxide and titanium copper system mixed powder for alloy slurry；
(12) the supported copper graphene oxide of step (11) and titanium copper system mixed powder for alloy slurry are transferred to drying box
In dried, heating temperature be 70 DEG C, soaking time be 5~20h, vacuum degree be less than 100Pa, obtain supported copper graphite oxide
Alkene and titanium copper system mixed powder for alloy；
(13) the supported copper graphene oxide of step (11) and titanium copper system mixed powder for alloy are fitted into stainless steel capsule,
Then vacuumize process is carried out to jacket, until vacuum degree is 5 × 10-48~16h is kept the temperature when Pa, then by jacket welded seal；
(14) the sealing jacket of step (12) is subjected to hot isostatic pressing, heating temperature is 900~1200 DEG C, and heat preservation pressure is
120~140MPa, soaking time 2h prepare the fire-retardant graphene titanium matrix composites of 2#.
Embodiment 3
The fire-retardant graphene titanium matrix composites of 3#, including following compositions by mass percentage：Graphene oxide is
0.1wt%, Cu 13wt%, remaining is Ti.Preparation method is as follows：
(1) 300mg graphene oxides are put into 300mL deionized waters, are carried out at dispersion using ultrasonic cell disrupte machine
Reason, ultrasonic cell disrupte machine working time are 60~120min, and working frequency is vibration 2s, gap 3s, prepares graphite oxide
Alkene solution；
(2) by the CuCl of 1533mg2·2H2O is put into 600mL deionized waters, is stirred to and is completely dissolved, and 600mL is prepared
The CuCl of a concentration of 0.015mol/L2Solution；
(3) by 10566mg ascorbic acid (C6H8O6) be put into 300mL deionized waters, it is stirred to and is completely dissolved, prepare
The ascorbic acid solution of a concentration of 0.2mol/L of 300mL；
(4) NaBH4 of 113.4mg is put into 300mL deionized waters, is stirred to and is completely dissolved, prepare 300mL concentration
For the NaBH4 solution of 0.01mol/L；
(5) CuCl for a concentration of 0.015mol/L of 600mL for preparing step (2)2The graphite oxide of solution and step (1)
It after the mixing of alkene solution, is placed into constant temperature blender with magnetic force and is stirred, whipping temp is 50~80 DEG C, stirs profit after 30min
The NaOH solution of a concentration of 0.1mol/L of 180mL is added dropwise with titration pump, rate of addition 9mL/min continues to stir
Ascorbic acid solution (the C of a concentration of 0.2mol/L of 300mL of step (3) preparation is added dropwise after 30min6H8O6), rate of addition
For 10mL/min, continue to stir the NaBH for a concentration of 0.01mol/L of 300mL that step (4) preparation is added dropwise after 60min4It is molten
Liquid, rate of addition 10mL/min then proceed to stirring 60min, prepare graphene oxide reaction solution；
(6) the graphene oxide reaction solution of step (5) is transferred in the centrifuge tube of supercentrifuge and is detached, from
Scheming rotating speed is 5000r/min, when the liquid for centrifuging after 5min to centrifuge tube upper end is transparent, outwells and is isolated in centrifuge tube
Then transparency liquid is added deionized water and tests the pH value of graphene oxide reaction solution with pH meter；
(7) it repeats step (6) to continue that graphene oxide reaction solution is centrifuged, until pH value of solution is 7, prepare
Go out supported copper graphene oxide solution；
(8) the supported copper graphene oxide solution of step (7) is dry in vacuum drying chamber, drying temperature is 80 DEG C,
Drying time is 30h, and vacuum degree is less than 100Pa, supported copper graphene oxide powder is prepared, according to the graphene oxide of addition
Quality and CuCl2Contain copper mass in solution, it is to aoxidize stone in mass ratio that supported copper graphene oxide powder composition is prepared in calculating
Black alkene：34.5%, Cu：65.5%；
(9) quality of the quality and titanium copper series alloy powder of the supported copper graphene oxide powder of step (8) needed for calculating,
Detailed process is as follows：It needs to prepare the fire-retardant graphene titanium matrix composite quality of 3# to be 200g, then graphite oxide in composite material
The quality of alkene is 0.2g, Cu 26g, then it is 0.58g to need the quality of supported copper graphene oxide powder, and the quality of wherein copper is
0.38g, the then quality for obtaining titanium copper series alloy powder are 199.42g, and wherein the quality of copper is 25.62g；
(10) the 0.58g supported coppers graphene oxide powder of step (9) and 199.42g titanium copper series alloy powders are put into nothing
It in water-ethanol, is then stirred on mechanical stirring device, mixing speed is 500~1000r/min, and mixing time is
60~120min, whipping temp are no more than 80 DEG C, prepare supported copper graphene oxide and titanium copper system mixed powder for alloy slurry；
(11) the supported copper graphene oxide of step (10) and titanium copper system mixed powder for alloy slurry are transferred to drying box
In dried, heating temperature be 70 DEG C, soaking time be 5~20h, vacuum degree be less than 100Pa, obtain supported copper graphite oxide
Alkene and titanium copper system mixed powder for alloy；
(12) the supported copper graphene oxide of step (11) and titanium copper system mixed powder for alloy are fitted into stainless steel capsule,
Then vacuumize process is carried out to jacket, until vacuum degree is 1 × 10-38~16h is kept the temperature when Pa, then by jacket welded seal；
(13) the sealing jacket of step (12) is subjected to hot isostatic pressing, heating temperature is 900~1200 DEG C, and heat preservation pressure is
120~140MPa, soaking time 2h prepare the fire-retardant graphene titanium matrix composites of 3#.
Claims (7)
1. a kind of fire-retardant graphene titanium matrix composite, it is characterised in that：The composite material include by mass percentage with
Lower composition, graphene oxide：0.01~1wt%, remaining is titanium copper series alloy.
2. a kind of fire-retardant graphene titanium matrix composite according to claim 1, it is characterised in that：The titanium copper series alloy
Ingredient be by mass percentage：Cu：8~20wt%, Al：0~10wt%, V：0~10wt%, Mo：0~6wt%, Sn：0~
6wt%, Zr：0~6wt%, Cr：0~5wt%, Nb：0~5wt%, Ta：0~2wt%, Si：0~1wt%, O：0~
0.3wt%, remaining is Ti.
3. a kind of fire-retardant graphene titanium matrix composite according to claim 1, it is characterised in that：The composite material is pressed
Mass percent meter includes consisting of, graphene oxide：0.1~0.5wt%, Cu：13~18wt%, Al：1~5wt%,
Mo：0~4wt%, Zr：0~4wt%, O：0~0.1wt%, remaining is Ti.
4. a kind of method preparing fire-retardant graphene titanium matrix composite described in claim 1, it is characterised in that：This method includes
Following steps：
(1) the stannic oxide/graphene nano piece of 0.01~1wt% of titanium copper series alloy powder quality is added in deionized water, so
60~120min of decentralized processing is carried out using ultrasonic cell disrupte machine afterwards, working frequency is vibration 2s, gap 3s, prepares concentration
For the graphene oxide solution of 0.1~3.5g/L；
(2) by the CuCl of a concentration of 0.015mol/L2The graphene oxide solution of solution and step (1) is according to 2:1 volume ratio is mixed
It after conjunction, is placed on blender and is stirred, mixing speed is 100~1500r/min, and whipping temp is 50~80 DEG C, stirring
The NaOH solution of a concentration of 0.1mol/L is added dropwise after 30~120min using titration pump, NaOH solution and CuCl is added dropwise2It is molten
The volume ratio of liquid is 3:10, continue the ascorbic acid solution that a concentration of 0.2mol/L is added dropwise after 30~120min of stirring, drop
Add ascorbic acid solution and CuCl2The volume ratio of solution is 1:2, continue to be added dropwise after 60~120min of stirring a concentration of
1/2 NaBH of 0.01mol/L4NaBH is added dropwise in solution4Solution and CuCl2The volume ratio of solution is 1:2, then proceed to stirring 60
~120min prepares graphene oxide reaction solution；
(3) the graphene oxide reaction solution of step (2) is transferred in the centrifuge tube of centrifuge and is detached, centrifuge speed
For 2000~6000r/min, when the liquid for centrifuging after 2~5min to centrifuge tube upper end is transparent, outwells in centrifuge tube and isolate
Transparency liquid, then be added deionized water and with pH meter test graphene oxide reaction solution pH value；
(4) step (3) is repeated to continue that graphene oxide reaction solution is centrifuged, until pH value of solution is 6.8~7.2,
Supported copper graphene oxide solution is obtained, then supported copper graphene oxide solution is transferred in drying box and is dried, is added
Hot temperature is 60~80 DEG C, and soaking time is 12~36h, prepares supported copper graphene oxide powder；
(5) the supported copper graphene oxide powder of step (4) and titanium copper series alloy powder are put into absolute ethyl alcohol, then in machine
It is stirred on tool agitating device, mixing speed is 500~2000r/min, and mixing time is 30~180min, stirring temperature
Degree is no more than 80 DEG C, prepares supported copper graphene oxide and titanium copper system mixed powder for alloy slurry；
(6) the supported copper graphene oxide of step (5) and titanium copper system mixed powder for alloy slurry are transferred in drying box and are carried out
Drying, heating temperature are 50~80 DEG C, and soaking time is 5~20h, obtain supported copper graphene oxide and the mixing of titanium copper series alloy
Powder；
(7) the supported copper graphene oxide of step (6) and titanium copper system mixed powder for alloy are fitted into stainless steel capsule, it is then right
Jacket carries out vacuumize process, until vacuum degree is less than 5 × 10-38~16h is kept the temperature when Pa, then by jacket welded seal；
(8) by the sealing jacket of step (7) carry out hot isostatic pressing, heating temperature be 900~1300 DEG C, heat preservation pressure be 100~
150MPa, soaking time are 2~4h, prepare fire-retardant graphene titanium matrix composite.
5. a kind of preparation method of fire-retardant graphene titanium matrix composite according to claim 4, it is characterised in that：It is described
Blender is substituted by magnetic stirring apparatus.
6. a kind of preparation method of fire-retardant graphene titanium matrix composite according to claim 4, it is characterised in that：It is described
Titanium copper series alloy powder is spherical or subsphaeroidal, and oxygen content is less than 1000ppm, and grain size is 30~150 μm.
7. a kind of preparation method of fire-retardant graphene titanium matrix composite according to claim 4, it is characterised in that：It is described
Hot isostatic pressing can be by a kind of replacement in hot isostatic pressing and extruding, hot isostatic pressing and forging, hot isostatic pressing and rolling.
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| CN106191524A (en) * | 2016-08-30 | 2016-12-07 | 张忠世 | A kind of Ti 456 titanium alloy and preparation and application |
| CN107557612A (en) * | 2017-07-27 | 2018-01-09 | 中国航发北京航空材料研究院 | A kind of graphene enhancing titanium-based nano composite and preparation method |
| CN107598175A (en) * | 2017-07-27 | 2018-01-19 | 中国航发北京航空材料研究院 | A kind of graphene and titanium alloy composite powder ball-milling preparation method |
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| CN106191524A (en) * | 2016-08-30 | 2016-12-07 | 张忠世 | A kind of Ti 456 titanium alloy and preparation and application |
| CN107557612A (en) * | 2017-07-27 | 2018-01-09 | 中国航发北京航空材料研究院 | A kind of graphene enhancing titanium-based nano composite and preparation method |
| CN107598175A (en) * | 2017-07-27 | 2018-01-19 | 中国航发北京航空材料研究院 | A kind of graphene and titanium alloy composite powder ball-milling preparation method |
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| CN111378870A (en) * | 2020-04-22 | 2020-07-07 | 江苏大学 | SPS sintering titanium-based composite material and preparation method thereof |
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