CN109763047A - A kind of Mo-Ti-Zr-CNT molybdenum alloy composite material and preparation method of high intensity - Google Patents
A kind of Mo-Ti-Zr-CNT molybdenum alloy composite material and preparation method of high intensity Download PDFInfo
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Abstract
The invention discloses a kind of Mo-Ti-Zr-CNT molybdenum alloy composite material and preparation methods of high intensity, and TiH is adulterated in molybdenum as the carbon source of TZM molybdenum alloy using carbon nanotube substitution conventional graphite2、ZrH2And the molybdenum alloy obtained after CNT, each component are constituted by mass percentage are as follows: Ti 0.5%, Zr 0.1%, CNT 0.03%, surplus Mo.The present invention makes the hardness of the Mo-Ti-Zr-CNT molybdenum alloy composite material of preparation and yield strength be effectively improved by the optimization to techniques such as ball milling and discharge plasma sinterings.
Description
Technical field
The present invention relates to a kind of metallic composite and preparation method thereof, specifically a kind of Mo-Ti- of high intensity
Zr-CNT molybdenum alloy composite material and preparation method.
Background technique
Pure molybdenum is easy to oxidize at high temperature, and recrystallization temperature is low, and room temperature is not easy to be processed, by adding other yuan in molybdenum
Element develops the molybdenum alloy of many systems.Titanium, zirconium are added, the elements such as carbon can effectively improve the performance of molybdenum alloy, wherein
TZM molybdenum alloy is widely used for the industries such as aerospace, nuclear industry, medical treatment, machinery.
TZM molybdenum alloy main component is as follows: carbon (C)): 0.01%-0.04%；Titanium (Ti): 0.40%-0.55%；Zirconium
(Zr): 0.06%-0.12%；Surplus is molybdenum (Mo).TZM alloy mostly uses greatly powder metallurgy process at present.
In order to reduce material internal oxygen content, the intensity and performance of material are improved, related researcher uses many sides
Method.Wherein Xi'an Communications University Sun Jun team prepares high ductibility molybdenum alloy using liquid phase method, improves the draftability of molybdenum alloy
Energy.But be not suitable for being mass produced, it is expensive.There are also other preparation methods, such as solid-liquid doping hair to prepare molybdenum conjunction
Gold etc., but molybdenum alloy is applied in industrial production, powder metallurgic method is only best preparation method.
Summary of the invention
The present invention is intended to provide a kind of Mo-Ti-Zr-CNT molybdenum alloy composite material and preparation method of high intensity, uses
Carbon nanotube substitutes conventional graphite, as the carbon source of TZM molybdenum alloy, by techniques such as ball milling and discharge plasma sinterings
Optimization makes the hardness of the Mo-Ti-Zr-CNT molybdenum alloy composite material of preparation and yield strength be effectively improved.
Carbon nanotube has high conductivity, mechanical property is good, large specific surface area, surface chemistry energy as one of carbon material
The advantages that high, becomes one of present metal-base composites hot topic dopant material first choice.
High intensity Mo-Ti-Zr-CNT molybdenum alloy composite material of the invention, is that TiH is adulterated in molybdenum2、ZrH2And after CNT
The molybdenum alloy of acquisition, each component are constituted by mass percentage are as follows: Ti 0.5%, Zr 0.1%, CNT 0.03%, surplus Mo.
The preparation method of high intensity Mo-Ti-Zr-CNT molybdenum alloy composite material of the invention, includes the following steps:
Step 1: mixed powder
It is measured according to the ratio by load weighted molybdenum powder, TiH2Powder, ZrH2It is placed in mixing tank with carbon nanotube powders, is placed in three-dimensional
Mixed powder is carried out in mixed powder machine, the time is 2 hours；
Particle Sizes are as follows: TiH2Powder particles are having a size of 30-40 microns, ZrH2Powder particles are more having a size of 30-50 microns
Wall CNT powder particles are having a size of 30-50 nanometers, and Mo powder particles are having a size of 3-5 microns.
Step 2: ball milling
Step 1 is mixed the composite powder obtained after powder to be placed in ball grinder, the material of ball grinder and abrading-ball is WC, and revolving speed is
400r/min, ratio of grinding media to material 5:1 ball milling 10-25 hours, obtain composite mixed ball-milled powder；
Step 3: sintering
The ball-milled powder that step 2 is obtained is packed into graphite jig, then mold is put in discharge plasma sintering furnace, room temperature
Under to sintering stove evacuation, be successively warming up to 800 DEG C, 1600 DEG C and keep the temperature 5min respectively, in sintering process keep furnace chamber vacuum
Degree carries out vacuum-sintering, and control pressure is no more than 50MPa in sintering, and room temperature is down to after heat preservation to get Mo-Ti-Zr- is arrived
CNT molybdenum alloy composite material.
In sintering process, heating rate is 100 DEG C/min, and rate of temperature fall is 100 DEG C/min.
High-intensitive Mo-Ti-Zr-CNT molybdenum alloy composite material of the invention is under the preparation process of different Ball-milling Times, ball
Time consuming is 10-25 hours, is compared to hardness and yield strength.
The beneficial effects of the present invention are embodied in:
Multi-walled carbon nanotube is fiber tubular structure, is crimped for multi-layer graphene, and apparent activation energy is high, specific surface
Product is big, is more advantageous in mechanical milling process and Ti, and Zr is in connection, forms second-phase dispersion particle TiC and ZrC, enhances Grain-boundary Junctions
With joint efforts, intensity is improved.Powder, granule after ball milling is relatively uniform tiny, and sintered block particle refine to micron level, and
Second phase is transgranular to be evenly distributed in crystal boundary, so that hardness is improved, hardness number 260-295Hv.Meanwhile it being deposited in carbon nanotube
Under effect, the compression strength of material is also obviously improved, and after compression experiment, cylindrical sample is not crushed, and surface is only
There is crackle, yield strength significantly improves, yield strength 410-587MPa.
The present invention is described further with reference to the accompanying drawings and examples, and the objects and effects of the present invention will become more
Add obvious.
Detailed description of the invention
Fig. 1 is the SEM picture of Mo-Ti-Zr-CNT composite powder after ball milling.Show composite powder prepared by the present invention
Granularity is relatively uniform, and particle is tiny.
Fig. 2 is the metallograph after SPS is sintered after the corrosion of Mo-Ti-Zr-CNT composite material surface, shows sintered body particle
It is tiny, about 3 microns, and the second phase is evenly distributed, and it is transgranular to be evenly distributed in crystal boundary, be conducive to improve the strong of composite material
Degree.
Fig. 3 is ball milling 10 hours, and Mo-Ti-Zr-CNT composite material compression test true stress is answered after 15 hours, 25 hours
Varied curve, yield strength are respectively 410MPa, 445MPa and 587MPa.
Specific embodiment
Embodiment 1:
Mo-Ti-Zr-CNT molybdenum alloy composite material in the present embodiment, carbon nanotube are adulterated as carbon source, wherein each component
It is configured to wherein each component in mass ratio to constitute by mass percentage are as follows: Ti 0.5%, Zr 0.1%, CNT 0.03%, surplus
For Mo.
Particle Sizes are as follows: TiH2Powder particles are having a size of 30-40 microns, ZrH2Powder particles are more having a size of 30-50 microns
For wall CNT powder particles having a size of 30-50 nanometers, molybdenum powder particle size is 3-5 microns.
The preparation method of high intensity Mo-Ti-Zr-CNT molybdenum alloy composite material, includes the following steps: in the present embodiment
1, it mixes powder: doping ratio is pressed, by load weighted 29.811g molybdenum powder, 0.156g TiH2Powder, 0.031g ZrH2Powder and
0.009g carbon nanotube powders are placed in mixing tank, are placed in three-dimensional mixed powder machine and are carried out mixed powder, and the time is 2 hours.
2, ball milling: the composite powder after mixed powder is placed in ball grinder, and the material of ball grinder and abrading-ball is WC, revolving speed
Ball milling 10 hours, composite mixed ball-milled powder is obtained for 400r/min, ratio of grinding media to material 5:1.
3, it is sintered: ball-milled powder being packed into graphite jig, then grinding tool is put in discharge plasma sintering furnace, it is right at room temperature
It is sintered stove evacuation, 800 DEG C, 1600 DEG C is successively warming up to and keeps the temperature 5min respectively, furnace chamber vacuum degree is kept in sintering process, into
Row vacuum-sintering, control pressure is no more than 50MPa in sintering, and room temperature is down to after heat preservation to get multiple to Mo-Ti-Zr-CNT
Condensation material.In sintering process, heating rate is 100 DEG C/min, and rate of temperature fall is 100 DEG C/min.
Sintered composite material crystal grain is about 1.8 microns, and initial molybdenum powder particle size is 3-5 microns, ball milling 10 hours
Powder is refined, has achieved the effect that ball milling.Again because the second phase is evenly distributed, so that hardness is improved, hardness number
For 260Hv, higher than pure molybdenum is more, and the TZM alloy than the doping preparation of conventional graphite powder is also higher, has benefited from carbon nanotube
Doping.Meanwhile under the action of carbon nanotube, the compressive property of material is significantly improved, and yield strength has reached 410MPa, is answered
Change reaches 1/3, and compression sample is not crushed, so that high-intensitive Mo-Ti-Zr-CNT has some toughness, surface has a little thin
Crackle improves compression strength and yield strength.
Embodiment 2:
Mo-Ti-Zr-CNT molybdenum alloy composite material in the present embodiment, carbon nanotube are adulterated as carbon source, wherein each component
It is configured to wherein each component in mass ratio to constitute by mass percentage are as follows: Ti 0.5%, Zr 0.1%, CNT 0.03%, surplus
For Mo.
Particle Sizes are as follows: TiH2Powder particles are having a size of 30-40 microns, ZrH2Powder particles are more having a size of 30-50 microns
For wall CNT powder particles having a size of 30-50 nanometers, molybdenum powder particle size is 3-5 microns.
The preparation method of high intensity Mo-Ti-Zr-CNT molybdenum alloy composite material, includes the following steps: in the present embodiment
1, it mixes powder: doping ratio is pressed, by load weighted 49.685g molybdenum powder, 0.26g TiH2Powder, 0.051g ZrH2Powder and
0.015g carbon nanotube powders are placed in mixing tank, are placed in three-dimensional mixed powder machine and are carried out mixed powder, and the time is 2 hours.
2, ball milling: the composite powder after mixed powder is placed in ball grinder, and the material of ball grinder and abrading-ball is WC, revolving speed
Ball milling 15 hours, composite mixed ball-milled powder is obtained for 400r/min, ratio of grinding media to material 5:1.
3, it is sintered: ball-milled powder being packed into graphite jig, then grinding tool is put in discharge plasma sintering furnace, it is right at room temperature
It is sintered stove evacuation, 800 DEG C, 1600 DEG C is successively warming up to and keeps the temperature 5min respectively, furnace chamber vacuum degree is kept in sintering process, into
Row vacuum-sintering, control pressure is 50MPa in sintering, and room temperature is down to after heat preservation to get to Mo-Ti-Zr-CNT composite wood
Material.In sintering process, heating rate is 100 DEG C/min, and rate of temperature fall is 100 DEG C/min.
Sintered composite material crystal grain is about 0.6 micron, and initial molybdenum powder particle size is 3-5 microns, ball milling 10 hours
Powder particle size is about 1.8 microns, it is clear that powder is further refined after ball milling 15 hours.Again because the second phase is distributed
Uniformly, to improve hardness, hardness number 275Hv, than pure molybdenum, the TZM alloy and ball milling of the doping preparation of conventional graphite powder
10 hours will be high.Meanwhile under the action of carbon nanotube, the compressive property of material is significantly improved, and yield strength reaches
445MPa, strain reach 1/2, and compression sample is not crushed, so that high-intensitive Mo-Ti-Zr-CNT has original toughness, table
There are a little fine cracks in face, improves compression strength and yield strength.By changing preparation process (Ball-milling Time), Mo-Ti-
The intensity of Zr-CNT molybdenum alloy composite material is further improved.
Embodiment 3:
Mo-Ti-Zr-CNT molybdenum alloy composite material in the present embodiment, carbon nanotube are adulterated as carbon source, wherein each component
It is configured to wherein each component in mass ratio to constitute by mass percentage are as follows: Ti 0.5%, Zr 0.1%, CNT 0.03%, surplus
For Mo.
Particle Sizes are as follows: TiH2Powder particles are having a size of 30-40 microns, ZrH2Powder particles are more having a size of 30-50 microns
For wall CNT powder particles having a size of 30-50 nanometers, molybdenum powder particle size is 3-5 microns.
The preparation method of high intensity Mo-Ti-Zr-CNT molybdenum alloy composite material, includes the following steps: in the present embodiment
1, it mixes powder: doping ratio is pressed, by load weighted 49.685g molybdenum powder, 0.26g TiH2Powder, 0.051g ZrH2Powder and
0.015g carbon nanotube powders are placed in mixing tank, are placed in three-dimensional mixed powder machine and are carried out mixed powder, and the time is 2 hours.
2, ball milling: the composite powder after mixed powder is placed in ball grinder, and the material of ball grinder and abrading-ball is WC, revolving speed
Ball milling 25 hours, composite mixed ball-milled powder is obtained for 400r/min, ratio of grinding media to material 5:1.
3, it is sintered: ball-milled powder being packed into graphite jig, then grinding tool is put in discharge plasma sintering furnace, it is right at room temperature
It is sintered stove evacuation, 800 DEG C, 1600 DEG C is successively warming up to and keeps the temperature 5min respectively, furnace chamber vacuum degree is kept in sintering process, into
Row vacuum-sintering, control pressure is 50MPa in sintering, and room temperature is down to after heat preservation to get to Mo-Ti-Zr-CNT composite wood
Material.In sintering process, heating rate is 100 DEG C/min, and rate of temperature fall is 100 DEG C/min.
Sintered composite material crystal grain is about 1.2 microns, since powder is meticulous, to compare ball milling there are agglomeration
Powder particle size is bigger than normal within 15 hours, from subsequent data it is recognised that 25 hours powder particle sizes of ball milling can be into one
Step refinement.Again because the second phase is evenly distributed, to improve hardness, hardness number 295Hv is mixed than pure molybdenum, conventional graphite powder
The TZM alloy of miscellaneous preparation and ball milling 10 hours, ball milling 15 hours will be high.Meanwhile under the action of carbon nanotube, material
Compressive property significantly improve, yield strength has reached 587MPa, and strain reaches 1/3, and compression sample is not crushed, so that high-strength
The Mo-Ti-Zr-CNT of degree has original toughness, and there is a little crackle on surface, improves compression strength and yield strength.By not
With the comparison between preparation process, for high intensity Mo-Ti-Zr-CNT molybdenum alloy composite material in this patent, when ball milling
Between 25 hours be optimal preparation process.
Claims (6)
1. a kind of Mo-Ti-Zr-CNT molybdenum alloy composite material of high intensity, it is characterised in that: be to adulterate TiH in molybdenum2、ZrH2
And the molybdenum alloy obtained after CNT, each component are constituted by mass percentage are as follows: Ti 0.5%, Zr 0.1%, CNT 0.03%,
Surplus is Mo.
2. a kind of preparation method of high intensity Mo-Ti-Zr-CNT molybdenum alloy composite material described in claim 1, feature exist
In including the following steps:
Step 1: mixed powder
It is measured according to the ratio by load weighted molybdenum powder, TiH2Powder, ZrH2It is placed in mixing tank with carbon nanotube powders, is placed in three-dimensional mixed powder
Mixed powder is carried out in machine, the time is 2 hours；
Step 2: ball milling
Step 1 is mixed the composite powder obtained after powder to be placed in ball grinder, the material of ball grinder and abrading-ball is WC, ball milling 10-25
Hour, obtain composite mixed ball-milled powder；
Step 3: sintering
The ball-milled powder that step 2 is obtained is packed into graphite jig, then mold is put in discharge plasma sintering furnace, right at room temperature
It is sintered stove evacuation, 800 DEG C, 1600 DEG C is successively warming up to and keeps the temperature 5min respectively, room temperature is down to after heat preservation to get arriving
Mo-Ti-Zr-CNT molybdenum alloy composite material.
3. preparation method according to claim 2, it is characterised in that:
Particle Sizes are as follows: TiH2Powder particles are having a size of 30-40 microns, ZrH2Powder particles are having a size of 30-50 microns, multi wall CNT
Powder particles are having a size of 30-50 nanometers, and Mo powder particles are having a size of 3-5 microns.
4. preparation method according to claim 2, it is characterised in that:
In step 2, rotational speed of ball-mill 400r/min, ratio of grinding media to material 5:1.
5. preparation method according to claim 2, it is characterised in that:
In step 3, furnace chamber vacuum degree is kept in sintering process, carries out vacuum-sintering, control pressure is no more than 50MPa in sintering.
6. preparation method according to claim 2 or 5, it is characterised in that:
In step 3, in sintering process, heating rate is 100 DEG C/min, and rate of temperature fall is 100 DEG C/min.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111041316A (en) * | 2019-12-18 | 2020-04-21 | 合肥工业大学 | High-strength Mo-Hf-CNT molybdenum-based composite material and preparation method thereof |
| CN111872401A (en) * | 2020-07-30 | 2020-11-03 | 合肥工业大学 | Discharge plasma diffusion bonding method of ODSW/TZM alloy |
| CN115927898A (en) * | 2022-12-08 | 2023-04-07 | 西安理工大学 | TiC particle reinforced high-strength TZM-based composite material and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111041316A (en) * | 2019-12-18 | 2020-04-21 | 合肥工业大学 | High-strength Mo-Hf-CNT molybdenum-based composite material and preparation method thereof |
| CN111872401A (en) * | 2020-07-30 | 2020-11-03 | 合肥工业大学 | Discharge plasma diffusion bonding method of ODSW/TZM alloy |
| CN115927898A (en) * | 2022-12-08 | 2023-04-07 | 西安理工大学 | TiC particle reinforced high-strength TZM-based composite material and preparation method thereof |
| CN115927898B (en) * | 2022-12-08 | 2024-03-19 | 西安理工大学 | TiC particle reinforced high-strength TZM-based composite material and preparation method thereof |
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Application publication date: 20190517 |