CN109554573B - Preparation method and application of magnesium alloy containing graphene refiner - Google Patents
Preparation method and application of magnesium alloy containing graphene refiner Download PDFInfo
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- CN109554573B CN109554573B CN201910049713.XA CN201910049713A CN109554573B CN 109554573 B CN109554573 B CN 109554573B CN 201910049713 A CN201910049713 A CN 201910049713A CN 109554573 B CN109554573 B CN 109554573B
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 95
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 36
- 239000000956 alloy Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 21
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 20
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 19
- 239000011777 magnesium Substances 0.000 claims abstract description 19
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 10
- 238000010907 mechanical stirring Methods 0.000 claims abstract description 8
- 229910018503 SF6 Inorganic materials 0.000 claims abstract description 7
- 230000008018 melting Effects 0.000 claims abstract description 7
- 238000002844 melting Methods 0.000 claims abstract description 7
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229960000909 sulfur hexafluoride Drugs 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 9
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005096 rolling process Methods 0.000 claims description 3
- 238000005242 forging Methods 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 abstract description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000007670 refining Methods 0.000 abstract description 5
- 239000007769 metal material Substances 0.000 abstract description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 2
- 238000007711 solidification Methods 0.000 abstract description 2
- 230000008023 solidification Effects 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 230000006911 nucleation Effects 0.000 abstract 1
- 238000010899 nucleation Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 5
- 239000002135 nanosheet Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- QRNPTSGPQSOPQK-UHFFFAOYSA-N magnesium zirconium Chemical compound [Mg].[Zr] QRNPTSGPQSOPQK-UHFFFAOYSA-N 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
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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
- C22C1/10—Alloys containing non-metals
- C22C1/1036—Alloys containing non-metals starting from a melt
-
- 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
- C22C1/10—Alloys containing non-metals
- C22C1/1036—Alloys containing non-metals starting from a melt
- C22C1/1057—Reactive infiltration
- C22C1/1063—Gas reaction, e.g. lanxide
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
Abstract
A preparation method and application of a magnesium alloy containing a graphene refiner relate to a preparation method and application of a refiner. The invention aims to solve the problems that the grain refining method in magnesium and magnesium alloy is limited and the grains are easy to grow; firstly, heating magnesium and magnesium alloy in a crucible under the protection of mixed atmosphere of sulfur hexafluoride and carbon dioxide, melting the metal, and then adding CO2And introducing gas into the magnesium alloy melt, keeping mechanical stirring, and generating graphene through magnesium thermal reaction and nano magnesium oxide on the surface of the graphene, namely the grain refiner. Solidifying magnesium and magnesium alloy containing a grain refiner, then placing the prepared alloy containing the grain refiner into a required magnesium alloy system, refining an alloy melt, forming more nucleation particles by graphene and magnesium oxide on the surface in the solidification process, and simultaneously preventing the grains from growing. Thereby obtaining the cast magnesium alloy with fine grain structure. The invention is applied to the field of manufacture of non-ferrous metal materials.
Description
Technical Field
The invention relates to the field of non-ferrous metal material manufacturing, in particular to a preparation method and application of a refiner.
Background
The grain size has an important influence on the mechanical properties of the metal material, because the grain boundary can block the movement of dislocation in a slip plane, and the effect of blocking the dislocation is more obvious when the grain is finer. In magnesium alloys, the grain refining effect is generally more pronounced than in other alloys. In order to improve the mechanical property of the magnesium alloy in the preparation process, a fine grain structure needs to be obtained. The usual methods are mechanical vibration, electromagnetic stirring, high-speed shearing, ultrasonic treatment, etc. However, these methods have high requirements for equipment and have great limitations for large-scale industrial application. Under industrial production conditions, the addition of grain refiners is the simplest and most efficient method, for example grain refinement can be achieved by using a magnesium-zirconium master alloy. However, rare earth materials are scarce in resources, so that the manufacturing cost of the materials is increased. Therefore, the development of a novel low-cost grain refiner has great practical significance.
Disclosure of Invention
The invention aims to solve the problems that the grain refining method in magnesium and magnesium alloy is limited and the grains are easy to grow. The method for preparing the graphene refiner of the novel magnesium alloy is simple in process, low in cost and applicable to large-scale industrial manufacturing.
The invention relates to a preparation method of a magnesium alloy containing a graphene refiner, which comprises the following steps:
firstly, heating and melting magnesium alloy in a crucible under the protection of mixed atmosphere of sulfur hexafluoride and carbon dioxide to obtain magnesium alloy melt; wherein the heating temperature is 660-800 ℃;
secondly, the CO with the purity of 99.9 percent and the flow rate of 1L/min to 5L/min is mixed2Continuously introducing gas into the magnesium alloy melt, and keeping mechanical stirring at the temperature of 660-800 ℃ to perform magnesium thermal reaction until 5-50% of magnesium in the magnesium alloy participates in the reaction; wherein the stirring speed is 500r/min-2500 r/min;
and thirdly, standing the alloy obtained by the reaction in the second step for 5-20 min, and then carrying out water condensation on the alloy to obtain the magnesium alloy containing the graphene refiner.
The magnesium alloy containing the graphene refiner is prepared by the method and is used for preparing fine-grain magnesium alloy.
The invention has the following advantages:
the traditional casting equipment can be utilized in the preparation process of the grain refiner, and the technical field can be easily mastered by operators. The raw material sources in the preparation process are wide. Therefore, the magnesium alloy grain refiner obtained by the method has great industrial application value. The key point of the preparation is that the grain refinement of the magnesium alloy is carried out in two steps, wherein the first step is to prepare graphene and graphene nanosheets containing high volume fractions by utilizing a magnesium thermal reaction, and the second step is to place the magnesium alloy containing a refiner into the magnesium alloy needing the grain refinement, so that the industrial application operation is simple and convenient.
According to the method, carbon dioxide is used as one of raw materials, graphene and graphene nanosheets prepared through a magnesium thermal reaction are used as grain refiners, the rare earth material grain refiners are replaced, and the cost is reduced. According to the invention, a small amount of magnesium alloy containing the graphene grain refiner with high volume fraction is prepared through a small crucible, and then the magnesium alloy is added into the magnesium alloy melted in a large crucible as required to prepare the fine-grain magnesium alloy. By the method, the problems that the requirement on equipment is high, the condition is harsh, and the method is not suitable for industrial mass production when the fine magnesium alloy is prepared by directly introducing carbon dioxide into the large crucible for melting the magnesium alloy can be solved.
Drawings
FIG. 1 is a flow diagram of a grain refiner refined alloy made according to the present invention;
FIG. 2 is an EDS photograph of the grain refiner prepared in example 1; wherein (a) SEM image, (b) is distribution of carbon, (c) is distribution of magnesium (d) is distribution of oxygen;
FIG. 3 is a metallographic photograph of a magnesium-zinc alloy cast state prepared in example 1; wherein A is an unrefined alloy, and B is a refined alloy;
FIG. 4 is a bar graph comparing hardness before and after refining for the Mg-Zn alloy prepared in example 1;
FIG. 5 is a metallographic photograph of a magnesium-zinc alloy prepared in example 1 after being deformed by extrusion; wherein A is an unrefined alloy, and B is a refined alloy.
Detailed Description
The first embodiment is as follows: the preparation method of the magnesium alloy containing the graphene refiner comprises the following steps:
firstly, heating and melting magnesium alloy in a crucible under the protection of mixed atmosphere of sulfur hexafluoride and carbon dioxide to obtain magnesium alloy melt; wherein the heating temperature is 660-800 ℃;
secondly, the CO with the purity of 99.9 percent and the flow rate of 1L/min to 5L/min is mixed2Continuously introducing gas into the magnesium alloy melt, and keeping mechanical stirring at the temperature of 660-800 ℃ to perform magnesium thermal reaction until 5-50% of magnesium in the magnesium alloy participates in the reaction; wherein the stirring speed is 500r/min-2500 r/min;
and thirdly, standing the alloy obtained by the reaction in the second step for 5-20 min, and then carrying out water condensation on the alloy to obtain the magnesium alloy containing the graphene refiner.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the magnesium alloy is ZK60 magnesium alloy. The rest is the same as the first embodiment.
The third concrete implementation mode: the first difference between the present embodiment and the specific embodiment is: CO 22The flow rate of the gas is 3L/min-5L/min. The rest is the same as the first embodiment.
The fourth concrete implementation mode: the first difference between the present embodiment and the specific embodiment is: the mechanical stirring is maintained at a temperature of 720 ℃ to 800 ℃. The rest is the same as the first embodiment.
The fifth concrete implementation mode: the first difference between the present embodiment and the specific embodiment is: the stirring speed is 1500r/min-2500 r/min. The rest is the same as the first embodiment.
The sixth specific implementation mode: the first difference between the present embodiment and the specific embodiment is: and standing the alloy for 10-20 min. The rest is the same as the first embodiment.
The seventh embodiment: the magnesium alloy containing the graphene refiner is prepared by the method of the first embodiment and is used for preparing fine-grain magnesium alloy.
The specific implementation mode is eight: the seventh embodiment is different from the seventh embodiment in that: the operation of preparing the fine-grain magnesium alloy from the magnesium alloy containing the graphene refiner is as follows:
firstly, when the magnesium alloy is smelted, the prepared magnesium alloy containing the graphene refiner is put into the melted magnesium alloy which needs to be refined, and after the alloy is uniformly mixed, the magnesium alloy is cooled and solidified;
and secondly, carrying out deformation treatment on the obtained magnesium alloy to finish the preparation of the fine-grain magnesium alloy.
The rest is the same as the seventh embodiment.
The specific implementation method nine: the seventh embodiment is different from the seventh embodiment in that: and putting the prepared magnesium alloy containing the graphene refiner into the magnesium alloy which needs to be refined and is melted at the temperature of 750 ℃. The rest is the same as the seventh embodiment.
The detailed implementation mode is ten: the seventh embodiment is different from the seventh embodiment in that: the deformation treatment is rolling, extrusion and forging. The rest is the same as the seventh embodiment.
The invention is not limited to the above embodiments, and one or a combination of several embodiments may also achieve the object of the invention.
The beneficial effects of the present invention are demonstrated by the following examples:
example 1
The preparation method of the fine-grain magnesium alloy of the embodiment is as follows:
firstly, heating and melting 400gZ6 magnesium alloy in a crucible under the protection of mixed atmosphere of sulfur hexafluoride and carbon dioxide, wherein the heating temperature is 700 ℃;
secondly, the CO with the flow rate of 1L/min and the volume percentage of 99.9 percent is mixed2Continuously introducing gas into the magnesium alloy melt for 15min, and keeping mechanical stirring, wherein the stirring speed is 1500r/min, and the temperature is kept at 700 ℃;
and thirdly, standing the alloy for 10min, and carrying out water condensation on the alloy.
Fourthly, taking 300g of the solidified Z6 magnesium alloy containing the grain refiner, placing the solidified Z6 magnesium alloy into the molten 1000gZ6 magnesium alloy, keeping the mixture for 20 minutes to uniformly mix the two alloys, and cooling and solidifying the alloys in the air.
And fourthly, extruding the cast material at the extrusion temperature of 300 ℃ in an extrusion ratio of 14: 1.
The flow chart of the fine grain magnesium alloy prepared in this example is shown in fig. 1. The black part is the graphene nanosheet, and the white part is magnesium oxide.
Fig. 2 is an EDS photograph of the grain refiner of the magnesium-zinc alloy prepared in this example, wherein (a) is an SEM image, (b) is a distribution of carbon, and (c) is a distribution of magnesium, and (d) is a distribution of oxygen. The existence of the grain refiner of the magnesium oxide and the graphene nanosheet can be clearly observed from the figure.
FIG. 3 is a metallographic photograph of a magnesium-zinc alloy prepared according to this example shown in FIG. 1, wherein (1) is an unrefined alloy; (2) the alloy is refined. The metallographic photograph shows that the crystal grains are refined after carbon dioxide is introduced into the alloy, which shows that the existence of the reaction product magnesium oxide and the graphene nanosheets enables the alloy to form more crystal nuclei in the solidification process, and simultaneously inhibits the growth of the crystal grains in the alloy, so that the crystal grains are refined.
Fig. 4 is a bar graph comparing the hardness before and after the magnesium-zinc alloy prepared by the embodiment is refined, and it can be clearly found from the bar graph that the hardness of the alloy after the grain refinement is obviously improved. The mechanical property of the material is obviously improved.
FIG. 5 is a metallographic photograph of the magnesium-zinc alloy prepared in the present example after being subjected to extrusion deformation. Wherein, FIG. 1 is an unrefined alloy; FIG. 2 shows the alloy after thinning. From the metallographic photograph, it can be found that the grain growth of the magnesium alloy can be inhibited due to the existence of the grain refiner, so that the material obtains a fine crystalline structure.
Example 2:
the preparation method of the fine-grain magnesium alloy of the embodiment is as follows:
firstly, 400g of ZK60 is heated and melted in a crucible under the protection of a mixed atmosphere of sulfur hexafluoride and carbon dioxide, and the heating temperature is 700 ℃.
Secondly, the CO with the flow rate of 1L/min and the volume percentage of 99.9 percent is mixed2Continuously introducing gas into the magnesium and magnesium alloy melt for 5min, and keeping mechanical stirring at the temperature of 720 ℃, wherein the stirring speed is 1500r/min, and the temperature is kept at 700 ℃;
and thirdly, standing the alloy for 10 min. The alloy is water-cooled to solidify.
And fourthly, taking 300g of the solidified ZK60 magnesium alloy containing the grain refiner, putting the solidified ZK60 magnesium alloy into the molten 1000gZK60 magnesium alloy, keeping for 20min to uniformly mix the two alloys, and cooling and solidifying the alloys in air.
And fifthly, rolling the as-cast material.
Example 3:
the preparation method of the fine-grain magnesium alloy of the embodiment is as follows:
firstly, heating 400g of pure magnesium in a crucible for melting under the protection of mixed atmosphere of sulfur hexafluoride and carbon dioxide, wherein the heating temperature is 700 ℃;
secondly, the CO with the flow rate of 1L/min and the volume percentage of 99.9 percent is mixed2Continuously introducing gas into the magnesium and magnesium alloy melt for 5min, and keeping mechanical stirring at the temperature of 720 ℃, wherein the stirring speed is 1500r/min, and the temperature is kept at 700 ℃;
and thirdly, taking 300g of the solidified pure magnesium alloy containing the grain refiner, putting the solidified pure magnesium alloy into 1000g of molten pure magnesium, keeping for 20min to uniformly mix the two alloys, and air-cooling and solidifying the alloys.
Claims (8)
1. A preparation method of magnesium alloy containing graphene refiner is characterized by comprising the following steps:
firstly, heating and melting magnesium alloy in a crucible under the protection of mixed atmosphere of sulfur hexafluoride and carbon dioxide to obtain magnesium alloy melt; wherein the heating temperature is 660-800 ℃;
secondly, the CO with the purity of 99.9 percent and the flow rate of 1L/min to 5L/min is mixed2Continuously introducing gas into the magnesium alloy melt, and keeping mechanical stirring at the temperature of 720-800 ℃ to perform magnesium thermal reaction until 5-50% of magnesium in the magnesium alloy participates in the reaction; wherein the stirring speed is 500r/min-2500 r/min;
standing the alloy obtained by the reaction in the step two for 5-20 min, and then carrying out water condensation on the alloy to obtain a magnesium alloy containing the graphene refiner; the magnesium alloy is Z6 magnesium alloy.
2. The method for preparing magnesium alloy containing graphene refiner according to claim 1, wherein the CO is CO2The flow rate of the gas is 3L/min-5L/min.
3. The method for preparing a magnesium alloy containing a graphene refiner according to claim 1, wherein the stirring speed is 1500r/min-2500 r/min.
4. The method for preparing the magnesium alloy containing the graphene refiner according to claim 1, wherein the alloy is kept still for 10-20 min.
5. The application of the magnesium alloy containing the graphene refiner is characterized in that the magnesium alloy containing the graphene refiner is prepared by the method of claim 1 and is used for preparing fine-grain magnesium alloy.
6. The application of the magnesium alloy containing the graphene refiner according to claim 5, wherein the operation of preparing the fine-grain magnesium alloy from the magnesium alloy containing the graphene refiner is as follows:
firstly, when the magnesium alloy is smelted, the prepared magnesium alloy containing the graphene refiner is put into a molten magnesium alloy to be refined, and after the two are uniformly mixed, the magnesium alloy is cooled and solidified;
and secondly, carrying out deformation treatment on the obtained magnesium alloy to finish the preparation of the fine-grain magnesium alloy.
7. The use of the magnesium alloy containing the graphene refiner as claimed in claim 6, wherein the prepared magnesium alloy containing the graphene refiner is put into the magnesium alloy which needs to be refined and is melted at the temperature of 750 ℃.
8. Use of a graphene refiner-containing magnesium alloy according to claim 6, wherein the deformation process is rolling, extruding and forging.
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|---|---|---|---|---|
| TW201300547A (en) * | 2011-06-30 | 2013-01-01 | Hon Hai Prec Ind Co Ltd | Graphene added magnesium alloy and magnesium alloy structural member using same |
| CN103773980A (en) * | 2014-03-04 | 2014-05-07 | 哈尔滨工业大学 | Preparation method of high-performance graphene nanosheet reinforced magnesium matrix composite |
| WO2017205281A1 (en) * | 2016-05-23 | 2017-11-30 | Terves Inc. | High conductivity magnesium alloy |
| CN107904428A (en) * | 2017-11-28 | 2018-04-13 | 北京工业大学 | A kind of magnesium alloy refiner of graphene-containing and preparation method thereof |
| CN108912493A (en) * | 2018-07-17 | 2018-11-30 | 中喜（宁夏）新材料有限公司 | A method of graphene wheel hub is produced using pulverized fuel ash carbon dioxide |
| CN109207787A (en) * | 2018-11-22 | 2019-01-15 | 哈尔滨工业大学 | A kind of preparation method of in-situ authigenic graphene enhancing magnesium-based composite material |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201300547A (en) * | 2011-06-30 | 2013-01-01 | Hon Hai Prec Ind Co Ltd | Graphene added magnesium alloy and magnesium alloy structural member using same |
| CN103773980A (en) * | 2014-03-04 | 2014-05-07 | 哈尔滨工业大学 | Preparation method of high-performance graphene nanosheet reinforced magnesium matrix composite |
| WO2017205281A1 (en) * | 2016-05-23 | 2017-11-30 | Terves Inc. | High conductivity magnesium alloy |
| CN107904428A (en) * | 2017-11-28 | 2018-04-13 | 北京工业大学 | A kind of magnesium alloy refiner of graphene-containing and preparation method thereof |
| CN108912493A (en) * | 2018-07-17 | 2018-11-30 | 中喜（宁夏）新材料有限公司 | A method of graphene wheel hub is produced using pulverized fuel ash carbon dioxide |
| CN109207787A (en) * | 2018-11-22 | 2019-01-15 | 哈尔滨工业大学 | A kind of preparation method of in-situ authigenic graphene enhancing magnesium-based composite material |
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