US20110247778A1 - Method of synthesizing metal -based composite material by melt reaction in coupling magnetic field and ultrasonic field - Google Patents
Method of synthesizing metal -based composite material by melt reaction in coupling magnetic field and ultrasonic field Download PDFInfo
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- US20110247778A1 US20110247778A1 US13/126,510 US200913126510A US2011247778A1 US 20110247778 A1 US20110247778 A1 US 20110247778A1 US 200913126510 A US200913126510 A US 200913126510A US 2011247778 A1 US2011247778 A1 US 2011247778A1
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- magnetic field
- ultrasonic
- composite material
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- melt
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 36
- 230000008878 coupling Effects 0.000 title claims abstract description 34
- 238000010168 coupling process Methods 0.000 title claims abstract description 34
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 32
- 239000002184 metal Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 29
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 14
- 239000002131 composite material Substances 0.000 title claims description 39
- 239000002245 particle Substances 0.000 claims abstract description 53
- 238000011065 in-situ storage Methods 0.000 claims abstract description 36
- 238000005266 casting Methods 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000011156 metal matrix composite Substances 0.000 claims abstract description 19
- 239000011159 matrix material Substances 0.000 claims abstract description 18
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 15
- 238000007670 refining Methods 0.000 claims abstract description 9
- 239000000376 reactant Substances 0.000 claims abstract description 6
- 239000000155 melt Substances 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 18
- 238000009210 therapy by ultrasound Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 9
- 239000011819 refractory material Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 description 19
- 238000003756 stirring Methods 0.000 description 19
- 230000008018 melting Effects 0.000 description 11
- 238000002844 melting Methods 0.000 description 11
- 230000005672 electromagnetic field Effects 0.000 description 9
- 229910020148 K2ZrF6 Inorganic materials 0.000 description 8
- 229910020261 KBF4 Inorganic materials 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 238000004220 aggregation Methods 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000002893 slag Substances 0.000 description 6
- 229910007948 ZrB2 Inorganic materials 0.000 description 4
- VWZIXVXBCBBRGP-UHFFFAOYSA-N boron;zirconium Chemical compound B#[Zr]#B VWZIXVXBCBBRGP-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000009749 continuous casting Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 230000002500 effect on skin Effects 0.000 description 2
- 239000011208 reinforced composite material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 208000012868 Overgrowth Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010952 in-situ formation Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/10—Supplying or treating molten metal
- B22D11/11—Treating the molten metal
- B22D11/114—Treating the molten metal by using agitating or vibrating means
- B22D11/115—Treating the molten metal by using agitating or vibrating means by using magnetic fields
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D1/00—Treatment of fused masses in the ladle or the supply runners before casting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D27/00—Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
- B22D27/02—Use of electric or magnetic effects
Definitions
- the invention relates to the technical field of novel composite material synthesis, in particular to a novel method of synthesizing particle reinforced metal matrix composite material by in-situ melt reaction in coupling electromagnetic field and ultrasonic field.
- Particle reinforced metal matrix composite material has a wide application prospect in the fields of advanced electric and electronic devices, aviation spacecrafts, machine, bridge tunnel engineering, etc. because of its excellent mechanical properties and physical and chemical properties owing to its composite structure and has been one of research hotspots of metal matrix composite material in recent years.
- in-situ reaction synthesis method is the primary method of preparing particle reinforced metal matrix composite material, its principle is that alloying elements or compounds which can generate second phase are added in metal matrix melt to produce in situ particle reinforced composite material by generating particle phase by in-situ reaction with metal melt at a certain temperature. Because of in situ formation of particle phase, the composite prepared by the method has clean bonding interfaces between particles and metal matrix, good wettability and high bonding strength.
- the technique has a series of problems of difficult control of reaction process, easy growth even aggregation of particle phase, and uneven distribution.
- Chinese patent CN 1958816 (Date of publication: 2007.05.09, Title: technique for preparing composite material of aluminum based surface enhanced by in situ particle through powered ultrasonic method) provides a technique for preparing in situ particle reinforced (Al 3 Ti phase) aluminum based surface composite material through a powered ultrasonic method, causing reinforced phase to be distributed evenly in the surface layer of matrix and interfaces to be bonded better.
- the effect of exerting single electromagnetic field or ultrasonic field on synthesizing particle reinforced composite material by in-situ reaction is unsatisfied.
- the action intensity of the magnetic field in metal decays exponentially due to insurmountable skin effect of the electromagnetic field in metal melt, and the effective depth of the electromagnetic field acting in the melt is limited, especially when employing a large-volume bath or an electromagnetic field with higher frequency, the difference of the effect of the electromagnetic field in the melt is significant, namely, the effect of the electromagnetic field in the melt shows severe nonuniformity, the effect of the electromagnetic field is weak in the central area and strong at the edge area.
- ultrasonic wave is mechanical sparse-dense vibration wave which belongs to longitudinal wave
- ultrasonic wave has obvious directivity, and meanwhile, the ultrasonic wave also decays seriously in metal melt
- ultrasonic effect mainly concentrates in the cylindrical area under an amplitude transformer, namely, the effect of the ultrasonic field concentrates on the central area of the melt and is weak at the edge area of the melt.
- the invention provides a novel method of in-situ synthesizing particle reinforced metal matrix composite material by coupling electromagnetic field and ultrasonic field.
- An aspect of the invention is to provide a method of synthesizing in situ particle reinforced metal matrix composite material by melt reaction in coupling magnetic field and ultrasonic field, which is used for preparing high-performance in-situ particle reinforced metal matrix composite material.
- the basic principle of the invention lies in simultaneously exerting magnetic field and high-energy ultrasonic field during synthesis of in-situ particle reinforced metal matrix composite material, utilizing magnetochemistry principle of magnetic field generating electromagnetic force, magnetization and eddy current induction heat in melt and sonochemistry principle of high-energy ultrasonic field generating ultrasonic cavitation and ultrasonic current impact to perform coupling during synthesizing the composite material so as to achieve the goals of controlling the distribution of particle phase, inhibiting the growth and aggregation of particles and changing the thermodynamic and dynamic conditions of in-situ synthesis reaction, thereby realizing the synthesis of the particle reinforced metal matrix composite material by coupling magnetochemistry of magnetic field and sonochemistry of high-energy ultrasonic filed.
- the principle of the method is described as follows by combining FIG. 1 to realize the scheme:
- Composite material melt 2 is synthesized in a bath (or melting pot) 1 made of thermal-insulating refractory material, a high-energy ultrasonic amplitude transformer 3 is inserted into the upper part of the bath (or melting pot), the melt undergoes ultrasonic treatment, a magnetic field 4 is exerted to the outer side of the bath (or melting pot).
- the magnetic field can be exerted in different modes according to preparation methods of the composite material and effects required. Therefore, the exerted magnetic field can be high-power pulse magnetic filed, high-frequency oscillating magnetic field or low-frequency alternating magnetic field.
- the exerted magnetic field 4 is high-power pulse magnetic filed, namely, high-power pulse magnetic filed is coupled with ultrasonic field.
- the high-power pulse magnetic field generates a pulse electromagnetic force, a pulse magnetizing force and joule heat produced by induced current, which accelerates in-situ chemical reaction and disperses particle phase.
- the pulse magnetic filed decays in a certain extent in the metal melt, and under the effect of the magnetic field, the reaction is strong at the edge area of the melt and weak at the central area, so the magnetic field shall be coupled with the high-energy ultrasonic field which has powered supersonic generating cavitation effect and acoustic streaming impact in the melt, wherein the cavitation effect controls the aggregation of particles, and the acoustic streaming impact plays a role of stirring in micro area. Because the effect of ultrasonic field is strong at the central area and weak at the edge area, the magnetic field and the ultrasonic field just compensate for each other to accelerate in-situ reaction by coupling, achieving the goals of fast formation and dispersion of particle phase.
- the exerted magnetic field 4 can be high-frequency oscillating magnetic field which has skin effect in the melt and thus centrally acts on the edge of the melt and generates an electromagnetic force to particles in the composite material melt to control the aggregation of the particles.
- the ultrasonic field mainly acts on the middle area of the bath.
- the magnetic field 4 can be selected as low-frequency stirring magnetic field coupling with power ultrasonic field if the requirements on size and distribution of particles of the composite material are lower. Especially when the amount of metal to be treated is large enough to be in tons, because of the limitations of present high-frequency oscillating magnetic field and high-power pulse magnetic field, coupling low-power stirring magnetic field and high-energy ultrasonic field also can be adopted to obtain an ideal effect.
- the principle lies in high-energy ultrasonic field generating cavitation effect and acoustic streaming impact in the melt, wherein cavitation effect controls the aggregation of particles, and acoustic streaming impact plays a role of stirring in micro area; the exerted low-frequency stirring magnetic field 4 performs electromagnetic stirring to the whole bath, so the ultrasonic stirring effect is more obvious, and the local effect or concentrated effect of ultrasonic treatment can be controlled.
- a method of synthesizing metal matrix composite material by melt reaction in coupling magnetic field and ultrasonic field comprises: adjusting metal-base melt to the onset reaction temperature after refining, then adding reactant powder which generates reinforced particle phase by in-situ synthesis reaction with melt, simultaneously exerting magnetic field and high-energy ultrasonic field during the synthesis reaction, keeping the reacted melt stand until it is cooled to casting temperature after reaction, and casting.
- said exerted field can be high-power pulse magnetic field, high-frequency oscillating magnetic field or low-frequency alternating magnetic field.
- the invention has the following three technical schemes according to different exerted magnetic fields:
- the range of electromagnetic parameters of high-power pulse magnetic field is as follows: pulse current frequency is 0.1 Hz-10 Hz, pulse current density is 1 KA/m 2 -10 KA/m 2 , charging voltage is 1 KV-20 kV, and central magnetic field intensity is 0.5-20T. Electromagnetic parameters can be selected according to the size of the melting pot and the type of the melt, and the effect is remarkable if pulse magnetic field intensity in the melt is over 1T.
- the frequency of ultrasonic field is 10 kHz-30 kHz, and ultrasonic intensity is 0.5 kW/m 2 -60 kW/m 2 .
- the specific steps comprise: adjusting metal-base melt to onset reaction temperature after refining, then adding reagent which generates particle phase by in-situ reaction with the melt, turning on magnetic field, inserting an ultrasonic amplitude transformer below liquid level about 5-6 mm after the magnetic field is stable, turning on an ultrasonic device, ultrasonic treatment time being 60 s-600 s, turning off the ultrasonic device after time out, turning off the magnetic field, keeping the melt stand until it is cooled to the casting temperature, and casting.
- the method is especially suitable for preparing metal matrix composite material with small amount and having extremely high requirement for performance.
- the range of electromagnetic parameters of high-frequency oscillating magnetic field is as follows: high-frequency reference wave frequency is 10 kHz-30 kHz, amplitude modulation oscillating wave frequency is 1 Hz-30 Hz, power range is 0-100 kW, electromagnetic parameters can be adjusted according to the amount and type of melt, bath and stirring intensity, higher reference wave frequency is adopted for aluminum-based or copper-based melt, lower reference wave frequency is suitable for Fe-based, Ni-based or Zn-based melt, oscillating wave frequency is determined by the condition of stirring melt and related to the structure of a reactor and the type of the metal melt, preferably there is no strong turbulence in the melt.
- the frequency of ultrasonic field is 10 kHz-30 kHz, and ultrasonic intensity is 0.5 kW/m 2 -60 kW/m 2 .
- the specific steps comprise: adjusting metal-base melt to the onset reaction temperature after refining, then adding reactant powder which generates reinforced particle phase by in-situ synthesis reaction with melt, turning on magnetic field, inserting an ultrasonic amplitude transformer below liquid level about 5-6 mm after the magnetic field is stable, turning on an ultrasonic device, ultrasonic treatment time being 60 s-600 s, turning off the ultrasonic device after time out, turning off the magnetic field, keeping the melt stand until it is cooled to the casting temperature, and casting.
- the frequency of ultrasonic field is 10 kHz-30 kHz, and ultrasonic intensity is 0.5 kW/m 2 -60 kW/m 2 .
- the specific steps comprise: adjusting metal-base melt to the onset reaction temperature after refining, then adding reactant powder which generates reinforced particle phase by in-situ synthesis reaction with melt, turning on magnetic field, inserting an ultrasonic amplitude transformer below liquid level about 5-6 mm after the magnetic field is stable, turning on an ultrasonic device, ultrasonic treatment time being 60 s-600 s, turning off the ultrasonic device after time out, turning off the magnetic field, keeping the melt stand until it is cooled to the casting temperature, and casting.
- low-frequency alternating magnetic field can be rotating stirring magnetic field or travelling wave stirring magnetic field within the above range of parameters, rotating stirring magnetic field is exerted on the side surface of the bath, or travelling wave magnetic field is exerted on the bottom of the bath, the both belong to the technical scheme of the invention.
- the method can be used for small-batch production as well as large-scale industrial application.
- the composite material is synthesized by coupling magnetic field and ultrasonic field, the coupling of magnetic field and ultrasonic field causes particles to be finer and uniformly distributed;
- Magnetochemistry cooperates with sonochemistry to improve the thermodynamic conditions of in-situ reaction, which accelerates the in-situ reaction speed and controls the growth of particle phase.
- FIG. 1 is a schematic diagram of a device A used in the method of the invention
- FIG. 2 is a schematic diagram of a device B used in the method of the invention.
- FIG. 3 is a schematic diagram of a device of an embodiment
- FIG. 4 is SEM images of particle reinforced Al matrix composite material (Al 3 Zr (s) +ZrB 2(s) ) prepared in coupling high-power pulse magnetic field and ultrasonic field in Embodiment 1;
- FIG. 5 is SEM images of particle reinforced Al matrix composite material (Al 3 Zr (s) +ZrB 2(s) ) prepared in coupling high-frequency oscillating magnetic field and ultrasonic field in Embodiment 2;
- FIG. 6 is SEM images of particle reinforced Al matrix composite material (Al 3 Zr (s) +Al 2 O 3(s) ) prepared in coupling low-frequency stirring magnetic field and ultrasonic field in Embodiment 3.
- 1 is bath or melting pot made of thermal-insulating refractory material; 2 is composite material melt; 3 is ultrasonic amplitude transformer; 4 is magnetic field; and 5 is spray gun.
- Raw material metal matrix: pure Al; reaction salt: K 2 ZrF 6 +KBF 4 power, refined deaerating agent and slag skimming agent.
- the preparation comprises two steps:
- Composite material melt has good fluidity
- the obtained composite material casting billet has smooth outer surface, dense interior microstructure, and no defects of solidification structure such as porosity, shrinkage cavities, etc., and the size of particle is 0.2-0.6 nm ( FIG. 3 ).
- Raw material metal matrix: pure Al; reaction salt: K 2 ZrF 6 +KBF 4 power, refined deaerating agent and slag skimming agent.
- the preparation comprises two steps:
- a device as shown in FIG. 2 pouring refined metal liquid in accordance with requirement of starting temperature (900° C.) into a thermal-insulated composite material bath 1 from a metal refining thermal-insulating furnace, spraying K 2 ZrF 6 +KBF 4 powder into the bath 1 by an Ar gas spray gun 5 , after spraying powder, turning on high-frequency oscillating magnetic field 4 with high-frequency reference wave frequency of 20 kHz, maximum current of 80 A and oscillating wave frequency of 25 Hz, and the waveform of oscillating wave is sine wave; next, inserting an ultrasonic amplitude transformer 3 into a bath by the depth of about 5 mm, turning on an ultrasonic device with ultrasonic field frequency of 20 kHz and ultrasonic intensity of 10 kW/m 2 , and ultrasonic treatment time being 5 minutes; after ultrasonic treatment, continually exerting high-frequency magnetic field for 3 minutes, then turning off magnetic field power, keeping the melt stand until temperature falls to 730° C., deslagging, and casting a round billet with diameter
- Composite material melt has good fluidity
- the obtained composite material casting billet has smooth outer surface, dense interior tissue, and no defects of loose and shrinkage cavities in frozen tissue, and the size of particle is 1-5 nm ( FIG. 4 ).
- Raw material metal matrix: pure Al; solid powder: industrial zirconium carbonate (Zr(CO 3 ) 2 ) power, refined deaerating agent and slag skimming agent.
- the preparation comprises two steps:
- Composite material melt has good fluidity
- the obtained composite material casting billet has smooth outer surface, dense interior tissue, and no defects of loose and shrinkage cavities in frozen tissue, the size of particle is 1-5 ⁇ m ( FIG. 5 ).
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- Mechanical Engineering (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102349789A CN101391290B (zh) | 2008-11-05 | 2008-11-05 | 一种磁场与超声场耦合作用下熔体反应合成金属基复合材料的方法 |
| CN200810234978.9 | 2008-11-05 | ||
| PCT/CN2009/000252 WO2010051675A1 (fr) | 2008-11-05 | 2009-03-10 | Procédé de synthèse d'un matériau composite à base de métal par réaction à l'état fondu dans un champ magnétique et un champ d'ultrasons couplés |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US20110247778A1 true US20110247778A1 (en) | 2011-10-13 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US13/126,510 Abandoned US20110247778A1 (en) | 2008-11-05 | 2009-03-10 | Method of synthesizing metal -based composite material by melt reaction in coupling magnetic field and ultrasonic field |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US20110247778A1 (fr) |
| CN (1) | CN101391290B (fr) |
| WO (1) | WO2010051675A1 (fr) |
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| JP3456311B2 (ja) * | 1995-07-12 | 2003-10-14 | Ｊｆｅスチール株式会社 | 複層鋳片の連続鋳造方法 |
| JP3421535B2 (ja) * | 1997-04-28 | 2003-06-30 | トヨタ自動車株式会社 | 金属基複合材料の製造方法 |
| JP3007947B2 (ja) * | 1997-09-22 | 2000-02-14 | 工業技術院長 | 金属組織微細化法 |
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| CN1324159C (zh) * | 2005-06-06 | 2007-07-04 | 辽宁工学院 | 磁场与超声波联合处理金属熔体制备纳米晶铸锭的方法及专用设备 |
| CN101020973B (zh) * | 2006-02-14 | 2010-12-08 | 丁刚 | 多元相增强金属复合材料制造工艺及设备 |
| CN101199989B (zh) * | 2007-10-17 | 2010-06-02 | 江苏大学 | 异频复合电磁场下连续铸造颗粒增强金属基复合材料的方法 |
-
2008
- 2008-11-05 CN CN2008102349789A patent/CN101391290B/zh active Active
-
2009
- 2009-03-10 WO PCT/CN2009/000252 patent/WO2010051675A1/fr not_active Ceased
- 2009-03-10 US US13/126,510 patent/US20110247778A1/en not_active Abandoned
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| EP3112486A4 (fr) * | 2014-01-28 | 2017-11-15 | China Nuclear Power Engineering Company Ltd. | Procédé de production d'une feuille de matériau absorbant neutronique b 4c/al par laminage en coulée continue |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN101391290A (zh) | 2009-03-25 |
| WO2010051675A1 (fr) | 2010-05-14 |
| CN101391290B (zh) | 2010-12-08 |
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