CN102303353B - Gel-casting preparation method for gradient material in moving magnetic field - Google Patents
Gel-casting preparation method for gradient material in moving magnetic field Download PDFInfo
- Publication number
- CN102303353B CN102303353B CN201110178697.8A CN201110178697A CN102303353B CN 102303353 B CN102303353 B CN 102303353B CN 201110178697 A CN201110178697 A CN 201110178697A CN 102303353 B CN102303353 B CN 102303353B
- Authority
- CN
- China
- Prior art keywords
- magnetic field
- moving magnetic
- fgm
- gradient material
- slurry
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Abstract
The invention discloses a gel-casting preparation method for a gradient material in a moving magnetic field. The method comprises the following steps of: (1) preparation of a casting mold; (2) mixing powder with different magnetisms with water or a non-aqueous solvent according to a certain ratio, and then stirring to prepare evenly-dispersed paste in a ball mill and casting; (3) exerting the moving magnetic field with the intensity of 0.1-10 T to act once or repeatedly; and (4) drying and sinter-molding. The method disclosed by the invention has the advantages that: gradient materials with different composition distributions can be obtained through changing the intensity of the magnetic field, the moving speed and the acting times of the magnetic field; with the adoption of the developed ceramic gel-casting forming process, the procedure for manufacturing the gradient materials is simplified, the cost for manufacturing the gradient materials is lowered, and the performance of the gradient materials is enhanced.
Description
Technical field
The gel injection moulding preparation that the present invention relates to functionally gradient material (FGM) in a kind of moving magnetic field, belongs to field of material preparation.
Background technology
Ceramic material has been widely used in the industrial circles such as electronics, machinery, national defence because of its unique performance.But be difficult to carry out machined after ceramic material sintering, old friends are seeking the dead size forming method of complicated shape ceramic component always, this has become the key link that guarantees ceramic component quality and make developed material acquisition practical application.The forming method of ceramic material, generally can be divided into dry method and the large class of wet method two.Comparatively speaking, wet therapy forming process equipment is simple, molding blank component is even, defect is few, be easy to the advantages such as moulding complicated shape part, practicality is stronger, but all there are some problems in traditional wet moulding technology, if injection forming is to absorb water to realize by plaster mold, cause in base substrate, to form density gradient and distribute and inhomogeneous deformation, and blank strength is low, is easy to damage.Injection moulding or injection moulding need add mass fraction up to 20% wax or organic matter, cause skimming processes loaded down with trivial details, and the thawing of bonding agent or evaporation make the strength decreased of base substrate, easily form defect and even collapse.These problems have improved the production cost of ceramic material, have reduced the stability of its quality.The beginning of the nineties, U.S.'s Oak Ridge National Laboratory has been invented a kind of brand-new ceramic material wet moulding technology---Gelcasting Technique, and main production process is: mix → moulding (solidifying) → eliminating medium of ceramic raw material and medium → dry → sintering.
Gel casting forming is the technology that a kind of practicality is very strong, and it has following distinguishing feature: (1) applicable to various ceramic materials, the ceramic part of the various complicated shapes of moulding and size.(2) due to type-approval process, operation is completely separated with injection molding, and sizing forms the cancellated gelinite of interlinkage by organic monomer in-situ polymerization in slurry and realizes.So molding blank component evenly, even density, defect be few.(3) slurry to solidify shaping time shorter and controlled.Different according to the addition of polymerization temperature and catalyst, solidify shaping time general controlled at 5～60 min.(4) this technique mould therefor is without punch die, and to mould without specific (special) requirements, can be metal, glass or plastics etc.(5) in base substrate, content of organics is less, and its mass fraction is generally 3%～5%.But intensity is higher, generally more than 10MPa.Can carry out machined (car, mill, plane, milling, boring, saw etc.) to base substrate, thereby cancel or reduce the processing after sintering.(6) this is a kind of dead size forming technique.Due to component and the even density of base substrate, thereby in dry and sintering process, can not be out of shape shape and size ratio when sintered body can keep moulding.(7) ceramic material used is high solid phase (volume parts is not less than 50%), low viscosity (being less than 1Pas).The solid concentration of slurry is density, intensity and the inhomogeneity factor that affects molding blank, and the magnitude relationship of viscosity is to the become quality of base substrate shape and the exhaust effect of slurry.
FGM (FGM) is under the condition for high temperature, thermal cycle and large temperature fall, can work repeatedly and the class new material developed, and so harsh environment for use requires material to have excellent heat shock resistance and thermal fatigue property.At present, FGM main preparation methods has powder compacting, physical vaporous deposition (PVD), chemical vapour deposition technique (CVD), plasma spraying, electrocasting, galvanoplastic etc.Powder compacting method is by composition gradient lamination structures such as the feed particulate material such as metal, pottery and whiskers, through compacting, sintering and make FGM.Heat-stable ceramic is for temperature end, and metal material or plastics are for low-temperature end.For reinforced metal forms mutually or improves ceramic phase toughness, can mix whisker.Chemical vapour deposition technique is that halide gas is added to thermal decomposition, metal or semimetal is deposited on substrate surface, or the mists such as the carbide of generation, chloride are sent into reaction tube, makes the Compound deposition of heating generation on substrate.Electrocasting is with metal salt solution, through electrodeposition process, to separate out layer of metal or alloy on parent form surface. then peels off and obtains the goods contrary with establishing type surface convex-concave.Physical vaporous deposition is to make the metal of heating evaporation be deposited on the method for carrying out coating on substrate, in metal, semimetal, sends into after the reacting gas such as oxygen, nitrogen and hydrocarbon, and the potteries such as synthesis oxide, chloride and carbide, and be deposited on substrate.Physical vaporous deposition has vacuum coating, sputter and ion plating etc.Vacuum coating is that merely heating of metal makes its hydatogenesis; Sputtering method is to hit by electronics or ion, and the metal sputtering out is deposited on substrate; Ion plating is by metal vapors ionization, obtains the deposit that caking property is good and fine and close.The thickness of electroforming metal or alloy can be 50 microns to tens centimetres.
But these preparation methods all exist important limitation.As powder compacting is difficult to realize material component continuous and even variation; Vapour deposition is difficult to obtain large thickness material; Self-propagating combustion density is lower; Plasma spraying be respectively coated with the interface that interlayer exists composition sudden change; Etc..These methods require complicated technique or equipment, lack easy preparation method, are the major reasons that limitation function functionally gradient material (FGM) further develops.Therefore,, if ripe metal or ceramic forming material means can be used for preparing FGM, have great importance undoubtedly and vast potential for future development.Utilize the difference of magnetic property between metal and ceramic constituent element, our group adopted gel injection-moulding method successfully to prepare functionally gradient material (FGM) in 2003 in magnetostatic field.This technology has been authorized patent of invention, patent No. CN03116449.8, patent name " preparing gelatin mold made from functional gradient material in static magnetic field ".，Ben group was improved to pulsed magnetic field in 2006 by magnetostatic field subsequently, and successfully prepared functionally gradient material (FGM).This technology has been authorized patent of invention, patent No. CN200610053249.4, patent name " strong magnetic-weak magnetic gradient material gel injection mould preparation method in pulsed magnetic field ".
In the past few years, our group updates on original experiment basis, and makes a breakthrough.On the basis of gel injection-moulding, utilize moving magnetic field to replace magnetostatic field and pulsed magnetic field, successfully prepared the continuous functionally gradient material (FGM) of composition.With under magnetostatic field and pulsed magnetic field, prepare functionally gradient material (FGM) and compare, utilize moving magnetic field to prepare functionally gradient material (FGM), can replace gradient magnetic with the magnetic field of a motion, for the larger system of magnetic contrast, no longer need to obtain high magnetic field gradient by large magnetic field intensity, thereby can in less magnetic field, obtain large component gradient, high magnetic field intensity can make the System forming gradient that magnetic contrast is less.The method has advantages of repeated multiple times simultaneously.Can the restraining force of controlling magnetic field to magnetic constituent element by adjusting magnetic field intensity, movement velocity and magnetic fields number of times, further control the component distributing in material.
The present invention has two or more in slurry of the material composition of different magnetic, adopt gel injection-moulding method consolidation, in curing molding process, occur once or repeated multiple times relative motion with magnetic field, thereby obtain the component gradient along Movement in Magnetic Field direction, then sintering is prepared functionally gradient material (FGM).
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, the gel injection moulding preparation of functionally gradient material (FGM) in a kind of moving magnetic field is provided.
In moving magnetic field, the step of the gel injection moulding preparation of functionally gradient material (FGM) is as follows:
1) casting mold is prepared
Adopt steel, iron, glass or plastics etc. as mold materials, utilize casting and injection moulding process to make mould base substrate, then machining goes out dies cavity;
2) slurry preparation
By particle size, be that two or more of 0.1～100 μ m have in the metal of different magnetic or compound and become mixed-powder by the weight ratio of 0.1～10:1; Organic monomer and methylene-bisacrylamide crosslinking agent dissolve in deionized water by the weight ratio of 6～24:1, are made into the premixed liquid that organic matter quality mark is 10～25%; Mixed-powder is added in premixed liquid, add dispersant simultaneously, ball milling 1～10h in ball mill, ultrasonic dispersionization is processed 1～15min, obtains disperse slurry, and regulating pH is 5～12, in slurry, solid volume content is 50～70%, the humidity of slurry is 20%～50%, and temperature is 20～50 ℃, and viscosity is 1～100mPas;
3) casting in moving magnetic field
By adding initator and catalyst in disperse slurry, account for 0.1 ‰～5% of stock quality, after stirring, inject mould, mould applies above moving magnetic field outward 1 time, magnetic field intensity is 0.1～10T, and movement velocity is 0.1～500mm/s, and the direction of motion and magnetic direction are 0～180 °;
4) gel, dry, sintering
Slurry is placed in to the baking oven gel 5～60min of 60～80 ℃, then in drying at room temperature, is placed in punching block; under the pressure of 0.1～1GPa, suppress; sinter molding in the protection of the environment of argon gas or nitrogen, sintering temperature, between 600～1400 ℃, cools to 100～300 ℃ of taking-ups with the furnace.
The described metal with different magnetic or compound are Fe, Co, Ni alloy, ferrite or rare earth permanent-magnet powder.The described metal with different magnetic or compound are Al, Cu, Mg or Sb alloy.The described metal with different magnetic or compound are ZrO
2, SiC, AlN, Si
3n
4, B
4c, SiO
2, TiC, Y
2o
3or Al
2o
3.Described moving magnetic field is the magnetic field being produced by electromagnet, permanent magnet or superconducting magnet.Described dispersant is ammonium polyacrylate, SD-38, JA-281 or D3005, and dispersant is stock quality 0.05%～0.50%.Described pH value is that employing mass fraction is that 15～38% concentrated ammonia liquors and mass fraction are that 15%～40% concentrated hydrochloric acid regulates.Described organic monomer is acrylamide, Methacrylamide or vinyl pyrrole ketone.Described initator is that mass fraction is 1～5% the persulfuric acid aqueous solution, and addition is stock quality 0.3～3%.Described catalyst is tetramethylethylenediamine content, and addition is stock quality 0.5～5 ‰.
The present invention compared with prior art has beneficial effect:
1) by applying moving magnetic field, change magnetic field intensity, movement velocity and magnetic fields number of times, can in very large composition range, prepare the functionally gradient material (FGM) of various thickness, composition changes continuously and is controlled.
2) with under magnetostatic field and pulsed magnetic field, prepare functionally gradient material (FGM) and compare, utilize moving magnetic field to prepare functionally gradient material (FGM), can replace gradient magnetic with the magnetic field of a motion, for the larger system of magnetic contrast, no longer need to obtain high magnetic field gradient by large magnetic field intensity, thereby can in less magnetic field, obtain large component gradient, high magnetic field intensity can make the System forming gradient that magnetic contrast is less.The method has advantages of repeated multiple times simultaneously.
3) utilize ripe gel injection-moulding technique to make to prepare operation simplification, the cost of functionally gradient material (FGM).
Accompanying drawing explanation
Fig. 1 is slurry model schematic diagram while just having injected;
Fig. 2 is moving magnetic field effect disposed slurry model schematic diagram;
In figure: electromagnet, permanent magnet or superconducting magnet 1, the magnetic field 2 producing, mould 3, weak magnetic particle 4, compared with ferromagnetism particle 5, Movement in Magnetic Field direction 6.
The specific embodiment
Functionally gradient material (FGM) preparation method of the present invention be by two or more have the metal of different magnetic or compound (as Fe, Co, Ni alloy, ferrite and rare earth permanent-magnet powder, Al, Cu, Mg, Sb alloy, ZrO
2, SiC, AlN, Si
3n
4, B
4c, SiO
2, TiC, Y
2o
3, Al
2o
3deng) and solvent composition slurry, pour into dies cavity, in moving magnetic field, be shaped.The stronger constituent element of magnetic in slurry is subject to the repeated action of moving magnetic field, along Movement in Magnetic Field direction, moves, thus forming component gradient.The blank obtaining is made functionally gradient material (FGM) after polymerization, dry, compacting, sintering.
In moving magnetic field, the step of the gel injection moulding preparation of functionally gradient material (FGM) is as follows:
1) casting mold is prepared
Adopt steel, iron, glass or plastics etc. as mold materials, utilize casting and injection moulding process to make mould base substrate, then machining goes out dies cavity.
2) slurry preparation
By particle size, be that two or more of 0.1～100 μ m have in the metal of different magnetic or compound and become mixed-powder by the weight ratio of 0.1～10:1; Organic monomer and methylene-bisacrylamide crosslinking agent dissolve in deionized water by the weight ratio of 6～24:1, are made into the premixed liquid that organic matter quality mark is 10～25%; Mixed-powder is added in premixed liquid, add dispersant simultaneously, ball milling 1～10h in ball mill, ultrasonic dispersionization is processed 1～15min, obtains disperse slurry, and regulating pH is 5～12, in slurry, solid volume content is 50～70%, the humidity of slurry is 20%～50%, and temperature is 20～50 ℃, and viscosity is 1～100mPas.
3) casting in moving magnetic field
By adding initator and catalyst in disperse slurry, account for 0.1 ‰～5% of stock quality, after stirring, inject mould, mould applies above moving magnetic field outward 1 time, magnetic field intensity is 0.1～10T, and movement velocity is 0.1～500mm/s, and the direction of motion and magnetic direction are 0～180 °.Moving magnetic field is produced by electromagnet, permanent magnet or superconducting magnet.In moving magnetic field, the effect that is subject to magnetic force compared with ferromagnetism particle is greater than compared with sub magnetic debris, will be along the migration of Movement in Magnetic Field direction, forming component gradient.Reduce magnetic field intensity, magnetic field reduces the restraining force compared with ferromagnetism constituent element, and component gradient reduces; Improve magnetic field intensity, improve the restraining force compared with ferromagnetism constituent element in magnetic field, and component gradient increases.When Movement in Magnetic Field speed is too large, magnetic field reduced the action time compared with ferromagnetism constituent element, and component gradient reduces; Along with the reduction of movement velocity, improved the action time compared with ferromagnetism constituent element in magnetic field, and component gradient increases.Adjustment magnetic field intensity is 0.1～10T, and movement velocity, at the OK range of 0.1～500mm/s, obtains the sample of required component gradient.Swing die, can reduce viscosity if desired, and deaeration improves green strength.
4) gel, dry, sintering
Slurry is placed in to the baking oven gel 5～60min of 60～80 ℃, then in drying at room temperature, is placed in punching block; under the pressure of 0.1～1GPa, suppress; sinter molding in the protection of the environment of argon gas or nitrogen, sintering temperature, between 600～1400 ℃, cools to 100～300 ℃ of taking-ups with the furnace.
The described metal with different magnetic or compound are Fe, Co, Ni alloy, ferrite or rare earth permanent-magnet powder.The described metal with different magnetic or compound are Al, Cu, Mg or Sb alloy.The described metal with different magnetic or compound are ZrO
2, SiC, AlN, Si
3n
4, B
4c, SiO
2, TiC, Y
2o
3or Al
2o
3.Described moving magnetic field is the magnetic field being produced by electromagnet, permanent magnet or superconducting magnet.Described dispersant is ammonium polyacrylate, SD-38, JA-281 or D3005, and dispersant is stock quality 0.05%～0.50%.Described pH value is that employing mass fraction is that 15～38% concentrated ammonia liquors and mass fraction are that 15%～40% concentrated hydrochloric acid regulates.Described organic monomer is acrylamide, Methacrylamide or vinyl pyrrole ketone.Described initator is that mass fraction is 1～5% the persulfuric acid aqueous solution, and addition is stock quality 0.3～3%.Described catalyst is tetramethylethylenediamine content, and addition is stock quality 0.5～5 ‰.
The injection moulding forming method that the aqueous solution of take is solvent has the following advantages: (1) dry run is simpler.(2) can avoid the problem of environmental pollution that uses nonaqueous solvents to bring.
The functionally gradient material (FGM) of the various thickness that can prepared composition in very large range change by the present invention, and composition changes continuously.Finished product internal flaw is few, and close structure has excellent heat shock resistance and thermal fatigue property.
Embodiment 1:
1) adopt stainless punching block, mould inside die cavity is the cuboid of 30mm * 10mm * 5mm.
2) slurry preparation
Average particle size particle size is the BaO6Fe of 3 μ m
2o
3powder and average particle size particle size are the Al of 0.9 μ m
2o
3powder forms mixed-powder in proportion at 1: 10; Organic monomer acrylamide (AM) and crosslinking agent methylene-bisacrylamide (MBAM) are dissolved in deionized water by the weight ratio of 12:1, be made into the premixed liquid that organic matter quality mark is 15%; Mixed-powder is added in premixed liquid, add content is the dispersant ammonium polyacrylate of stock quality umber 0.1% simultaneously, ball milling 8h in ball mill, ultrasonic dispersionization is processed 10min, obtains disperse slurry, and in slurry, solid volume content is 60%, then with the concentrated hydrochloric acid of 25% concentrated ammonia liquor and 36%, regulating pH value is 7.8, the humidity of slurry is 30%, and temperature is 30 ℃, and viscosity is 34mPas;
3) casting in moving magnetic field
By adding concentration the persulfuric acid aqueous solution initator that is 3wt.% and the tetramethylethylenediamine catalyst that accounts for stock quality 2 ‰ that accounts for stock quality 1% in disperse slurry, after stirring, inject mould, mould applies moving magnetic field outward.The magnetic circuit that moving magnetic field consists of a pair of NdFeB magnet is produced, and magnetic field intensity is 0.1T, and Movement in Magnetic Field speed is 0.5mm/s, direction of motion vertical magnetic field direction, and effect number of times is 10 times.
4) gel, dry, sintering
Slurry is placed in to the baking oven gel 15min of 60 ℃, then in drying at room temperature.Green compact are placed in to punching block, under the pressure of 0.1GPa, suppress.Sintering green compact under the protection of the environment of argon gas.Heating rate with 200 ℃/h is heated to 500 ℃ of insulation 2h, then with 200 ℃/h, is heated to l350 ℃, insulation 1h.Cool to 200 ℃ of taking-ups with the furnace.
The sample prepared to example 1 carries out electron probe line analysis, finds that its composition changes continuously, and barium ferrite reduces to 0% of opposite side by 92% of a side, and sample interior exists without macroscopic interface.To the sample thermal shock test that circulates, under 800 ℃ of temperature difference, chilling condition, through 100 circulations, there is not crackle.
Embodiment 2:
1) adopt stainless steel mould, mould inside die cavity is the cuboid of 30mm * 10mm * 5mm.
2) slurry preparation
Average particle size particle size is that aluminium powder and the average particle size particle size of 50 μ m is the Al of 2.2 μ m
2o
3powder forms mixed-powder in proportion at 1: 1; Organic monomer Methacrylamide and crosslinking agent methylene-bisacrylamide (MBAM) are dissolved in deionized water by the weight ratio of 24:1, be made into the premixed liquid that organic matter quality mark is 15%; Mixed-powder is added in premixed liquid, add content is the dispersant D3005 of stock quality umber 0.3% simultaneously, ball milling 6h in ball mill, ultrasonic dispersionization is processed 8min, obtains disperse slurry, and in slurry, solid volume content is 60%, then with the concentrated hydrochloric acid of 38% concentrated ammonia liquor and 15%, regulating pH value is 10, the humidity of slurry is 40%, and temperature is 33 ℃, and viscosity is 40mPas;
3) casting in moving magnetic field
By adding concentration the persulfuric acid aqueous solution initator that is 2wt.% and the tetramethylethylenediamine catalyst that accounts for stock quality 2 ‰ that accounts for stock quality 2% in disperse slurry, after stirring, inject stainless steel mould, mould applies moving magnetic field outward.Moving magnetic field is produced by superconducting magnet, and magnetic field intensity is 10T, and Movement in Magnetic Field speed is 500mm/s, direction of motion vertical magnetic field direction, and effect number of times is 5 times.
4) gel, dry, sintering
Slurry is placed in to the baking oven gel 15min of 75 ℃, then in drying at room temperature.Green compact are placed in to punching block, under the pressure of 1GPa, suppress.The green compact that obtain are sintering under nitrogen protection.Heating rate with 200 ℃/h is heated to 500 ℃ of insulation 2h, then with 200 ℃/h, is heated to l000 ℃, insulation 2h.Cool to 200 ℃ of taking-ups with the furnace.
The sample prepared to example 2 carries out electron probe line analysis, finds that its composition changes continuously, and Al is 0% by 96% of a side to opposite side, without macroscopic interface, exists.To the thermal shock test that circulates of the sample of gained, under 800 ℃ of temperature difference, chilling condition, through 80 circulations, there is not crackle.
Embodiment 3:
1) adopt cast iron die, mould inside die cavity is the cuboid of 30mm * 10mm * 5mm.
2) slurry preparation
Average particle size particle size is the SmCo of 6 μ m
5powder and average particle size particle size are the ZrO of 2.2 μ m
2powder forms mixed-powder in proportion at 1: 2; Organic monomer Methacrylamide and crosslinking agent methylene-bisacrylamide (MBAM) are dissolved in deionized water by the weight ratio of 15:1, be made into the premixed liquid that organic matter quality mark is 20%; Mixed-powder is added in premixed liquid, add content is the dispersant SD-38 of stock quality umber 0.3% simultaneously, ball milling 6h in ball mill, ultrasonic dispersionization is processed 8min, obtains disperse slurry, and in slurry, solid volume content is 65%, then with the concentrated hydrochloric acid of 25% concentrated ammonia liquor and 30%, regulating pH value is 8.2, the humidity of slurry is 30%, and temperature is 30 ℃, and viscosity is 40mPas;
3) casting in moving magnetic field
By adding concentration the persulfuric acid aqueous solution initator that is 1wt.% and the tetramethylethylenediamine catalyst that accounts for stock quality 3 ‰ that accounts for stock quality 2% in disperse slurry, after stirring, inject cast iron die, mould applies moving magnetic field outward.Moving magnetic field is produced by electromagnet, and magnetic field intensity is 1.0T, and Movement in Magnetic Field speed is 15mm/s, direction of motion vertical magnetic field direction, and effect number of times is 15 times.
4) gel, dry, sintering
Slurry is placed in to the baking oven gel 12min of 70 ℃, then in drying at room temperature.Green compact are placed in to punching block, under the pressure of 0.8GPa, suppress.The green compact that obtain are sintering under nitrogen protection.Heating rate with 300 ℃/h is heated to 500 ℃ of insulation 1.5h, then with 200 ℃/h, is heated to l200 ℃, insulation 2h.Cool to 300 ℃ of taking-ups with the furnace.
The sample prepared to example 3 carries out electron probe line analysis, finds that its composition changes continuously, SmCo
5by 96% of a side, to opposite side, be 0%, without macroscopic interface, exist.To the thermal shock test that circulates of the sample of gained, under 800 ℃ of temperature difference, chilling condition, through 150 circulations, there is not crackle.
Embodiment 4:
1) adopt glass mold, mould inside die cavity is the cuboid of 30mm * 10mm * 5mm.
2) slurry preparation
Average particle size particle size is that the nickel by powder of 3 μ m and TiC powder that average particle size particle size is 0.9 μ m form mixed-powder in proportion at 5: 1; Organic monomer vinyl pyrrole ketone and crosslinking agent methylene-bisacrylamide (MBAM) are dissolved in deionized water by the weight ratio of 20:1, be made into the premixed liquid that organic matter quality mark is 12%; Mixed-powder is added in premixed liquid, add content is the dispersant JA-281 of stock quality umber 0.2% simultaneously, ball milling 8h in ball mill, ultrasonic dispersionization is processed 10min, obtains disperse slurry, and in slurry, solid volume content is 69%, then with the concentrated hydrochloric acid of 30% concentrated ammonia liquor and 25%, regulating pH value is 9, the humidity of slurry is 35%, and temperature is 33 ℃, and viscosity is 55mPas;
3) casting in moving magnetic field
To in disperse slurry, add concentration the persulfuric acid aqueous solution initator that is 1wt.% and the tetramethylethylenediamine catalyst that accounts for stock quality 5 ‰ that accounts for stock quality 5%, implantation glass mould after stirring, mould applies moving magnetic field outward.The magnetic circuit that moving magnetic field consists of a pair of NdFeB permanent magnet produces, and magnetic field intensity is 0.2T, and Movement in Magnetic Field speed is 0.5mm/s, direction of motion vertical magnetic field direction, and effect number of times is 20 times.
4) gel, dry, sintering
Slurry is placed in to the baking oven gel 10min of 80 ℃, then in drying at room temperature.Green compact are placed in to punching block, under the pressure of 0.6GPa, suppress.The green compact that obtain are sintering under nitrogen protection.Heating rate with 200 ℃/h is heated to 500 ℃ of insulation 2h, then with 200 ℃/h, is heated to l250 ℃, insulation 1h.Cool to 200 ℃ of taking-ups with the furnace.
The sample prepared to example 4 carries out electron probe line analysis, finds that its composition changes continuously, and Ni powder is 0% by 94% of a side to opposite side, without macroscopic interface, exists.To the thermal shock test that circulates of the sample of gained, under 800 ℃ of temperature difference, chilling condition, through 150 circulations, there is not crackle.
Embodiment 5:
1) adopt mould of plastics, mould inside die cavity is the cuboid of 30mm * 10mm * 5mm.
2) slurry preparation
Average particle size particle size is that cobalt powder and the average particle size particle size of 1 μ m is the Si of 0.9 μ m
3n
4powder forms mixed-powder in proportion at 1: 5; Organic monomer acrylamide (AM) and crosslinking agent methylene-bisacrylamide (MBAM) are dissolved in deionized water by the weight ratio of 15:1, be made into the premixed liquid that organic matter quality mark is 20%; Mixed-powder is added in premixed liquid, add content is the dispersant D3005 of stock quality umber 0.5% simultaneously, ball milling 5h in ball mill, ultrasonic dispersionization is processed 15min, obtains disperse slurry, and in slurry, solid volume content is 65%, then with the concentrated hydrochloric acid of 20% concentrated ammonia liquor and 30%, regulating pH value is 9.5, the humidity of slurry is 30%, and temperature is 32 ℃, and viscosity is 40mPas;
3) casting in moving magnetic field
To in disperse slurry, add concentration the persulfuric acid aqueous solution initator that is 2wt.% and the tetramethylethylenediamine catalyst that accounts for stock quality 4 ‰ that accounts for stock quality 4%, injected plastic mould after stirring, mould applies moving magnetic field outward.Moving magnetic field is produced by electromagnet, and magnetic field intensity is 1.4T, and Movement in Magnetic Field speed is 20mm/s, direction of motion parallel magnetic field direction, and effect number of times is 5 times.
4) gel, dry, sintering
Slurry is placed in to the baking oven gel 15min of 70 ℃, then in drying at room temperature.Green compact are placed in to punching block, under the pressure of 0.1GPa, suppress.The green compact that obtain are sintering under argon shield.Heating rate with 200 ℃/h is heated to 500 ℃ of insulation 2h, then with 200 ℃/h, is heated to l000 ℃, insulation 2h.Cool to 300 ℃ of taking-ups with the furnace.
The sample prepared to example 5 carries out electron probe line analysis, finds that its composition changes continuously, and Co is 0% by 90% of a side to opposite side, without macroscopic interface, exists.To the thermal shock test that circulates of the sample of gained, under 800 ℃ of temperature difference, chilling condition, through 120 circulations, there is not crackle.
Claims (10)
1. a gel injection moulding preparation for functionally gradient material (FGM) in moving magnetic field, is characterized in that its step is as follows:
1) casting mold is prepared
Adopt steel, iron, glass or plastics as mold materials, utilize casting and injection moulding process to make mould base substrate, then machining goes out dies cavity;
2) slurry preparation
Two kinds of metal or compounds with different magnetic that are 0.1～100 μ m by particle size form mixed-powder by the weight ratio of 0.1～10:1; Organic monomer and methylene-bisacrylamide crosslinking agent dissolve in deionized water by the weight ratio of 6～24:1, are made into the premixed liquid that organic matter quality mark is 10～25%; Mixed-powder is added in premixed liquid, add dispersant simultaneously, ball milling 1～10h in ball mill, ultrasonic dispersionization is processed 1～15min, obtains disperse slurry, and regulating pH is 5～12, in slurry, solid volume content is 50～70%, the humidity of slurry is 20%～50%, and temperature is 20～50 ℃, and viscosity is 1～100mPas;
3) casting in moving magnetic field
By adding initator and catalyst in disperse slurry, account for 0.1 ‰～5% of stock quality, after stirring, inject mould, mould applies above moving magnetic field outward 1 time, magnetic field intensity is 0.1～10T, and movement velocity is 0.1～500mm/s, and the direction of motion and magnetic direction are 0～180 °;
4) gel, dry, sintering
Slurry is placed in to the baking oven gel 5～60min of 60～80 ℃, then in drying at room temperature, is placed in punching block; under the pressure of 0.1～1GPa, suppress; sinter molding in the protection of the environment of argon gas or nitrogen, sintering temperature, between 600～1400 ℃, cools to 100～300 ℃ of taking-ups with the furnace.
2. the gel injection moulding preparation of functionally gradient material (FGM) in a kind of moving magnetic field according to claim 1, is characterized in that the described metal with different magnetic or compound are Fe, Co, Ni alloy, ferrite or rare earth permanent-magnet powder.
3. the gel injection moulding preparation of functionally gradient material (FGM) in a kind of moving magnetic field according to claim 1, is characterized in that the described metal with different magnetic or compound are Al, Cu, Mg or Sb alloy.
4. the gel injection moulding preparation of functionally gradient material (FGM) in a kind of moving magnetic field according to claim 1, is characterized in that the described metal with different magnetic or compound are ZrO
2, SiC, AlN, Si
3n
4, B
4c, SiO
2, TiC, Y
2o
3or Al
2o
3.
5. the gel injection moulding preparation of functionally gradient material (FGM) in a kind of moving magnetic field according to claim 1, is characterized in that described moving magnetic field is the magnetic field being produced by electromagnet, permanent magnet or superconducting magnet.
6. the gel injection moulding preparation of functionally gradient material (FGM) in a kind of moving magnetic field according to claim 1, is characterized in that described dispersant is ammonium polyacrylate, SD-38, JA-281 or D3005, and dispersant is stock quality 0.05%～0.50%.
7. the gel injection moulding preparation of functionally gradient material (FGM) in a kind of moving magnetic field according to claim 1, is characterized in that described pH value is that employing mass fraction is that 15～38% concentrated ammonia liquors and mass fraction are that 15%～40% concentrated hydrochloric acid regulates.
8. the gel injection moulding preparation of functionally gradient material (FGM) in a kind of moving magnetic field according to claim 1, is characterized in that described organic monomer is acrylamide, Methacrylamide or vinyl pyrrole ketone.
9. the gel injection moulding preparation of functionally gradient material (FGM) in a kind of moving magnetic field according to claim 1, is characterized in that described initator is that mass fraction is 1～5% the persulfuric acid aqueous solution, and addition is stock quality 0.3～3%.
10. the gel injection moulding preparation of functionally gradient material (FGM) in a kind of moving magnetic field according to claim 1, is characterized in that described catalyst is tetramethylethylenediamine content, and addition is stock quality 0.5～5 ‰.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110178697.8A CN102303353B (en) | 2011-06-29 | 2011-06-29 | Gel-casting preparation method for gradient material in moving magnetic field |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110178697.8A CN102303353B (en) | 2011-06-29 | 2011-06-29 | Gel-casting preparation method for gradient material in moving magnetic field |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102303353A CN102303353A (en) | 2012-01-04 |
| CN102303353B true CN102303353B (en) | 2014-01-29 |
Family
ID=45377319
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110178697.8A Active CN102303353B (en) | 2011-06-29 | 2011-06-29 | Gel-casting preparation method for gradient material in moving magnetic field |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102303353B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103862052B (en) * | 2012-12-17 | 2017-10-31 | 北京中科三环高技术股份有限公司 | A kind of manufacturing process of isotropism neodymium iron boron magnetic body |
| CN103447534B (en) * | 2013-09-06 | 2015-09-09 | 北京科技大学 | A kind of gel casting method based on organic physical gel |
| CN104972130B (en) * | 2015-06-28 | 2017-10-27 | 中国计量大学 | The gel injection moulding preparation of metal and ceramic gradient material in alternating magnetic field |
| CN105772635B (en) * | 2016-03-14 | 2018-05-15 | 扬州华铁铁路配件有限公司 | A kind of production method of cylinder jacket |
| CN114319871B (en) * | 2021-12-09 | 2022-11-04 | 浙江大学 | Surface treatment method for concrete containing ferromagnetic aggregate |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1445196A (en) * | 2003-04-14 | 2003-10-01 | 浙江大学 | Method for preparing gelatin mold made from functional gradient material in static magnetic field |
| CN1731537A (en) * | 2005-07-28 | 2006-02-08 | 上海大学 | Method for preparing original autogeny MgB2 superconductive material under pulsed magnetic field action |
| WO2006043407A1 (en) * | 2004-10-21 | 2006-04-27 | Murata Manufacturing Co., Ltd | Production method for non-ferromagnetic substance molded product, and non-ferromagnetic substance molded product |
| CN101224601A (en) * | 2008-01-25 | 2008-07-23 | 北京科技大学 | Magnetic field colloidal vibration pour mold forming method for hard magnet ferrite ceramics parts |
| CN101224600A (en) * | 2008-01-25 | 2008-07-23 | 北京科技大学 | Hard magnet ferrite ceramics parts magnetic field gel inject film forming method |
| JP4477830B2 (en) * | 2002-03-25 | 2010-06-09 | 太陽誘電株式会社 | Method for manufacturing piezoelectric ceramic component and piezoelectric ceramic component |
-
2011
- 2011-06-29 CN CN201110178697.8A patent/CN102303353B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4477830B2 (en) * | 2002-03-25 | 2010-06-09 | 太陽誘電株式会社 | Method for manufacturing piezoelectric ceramic component and piezoelectric ceramic component |
| CN1445196A (en) * | 2003-04-14 | 2003-10-01 | 浙江大学 | Method for preparing gelatin mold made from functional gradient material in static magnetic field |
| WO2006043407A1 (en) * | 2004-10-21 | 2006-04-27 | Murata Manufacturing Co., Ltd | Production method for non-ferromagnetic substance molded product, and non-ferromagnetic substance molded product |
| CN1731537A (en) * | 2005-07-28 | 2006-02-08 | 上海大学 | Method for preparing original autogeny MgB2 superconductive material under pulsed magnetic field action |
| CN101224601A (en) * | 2008-01-25 | 2008-07-23 | 北京科技大学 | Magnetic field colloidal vibration pour mold forming method for hard magnet ferrite ceramics parts |
| CN101224600A (en) * | 2008-01-25 | 2008-07-23 | 北京科技大学 | Hard magnet ferrite ceramics parts magnetic field gel inject film forming method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102303353A (en) | 2012-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101503299B (en) | Gel injection moulding preparation for gradient material in rotating magnetic field | |
| CN102211346B (en) | Method for preparing functionally graded material through pressure filtration forming in motional magnetic field | |
| CN102303353B (en) | Gel-casting preparation method for gradient material in moving magnetic field | |
| CN104493952A (en) | Gel-casting 3D printing preparation method for ceramic gradient material | |
| CN102925824A (en) | Preparation method for zirconium-based amorphous alloy as well as powder and large-sized block of zirconium-based amorphous alloy | |
| CN100548604C (en) | Strong magnetic-weak magnetic gradient material formed by slip casting preparation method in the pulsed magnetic field | |
| CN104401968B (en) | A kind of method preparing three-dimensional Graphene based on 3D printing foamed metal | |
| CN103667762B (en) | A kind of preparation method of low density porous metal material | |
| CN104353835A (en) | Part manufacturing method combining 3D (three-dimensional) printing with powder metallurgy | |
| CN107098700A (en) | A kind of high solids content BMN suspension inks printed suitable for direct write and preparation method thereof | |
| CN105543526A (en) | Method for preparing high-compactness titanium or titanium alloy by using gel casting formation | |
| CN1911619B (en) | Preparation method of strong magnetic-weak magnetic gradient material gel injection mould in pulse magnetic field | |
| CN103632834B (en) | A kind of preparation method of high-performance anisotropic Nd-Fe-B | |
| CN1187289C (en) | Method for preparing gelatin mold made from functional gradient material in static magnetic field | |
| CN105921752A (en) | Method for preparing invar alloy resonance bar | |
| CN106064241B (en) | A kind of preparation method of internal diameter controllable foam metal | |
| CN1206069C (en) | Press filtering process to form functional gradient material in static magnetic field | |
| CN105039830A (en) | Tape-casting preparing method of metal/ceramic functionally graded materials in alternating magnetic field | |
| CN1176768C (en) | Functional gradient material slip-casting formation preparation method in maynetostatic field | |
| CN114367663B (en) | Preparation method of fully-compact titanium alloy thin-wall part with complex shape | |
| CN111922345B (en) | Comprehensive utilization method of powder by-product generated in spray forming process and application of product | |
| CN104972126A (en) | Pressing filtration forming preparation method for metal/ceramic gradient materials in alternating magnetic field | |
| CN103343252B (en) | The preparation method of sintering Ti-Al base alloy porous material | |
| CN103436753B (en) | The alterant of silumin alloy melt and utilize the silumin preparation method of this alterant | |
| CN106082997B (en) | A kind of method that calcium oxide-based ceramic-mould is prepared by chemical vapor deposition means |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 310027 Hangzhou, Zhejiang Province, Xihu District, Zhejiang Road, No. 38, No. Patentee after: Zhejiang University Patentee after: Zhejiang Zhongyuan Magnetic Industry Co., Ltd. Address before: 310027 Hangzhou, Zhejiang Province, Xihu District, Zhejiang Road, No. 38, No. Patentee before: Zhejiang University Patentee before: Dongyang Zhongyuan Magnetic Industry Co., Ltd. |