CN107492432B - A kind of preparation method of Nd-Fe-B permanent magnet - Google Patents
A kind of preparation method of Nd-Fe-B permanent magnet Download PDFInfo
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- CN107492432B CN107492432B CN201710694538.0A CN201710694538A CN107492432B CN 107492432 B CN107492432 B CN 107492432B CN 201710694538 A CN201710694538 A CN 201710694538A CN 107492432 B CN107492432 B CN 107492432B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
- H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
- H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
- H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
- H01F1/0577—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together sintered
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
- H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
- H01F41/026—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets protecting methods against environmental influences, e.g. oxygen, by surface treatment
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
- H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
- H01F41/0266—Moulding; Pressing
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Abstract
The invention discloses a kind of preparation methods of Nd-Fe-B permanent magnet, belong to permanent magnet preparation technical field.It includes the preparation of neodymium iron co-precipitation；The homogeneous cladding of alum and chromium；The reduction of sodium borohydride and add boron, after high pressure hydrogen reduction form and be sintered；The passivation of sulfuric acid and potassium phosphate,monobasic.A kind of preparation method of Nd-Fe-B permanent magnet of the invention, at low cost, high-efficient, obtained product corrosion resistance is strong, and coercivity is big, the high Nd-Fe-B permanent magnet of maximum operating temperature.
Description
Technical field
The present invention relates to a kind of preparation methods of Nd-Fe-B permanent magnet, belong to permanent magnet preparation technical field.
Background technique
Neodymium iron boron is briefly a kind of magnet and magnet that we usually see the difference is that its excellent magnetism
Can and be referred to as " magnetic king ".
Contain a large amount of rear earth element nd, iron and boron in neodymium iron boron, characteristic is hard and crisp.Since surface is easily oxidized corruption
Erosion, neodymium iron boron must carry out surface coated treatment.Surface chemistry passivation is one of very good solution method.Neodymium iron boron is as rare earth
Permanent-magnet material it is a kind of with high magnetic energy product and coercivity, while so that Nd-Fe-B permanent magnet material is existed the advantages of high-energy density
It is applied widely in modern industry and electronic technology, to make the small of the equipment such as instrument and meter, electroacoustic motor, magnetic separation magnetization
Type, lightweight, slimming are possibly realized.The advantages of neodymium iron boron is cost performance height, has good mechanical property；Shortcoming exists
Low in operating temperature, temperature characterisitic is poor, and is easy to dusting corrosion, it is necessary to by adjusting its chemical component and take surface treatment side
Method is allowed to be improved, and can be only achieved the requirement of practical application.
Its conventional process flow: ingredient → melting ingot/gets rid of band → powder → die mould → sintering tempering → magnetic detection processed
→ mill processing → pin cuts processing → plating → finished product, and wherein ingredient is basis, and sintering tempering is crucial.
But since the antiseptic property of neodymium iron boron is poor, it is desirable to provide a kind of NdFeB material of new corrosion preventive and strength.
Summary of the invention
In view of this, the present invention provides a kind of preparation method of Nd-Fe-B permanent magnet, it is at low cost, it is high-efficient, it obtains
Product corrosion resistance is strong, and coercivity is big, the high Nd-Fe-B permanent magnet of maximum operating temperature.
The present invention solves above-mentioned technical problem by following technological means:
A kind of preparation method of Nd-Fe-B permanent magnet of the invention comprising following steps:
(1) mixture of ferrous sulfate, neodymium chloride, sodium carbonate and sodium hydroxide is configured to solution, be respectively put into
It in the container of sealing, is then conveyed outward using compressed gas as power, while being mixed together and being added in reactor with oxygen, reaction
Temperature is 50-55 DEG C, and residence time 5-10 second of material in the reactor, reaction process maintains pH1.5-2.0, after obtaining reaction
Slurry.
(2) it will be washed after slurries filtration, the CoCl of 15-20mg/l be added after washing according to mass ratio 1:52Solution, then
Polyethylene glycol is added and is dispersed with stirring 30-35min, the mixed solution of sulfuric acid alum and chromium sulfate is added later, adds urea thereafter
Solution, 120-125 DEG C reaction 2-2.5 hours, filtration washing, obtain cladding material.
(3) by after cladding material plus pure water pulp, sodium borohydride is added in the case where pH is 5.5-6.5, in 25-35 DEG C of reaction 2-3
Hour, it is then 210-230 DEG C in temperature, pressure is that hydrogen is passed through under 5-7Mpa, is reacted 3-3.5 hours, while mixing speed
For 300-350r/min, then filtration washing.
(4) sample after washing is added in the solution of paraffin and organic solvent composition, is mixed evenly, mixing
Temperature is 30-35 DEG C, is then vacuumized, while heated to 60-65 DEG C evaporates solvent completely, by parafilm wrap in material
Then compression moulding and sintering are passed through in outside, the mixed solution that sintered material is formed in the concentrated sulfuric acid and potassium phosphate,monobasic
Middle immersion 30-50 seconds, temperature when immersion are 5-15 DEG C, are then eluted with 5-15 DEG C of sodium bicarbonate solution to wash water and are
Property to get.
The ferrous sulfate, neodymium chloride, the mixture of sodium carbonate and sodium hydroxide, oxygen molar ratio be 6.8-6.9:
The molar ratio of 0.9-1.0:7-12:18-20, the sodium carbonate and sodium hydroxide is 3:1-1.2, when reactor is added, sulfuric acid
Ferrous iron solution, neodymium chloride solution, sodium carbonate and sodium hydroxide the flow velocity of mixture solution be 20-25m/s, the flow velocity of oxygen is
30-50m/s。
It is provided with cyclic structure on the reactor, ferrous sulfate feed pipe, neodymium chloride charging are provided in cyclic structure
The mixture feed pipe and oxygen feeding pipe of pipe, sodium carbonate and sodium hydroxide, ferrous sulfate feed pipe, neodymium chloride feed pipe, carbon
The mixture feed pipe and oxygen feeding pipe of sour sodium and sodium hydroxide are evenly distributed in cyclic structure and in the same plane, and
Perpendicular to cyclic structure, discharge port, ferrous sulfate feed pipe, neodymium chloride feed pipe, carbonic acid are provided on the axle center of cyclic structure
Sodium is connected to the mixture feed pipe of sodium hydroxide with oxygen feeding Guan Junyu discharge port, ferrous sulfate feed pipe, neodymium chloride into
The mixture feed pipe of expects pipe, sodium carbonate and sodium hydroxide and the bore of oxygen feeding pipe are 0.5-2mm, the bore of discharge port
For 2-5mm, the length of discharge port is 20-100cm.
The mass fraction of step (2) polyglycol solution is 0.01-0.02%, ferrous sulfate and sulfuric acid alum and sulfuric acid
The molar ratio of sulfuric acid alum and chromium sulfate is 50-60:0.7-0.8:1.0-1.2 in the mixed solution of chromium, and the concentration of urea liquid is
The mass ratio of the mixed solution of 2-3mol/l, urea liquid and sulfuric acid alum and chromium sulfate is 1:0.5-0.6.
The mass ratio of material is coated as 0.3-0.35:0.8-1.1 in sodium borohydride and step (2) in the step (3), is passed through
The quality of hydrogen is 0.1-0.2 times of cladding material quality.
The mass ratio of paraffin and organic solvent is 1:1-2 in the step (4), and the organic solvent is thiacyclohexane, washing
The mass ratio of the solution of sample and paraffin and organic solvent composition afterwards is 3-5:1, the mass fraction > 98% of sulfuric acid in the concentrated sulfuric acid,
The concentration of potassium phosphate,monobasic is 0.1-0.22mol/l.
Beneficial effects of the present invention:
(1) microreactor impinging stream reaction is used, the reaction time is short, and obtained iron neodymium co-precipitation particle is thin, reaches 100-
120nm, reaction efficiency is high, using urea homogeneous coprecipitation sulfuric acid alum and chromium sulfate, the uniform cladding of alum and chromium may be implemented, add
Enter cobalt ions as activator, reduce costs, while improving the consistency of cladding, while the micro addition of cobalt, does not influence
The performance of neodymium iron boron can refine the primary particle of reduction neodymium iron boron using high pressure hydrogen reduction, while alum and chromium may be implemented
Uniformly cladding and fine and close growth.It can be reduced simultaneously to avoid the oxidation of neodymium iron boron during the sintering process by the way of adding wax
The fugitive dust of neodymium iron boron reduces the loss of neodymium iron boron, and oxidation film and phosphorus may be implemented in the concentrated sulfuric acid and potassium phosphate,monobasic mixed liquor
Change the dual layer passivation of film, it is easy to operate.
(2) by the primary particle of refinement neodymium iron boron, coercivity is improved, by the cladding of alum and chromium, can be made with highest
With temperature, while the cladding of alum and chromium adds the dual layer passivation of oxidation film and phosphating coat, improves corrosion resistance.
(3) boron is restored while added using sodium borohydride, and the addition of the other boron of molecular level may be implemented, it is more uniform,
The performance of neodymium iron boron is more preferable.
Detailed description of the invention
The invention will be further described with reference to the accompanying drawings and examples.
Fig. 1 is the structural schematic diagram of reactor of the present invention.
Fig. 2 is the top view of reactor of the present invention.
Specific embodiment
Below with reference to attached drawing, the present invention is described in detail, as shown in Figure 1, 2: one kind of the invention of the present embodiment
The preparation method of Nd-Fe-B permanent magnet comprising following steps:
(1) mixture of ferrous sulfate, neodymium chloride, sodium carbonate and sodium hydroxide is configured to solution, be respectively put into
It in the container of sealing, is then conveyed outward using compressed gas as power, while being mixed together and being added in reactor with oxygen, reaction
Temperature is 50-55 DEG C, and residence time 5-10 second of material in the reactor, reaction process maintains pH1.5-2.0, after obtaining reaction
Slurry.
(2) it will be washed after slurries filtration, the CoCl of 15-20mg/l be added after washing according to mass ratio 1:52Solution, then
Polyethylene glycol is added and is dispersed with stirring 30-35min, the mixed solution of sulfuric acid alum and chromium sulfate is added later, adds urea thereafter
Solution, 120-125 DEG C reaction 2-2.5 hours, filtration washing, obtain cladding material.
(3) by after cladding material plus pure water pulp, sodium borohydride is added in the case where pH is 5.5-6.5, in 25-35 DEG C of reaction 2-3
Hour, it is then 210-230 DEG C in temperature, pressure is that hydrogen is passed through under 5-7Mpa, is reacted 3-3.5 hours, while mixing speed
For 300-350r/min, then filtration washing.
(4) sample after washing is added in the solution of paraffin and organic solvent composition, is mixed evenly, mixing
Temperature is 30-35 DEG C, is then vacuumized, while heated to 60-65 DEG C evaporates solvent completely, by parafilm wrap in material
Then compression moulding and sintering are passed through in outside, the mixed solution that sintered material is formed in the concentrated sulfuric acid and potassium phosphate,monobasic
Middle immersion 30-50 seconds, temperature when immersion are 5-15 DEG C, are then eluted with 5-15 DEG C of sodium bicarbonate solution to wash water and are
Property to get.
The ferrous sulfate, neodymium chloride, the mixture of sodium carbonate and sodium hydroxide, oxygen molar ratio be 6.8-6.9:
The molar ratio of 0.9-1.0:7-12:18-20, the sodium carbonate and sodium hydroxide is 3:1-1.2, when reactor is added, sulfuric acid
Ferrous iron solution, neodymium chloride solution, sodium carbonate and sodium hydroxide the flow velocity of mixture solution be 20-25m/s, the flow velocity of oxygen is
30-50m/s。
Cyclic structure 1 is provided on the reactor, be provided in cyclic structure 1 ferrous sulfate feed pipe 2, neodymium chloride into
The mixture feed pipe 4 and oxygen feeding pipe 5 of expects pipe 3, sodium carbonate and sodium hydroxide, ferrous sulfate feed pipe 2, neodymium chloride charging
The mixture feed pipe 4 and oxygen feeding pipe 5 of pipe 3, sodium carbonate and sodium hydroxide are evenly distributed in cyclic structure 1 and same
In plane, and perpendicular to cyclic structure 1, discharge port 6, ferrous sulfate feed pipe 2, chlorination are provided on the axle center of cyclic structure 1
The mixture feed pipe 4 and oxygen feeding pipe 5 of neodymium feed pipe 3, sodium carbonate and sodium hydroxide are connected to discharge port 6, and sulfuric acid is sub-
Iron feed pipe 2, neodymium chloride feed pipe 3, the mixture feed pipe 4 of sodium carbonate and sodium hydroxide and oxygen feeding pipe 5 bore
For 0.5-2mm, the bore of discharge port 6 is 2-5mm, and the length of discharge port is 20-100cm.
The mass fraction of step (2) polyglycol solution is 0.01-0.02%, ferrous sulfate and sulfuric acid alum and sulfuric acid
The molar ratio of sulfuric acid alum and chromium sulfate is 50-60:0.7-0.8:1.0-1.2 in the mixed solution of chromium, and the concentration of urea liquid is
The mass ratio of the mixed solution of 2-3mol/l, urea liquid and sulfuric acid alum and chromium sulfate is 1:0.5-0.6.
The mass ratio of material is coated as 0.3-0.35:0.8-1.1 in sodium borohydride and step (2) in the step (3), is passed through
The quality of hydrogen is 0.1-0.2 times of cladding material quality.
The mass ratio of paraffin and organic solvent is 1:1-2 in the step (4), and the organic solvent is thiacyclohexane, washing
The mass ratio of the solution of sample and paraffin and organic solvent composition afterwards is 3-5:1, the mass fraction > 98% of sulfuric acid in the concentrated sulfuric acid,
The concentration of potassium phosphate,monobasic is 0.1-0.22mol/l.
Embodiment 1
A kind of preparation method of Nd-Fe-B permanent magnet comprising following steps:
(1) mixture of ferrous sulfate, neodymium chloride, sodium carbonate and sodium hydroxide is configured to solution, be respectively put into
It in the container of sealing, is then conveyed outward using compressed gas as power, while being mixed together and being added in reactor with oxygen, reaction
Temperature is 52 DEG C, and 8 seconds residence times in the reactor of material, reaction process maintains pH1.65, the slurry after being reacted.
(2) it will be washed after slurries filtration, the CoCl of 17.5mg/l be added after washing according to mass ratio 1:52Solution, then plus
Enter polyethylene glycol and be dispersed with stirring 32.5min, the mixed solution of sulfuric acid alum and chromium sulfate is added later, it is molten to add urea thereafter
Liquid reacts 2.3 hours, filtration washing at 122 DEG C, obtains cladding material.
(3) will after cladding material plus pure water pulp, pH be 5.95 it is lower sodium borohydride is added, 29 DEG C reaction 2.3 hours, so
It is afterwards 220 DEG C in temperature, pressure is that hydrogen is passed through under 5.8Mpa, is reacted 3.23 hours, while mixing speed is 320r/min, so
Filtration washing afterwards.
(4) sample after washing is added in the solution of paraffin and organic solvent composition, is mixed evenly, mixing
Temperature is 32 DEG C, is then vacuumized, while heated to 62.5 DEG C evaporate solvent completely, by parafilm wrap outside material
Then compression moulding and sintering are passed through in face, by sintered material in the mixed solution that the concentrated sulfuric acid and potassium phosphate,monobasic form
It impregnates 39 seconds, temperature when immersion is 12.5 DEG C, and then being eluted with 12.5 DEG C of sodium bicarbonate solution to wash water is neutrality, i.e.,
?.
The ferrous sulfate, neodymium chloride, the mixture of sodium carbonate and sodium hydroxide, oxygen molar ratio be 6.85:0.95:
The molar ratio of 8:19, the sodium carbonate and sodium hydroxide is 3:1.1, and when reactor is added, ferrous sulfate solution, neodymium chloride are molten
The flow velocity of the mixture solution of liquid, sodium carbonate and sodium hydroxide is 22.5m/s, and the flow velocity of oxygen is 40m/s.
Cyclic structure 1 is provided on the reactor, be provided in cyclic structure 1 ferrous sulfate feed pipe 2, neodymium chloride into
The mixture feed pipe 4 and oxygen feeding pipe 5 of expects pipe 3, sodium carbonate and sodium hydroxide, ferrous sulfate feed pipe 2, neodymium chloride charging
The mixture feed pipe 4 and oxygen feeding pipe 5 of pipe 3, sodium carbonate and sodium hydroxide are evenly distributed in cyclic structure 1 and same
In plane, and perpendicular to cyclic structure 1, discharge port 6, ferrous sulfate feed pipe 2, chlorination are provided on the axle center of cyclic structure 1
The mixture feed pipe 4 and oxygen feeding pipe 5 of neodymium feed pipe 3, sodium carbonate and sodium hydroxide are connected to discharge port 6, and sulfuric acid is sub-
Iron feed pipe 2, neodymium chloride feed pipe 3, the mixture feed pipe 4 of sodium carbonate and sodium hydroxide and oxygen feeding pipe 5 bore
For 0.95mm, the bore of discharge port 6 is 3.5mm, and the length of discharge port is 80cm.
The mass fraction of step (2) polyglycol solution is 0.015%, ferrous sulfate and sulfuric acid alum and chromium sulfate
The molar ratio of sulfuric acid alum and chromium sulfate is 55:0.78:1.15 in mixed solution, and the concentration of urea liquid is 2.1mol/l, urea
The mass ratio of the mixed solution of solution and sulfuric acid alum and chromium sulfate is 1:0.56.
The mass ratio of material is coated as 0.33:0.95 in sodium borohydride and step (2) in the step (3), is passed through hydrogen
Quality is 0.15 times of cladding material quality.
The mass ratio of paraffin and organic solvent is 1:1.1 in the step (4), and the organic solvent is thiacyclohexane, washing
The mass ratio of the solution of sample and paraffin and organic solvent composition afterwards is 4:1, the mass fraction > 98% of sulfuric acid, phosphorus in the concentrated sulfuric acid
The concentration of a sour hydrogen potassium is 0.21mol/l.
Embodiment 2
A kind of preparation method of Nd-Fe-B permanent magnet comprising following steps:
(1) mixture of ferrous sulfate, neodymium chloride, sodium carbonate and sodium hydroxide is configured to solution, be respectively put into
It in the container of sealing, is then conveyed outward using compressed gas as power, while being mixed together and being added in reactor with oxygen, reaction
Temperature is 52 DEG C, and 8 seconds residence times in the reactor of material, reaction process maintains pH1.65, the slurry after being reacted.
(2) it will be washed after slurries filtration, the CoCl of 18.5mg/l be added after washing according to mass ratio 1:52Solution, then plus
Enter polyethylene glycol and be dispersed with stirring 32min, the mixed solution of sulfuric acid alum and chromium sulfate is added later, adds urea liquid thereafter,
It is reacted 2.3 hours at 122 DEG C, filtration washing, obtains cladding material.
(3) will after cladding material plus pure water pulp, pH be 5.95 it is lower sodium borohydride is added, 29 DEG C reaction 2.3 hours, so
It is afterwards 220 DEG C in temperature, pressure is that hydrogen is passed through under 5.8Mpa, is reacted 3.23 hours, while mixing speed is 320r/min, so
Filtration washing afterwards.
(4) sample after washing is added in the solution of paraffin and organic solvent composition, is mixed evenly, mixing
Temperature is 32 DEG C, is then vacuumized, while heated to 62.5 DEG C evaporate solvent completely, by parafilm wrap outside material
Then compression moulding and sintering are passed through in face, by sintered material in the mixed solution that the concentrated sulfuric acid and potassium phosphate,monobasic form
It impregnates 36 seconds, temperature when immersion is 12.5 DEG C, and then being eluted with 12.5 DEG C of sodium bicarbonate solution to wash water is neutrality, i.e.,
?.
The ferrous sulfate, neodymium chloride, the mixture of sodium carbonate and sodium hydroxide, oxygen molar ratio be 6.85:0.95:
The molar ratio of 8:18, the sodium carbonate and sodium hydroxide is 3:1.1, and when reactor is added, ferrous sulfate solution, neodymium chloride are molten
The flow velocity of the mixture solution of liquid, sodium carbonate and sodium hydroxide is 23m/s, and the flow velocity of oxygen is 40m/s.
Cyclic structure 1 is provided on the reactor, be provided in cyclic structure 1 ferrous sulfate feed pipe 2, neodymium chloride into
The mixture feed pipe 4 and oxygen feeding pipe 5 of expects pipe 3, sodium carbonate and sodium hydroxide, ferrous sulfate feed pipe 2, neodymium chloride charging
The mixture feed pipe 4 and oxygen feeding pipe 5 of pipe 3, sodium carbonate and sodium hydroxide are evenly distributed in cyclic structure 1 and same
In plane, and perpendicular to cyclic structure 1, discharge port 6, ferrous sulfate feed pipe 2, chlorination are provided on the axle center of cyclic structure 1
The mixture feed pipe 4 and oxygen feeding pipe 5 of neodymium feed pipe 3, sodium carbonate and sodium hydroxide are connected to discharge port 6, and sulfuric acid is sub-
Iron feed pipe 2, neodymium chloride feed pipe 3, the mixture feed pipe 4 of sodium carbonate and sodium hydroxide and oxygen feeding pipe 5 bore
For 0.95mm, the bore of discharge port 6 is 3.5mm, and the length of discharge port is 90cm.
The mass fraction of step (2) polyglycol solution is 0.015%, ferrous sulfate and sulfuric acid alum and chromium sulfate
The molar ratio of sulfuric acid alum and chromium sulfate is 55:0.78:1.12 in mixed solution, and the concentration of urea liquid is 2.1mol/l, urea
The mass ratio of the mixed solution of solution and sulfuric acid alum and chromium sulfate is 1:0.56.
The mass ratio of material is coated as 0.33:0.95 in sodium borohydride and step (2) in the step (3), is passed through hydrogen
Quality is 0.15 times of cladding material quality.
The mass ratio of paraffin and organic solvent is 1:1.11 in the step (4), and the organic solvent is thiacyclohexane, washing
The mass ratio of the solution of sample and paraffin and organic solvent composition afterwards is 4:1, the mass fraction > 98% of sulfuric acid, phosphorus in the concentrated sulfuric acid
The concentration of a sour hydrogen potassium is 0.20mol/l.
Embodiment 3
A kind of preparation method of Nd-Fe-B permanent magnet comprising following steps:
(1) mixture of ferrous sulfate, neodymium chloride, sodium carbonate and sodium hydroxide is configured to solution, be respectively put into
It in the container of sealing, is then conveyed outward using compressed gas as power, while being mixed together and being added in reactor with oxygen, reaction
Temperature is 52 DEG C, and 8 seconds residence times in the reactor of material, reaction process maintains pH1.6, the slurry after being reacted.
(2) it will be washed after slurries filtration, the CoCl of 16.5mg/l be added after washing according to mass ratio 1:52Solution, then plus
Enter polyethylene glycol and be dispersed with stirring 31min, the mixed solution of sulfuric acid alum and chromium sulfate is added later, adds urea liquid thereafter,
It is reacted 2.3 hours at 123 DEG C, filtration washing, obtains cladding material.
(3) will after cladding material plus pure water pulp, pH be 5.95 it is lower sodium borohydride is added, 29 DEG C reaction 2.3 hours, so
It is afterwards 220 DEG C in temperature, pressure is that hydrogen is passed through under 5.8Mpa, is reacted 3.23 hours, while mixing speed is 320r/min, so
Filtration washing afterwards.
(4) sample after washing is added in the solution of paraffin and organic solvent composition, is mixed evenly, mixing
Temperature is 32 DEG C, is then vacuumized, while heated to 62.5 DEG C evaporate solvent completely, by parafilm wrap outside material
Then compression moulding and sintering are passed through in face, by sintered material in the mixed solution that the concentrated sulfuric acid and potassium phosphate,monobasic form
It impregnates 36 seconds, temperature when immersion is 13.5 DEG C, and then being eluted with 12.5 DEG C of sodium bicarbonate solution to wash water is neutrality, i.e.,
?.
The ferrous sulfate, neodymium chloride, the mixture of sodium carbonate and sodium hydroxide, oxygen molar ratio be 6.85:0.95:
The molar ratio of 8:18, the sodium carbonate and sodium hydroxide is 3:1.1, and when reactor is added, ferrous sulfate solution, neodymium chloride are molten
The flow velocity of the mixture solution of liquid, sodium carbonate and sodium hydroxide is 22m/s, and the flow velocity of oxygen is 40m/s.
Cyclic structure 1 is provided on the reactor, be provided in cyclic structure 1 ferrous sulfate feed pipe 2, neodymium chloride into
The mixture feed pipe 4 and oxygen feeding pipe 5 of expects pipe 3, sodium carbonate and sodium hydroxide, ferrous sulfate feed pipe 2, neodymium chloride charging
The mixture feed pipe 4 and oxygen feeding pipe 5 of pipe 3, sodium carbonate and sodium hydroxide are evenly distributed in cyclic structure 1 and same
In plane, and perpendicular to cyclic structure 1, discharge port 6, ferrous sulfate feed pipe 2, chlorination are provided on the axle center of cyclic structure 1
The mixture feed pipe 4 and oxygen feeding pipe 5 of neodymium feed pipe 3, sodium carbonate and sodium hydroxide are connected to discharge port 6, and sulfuric acid is sub-
Iron feed pipe 2, neodymium chloride feed pipe 3, the mixture feed pipe 4 of sodium carbonate and sodium hydroxide and oxygen feeding pipe 5 bore
For 0.95mm, the bore of discharge port 6 is 3.5mm, and the length of discharge port is 90cm.
The mass fraction of step (2) polyglycol solution is 0.015%, ferrous sulfate and sulfuric acid alum and chromium sulfate
The molar ratio of sulfuric acid alum and chromium sulfate is 55:0.76:1.12 in mixed solution, and the concentration of urea liquid is 2.1mol/l, urea
The mass ratio of the mixed solution of solution and sulfuric acid alum and chromium sulfate is 1:0.56.
The mass ratio of material is coated as 0.33:0.95 in sodium borohydride and step (2) in the step (3), is passed through hydrogen
Quality is 0.15 times of cladding material quality.
The mass ratio of paraffin and organic solvent is 1:1.11 in the step (4), and the organic solvent is thiacyclohexane, washing
The mass ratio of the solution of sample and paraffin and organic solvent composition afterwards is 4:1, the mass fraction > 98% of sulfuric acid, phosphorus in the concentrated sulfuric acid
The concentration of a sour hydrogen potassium is 0.20mol/l.
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to compared with
Good embodiment describes the invention in detail, those skilled in the art should understand that, it can be to skill of the invention
Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this
In the scope of the claims of invention.
Claims (6)
1. a kind of preparation method of Nd-Fe-B permanent magnet, which comprises the following steps:
(1) mixture of ferrous sulfate, neodymium chloride, sodium carbonate and sodium hydroxide is configured to solution, is respectively put into sealing
Container in, then conveyed outward using compressed gas as power, at the same with oxygen be mixed together be added reactor in, reaction temperature
It is 50-55 DEG C, residence time 5-10 second in the reactor, reaction process maintains pH1.5-2.0, the slurry after being reacted；
(2) it will be washed after slurries filtration that step (1) obtains, the CoCl of 15-20mg/l be added after washing according to mass ratio 1:52It is molten
Then liquid is added polyethylene glycol and is dispersed with stirring 30-35min, the mixed solution of sulfuric acid alum and chromium sulfate is added later, adds again thereafter
Enter urea liquid, 120-125 DEG C reaction 2-2.5 hours, filtration washing, obtain cladding material；
(3) after the cladding material that step (2) obtains being added pure water pulp, sodium borohydride is added in the case where pH is 5.5-6.5, in 25-35
DEG C reaction 2-3 hour, be then 210-230 DEG C in temperature, pressure is to be passed through hydrogen under 5-7Mpa, reaction 3-3.5 hours, simultaneously
Mixing speed is 300-350r/min, then filtration washing；
(4) sample after step (3) washing is added in the solution of paraffin and organic solvent composition, is mixed evenly, mixing is stirred
The temperature mixed is 30-35 DEG C, then vacuumizes, while heated to 60-65 DEG C evaporates solvent completely, parafilm wrap is existed
Outside material, then pass through compression moulding and sintering, the mixing that sintered material is formed in the concentrated sulfuric acid and potassium phosphate,monobasic
It is impregnated 30-50 seconds in solution, temperature when immersion is 5-15 DEG C, is then eluted with 5-15 DEG C of sodium bicarbonate solution to wash water and is
Neutrality to get.
2. a kind of preparation method of Nd-Fe-B permanent magnet according to claim 1, it is characterised in that: the ferrous sulfate,
Neodymium chloride, the mixture of sodium carbonate and sodium hydroxide, oxygen molar ratio be 6.8-6.9:0.9-1.0:7-12:18-20, it is described
The molar ratio of sodium carbonate and sodium hydroxide is 3:1-1.2, when reactor is added, ferrous sulfate solution, neodymium chloride solution, carbonic acid
The flow velocity of the mixture solution of sodium and sodium hydroxide is 20-25m/s, and the flow velocity of oxygen is 30-50m/s.
3. a kind of preparation method of Nd-Fe-B permanent magnet according to claim 1, it is characterised in that: set on the reactor
Be equipped with cyclic structure (1), be provided in cyclic structure (1) ferrous sulfate feed pipe (2), neodymium chloride feed pipe (3), sodium carbonate and
The mixture feed pipe (4) and oxygen feeding pipe (5) of sodium hydroxide, ferrous sulfate feed pipe (2), neodymium chloride feed pipe (3), carbon
The mixture feed pipe (4) and oxygen feeding pipe (5) of sour sodium and sodium hydroxide are evenly distributed on cyclic structure (1) and same
In plane, and perpendicular to cyclic structure (1), discharge port (6), ferrous sulfate feed pipe are provided on the axle center of cyclic structure (1)
(2), the mixture feed pipe (4) of neodymium chloride feed pipe (3), sodium carbonate and sodium hydroxide and oxygen feeding pipe (5) with discharging
Mouthful (6) connection, ferrous sulfate feed pipe (2), neodymium chloride feed pipe (3), sodium carbonate and sodium hydroxide mixture feed pipe (4)
Bore with oxygen feeding pipe (5) is 0.5-2mm, and the bore of discharge port (6) is 2-5mm, and the length of discharge port is 20-
100cm。
4. a kind of preparation method of Nd-Fe-B permanent magnet according to claim 1, it is characterised in that: the step (2) is poly-
The mass fraction of ethylene glycol solution is sulfuric acid alum in the mixed solution of 0.01-0.02%, ferrous sulfate and sulfuric acid alum and chromium sulfate
Molar ratio with chromium sulfate is 50-60:0.7-0.8:1.0-1.2, and the concentration of urea liquid is 2-3mol/l, urea liquid and sulphur
The mass ratio of the mixed solution of sour alum and chromium sulfate is 1:0.5-0.6.
5. a kind of preparation method of Nd-Fe-B permanent magnet according to claim 1, it is characterised in that: in the step (3)
The mass ratio of cladding material is 0.3-0.35:0.8-1.1 in sodium borohydride and step (2), is passed through the quality of hydrogen as cladding material matter
0.1-0.2 times of amount.
6. a kind of preparation method of Nd-Fe-B permanent magnet according to claim 1, it is characterised in that: in the step (4)
The mass ratio of paraffin and organic solvent is 1:1-2, and the organic solvent is thiacyclohexane, sample and paraffin and organic solvent after washing
The mass ratio of the solution of composition is 3-5:1, and the mass fraction > 98% of sulfuric acid in the concentrated sulfuric acid, the concentration of potassium phosphate,monobasic is 0.1-
0.22mol/l。
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| CN110202324B (en) * | 2019-06-05 | 2021-03-12 | 浙江鑫盛永磁科技有限公司 | Process for manufacturing neodymium-iron-boron magnet |
| CN113838656B (en) * | 2020-06-23 | 2024-04-19 | 和也健康科技有限公司 | Preparation method of flexible bonding NdFeB magnet, product and application thereof |
| CN113827867B (en) * | 2020-06-23 | 2024-04-16 | 和也健康科技有限公司 | Physiotherapy bed with flexible bonding neodymium-iron-boron magnet |
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