CN107492432A - 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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- CN107492432A CN107492432A CN201710694538.0A CN201710694538A CN107492432A CN 107492432 A CN107492432 A CN 107492432A CN 201710694538 A CN201710694538 A CN 201710694538A CN 107492432 A CN107492432 A CN 107492432A
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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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- Manufacturing Cores, Coils, And Magnets (AREA)
Abstract
The invention discloses a kind of preparation method of Nd-Fe-B permanent magnet, belong to permanent magnet preparing technical field.It includes the preparation of neodymium iron co-precipitation；The homogeneous cladding of alum and chromium；The reduction of sodium borohydride and plus boron, high pressure hydrogen reduction aftershaping and sintering；The passivation of sulfuric acid and potassium phosphate,monobasic.A kind of preparation method of Nd-Fe-B permanent magnet of the present invention, cost is low, efficiency high, and 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 method of Nd-Fe-B permanent magnet, belong to permanent magnet preparing technical field.
Background technology
Neodymium iron boron, be briefly a kind of magnet, and our magnet for usually seeing except that, its excellent magnetic
Can and be referred to as " magnetic king ".
Contain substantial amounts of rear earth element nd, iron and boron in neodymium iron boron, its characteristic is hard and crisp.Because surface is easily oxidized corruption
Erosion, neodymium iron boron must carry out surface coated treatment.Surface chemistry passivation is one of good solution method.Neodymium iron boron is as rare earth
The a kind of of permanent-magnet material has high magnetic energy product and coercivity, while Nd-Fe-B permanent magnet material is existed the advantages of high-energy-density
It is applied widely in modern industry and electronic technology, so that the equipment such as instrument and meter, electroacoustic motor, magnetic separation magnetization is small
Type, lightweight, slimming are possibly realized.The advantages of neodymium iron boron is cost-effective, has good mechanical property；Weak point exists
Low in operating temperature, temperature characterisitic is poor, and is easy to dusting corrosion, it is necessary to by adjusting its chemical composition and taking surface treatment side
Method is allowed to be improved, and can be only achieved the requirement of practical application.
Its conventional technological process：Dispensing → melting ingot/gets rid of band → powder → die mould → sintering tempering → magnetic detection processed
→ mill processing → pin cuts processing → plating → finished product, and wherein dispensing is basis, and sintering tempering is crucial.
But because 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.
The content of the invention
In view of this, the invention provides a kind of preparation method of Nd-Fe-B permanent magnet, cost is low, efficiency high, 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 present invention, it comprises the following steps：
(1) mixture of ferrous sulfate, neodymium chloride, sodium carbonate and sodium hydroxide is configured to solution, be respectively put into
In the container of sealing, then conveyed outward using compressed gas as power, while be mixed together and added in reactor with oxygen, reaction
Temperature is 50-55 DEG C, and second residence time 5-10 of material in the reactor, course of reaction maintains pH1.5-2.0, after obtaining reaction
Slurry.
(2) will be washed after slurries filtration, according to mass ratio 1 after washing:5 add 15-20mg/l CoCl2Solution, then
Add polyethylene glycol and be dispersed with stirring 30-35min, the mixed solution with Sulphuric acid alum and chromium sulfate, urea liquid is added, in 120-
125 DEG C of 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, reacts 2-3 at 25-35 DEG C
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 into paraffin with the solution of organic solvent composition, being 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
Outside, then by compressing and sintering, the mixed solution that the material after sintering is formed in the concentrated sulfuric acid and potassium phosphate,monobasic
The middle immersion 30-50 seconds, temperature during immersion is 5-15 DEG C, in then being eluted with 5-15 DEG C of sodium bicarbonate solution and being to wash water
Property, produce.
The ferrous sulfate, neodymium chloride, sodium carbonate and the mixture of sodium hydroxide, the mol ratio of oxygen are 6.8-6.9:
0.9-1.0：7-12：18-20, the mol ratio of the sodium carbonate and sodium hydroxide is 3:1-1.2, when adding reactor, sulfuric acid
Ferrous iron solution, neodymium chloride solution, the flow velocity of mixture solution of sodium carbonate and sodium hydroxide are 20-25m/s, and the flow velocity of oxygen is
30-50m/s。
Cyclic structure is provided with the reactor, ferrous sulfate feed pipe, neodymium chloride charging are provided with 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 at grade, and
Perpendicular to cyclic structure, discharging opening, ferrous sulfate feed pipe, neodymium chloride feed pipe, carbonic acid are provided with the axle center of cyclic structure
Sodium connects with the mixture feed pipe of sodium hydroxide with oxygen feeding Guan Junyu discharging openings, and ferrous sulfate feed pipe, neodymium chloride enter
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 discharging opening
For 2-5mm, the length of discharging opening 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 mol ratio of sulfuric acid alum and chromium sulfate is 50-60 in the mixed solution of chromium:0.7-0.8:1.0-1.2 the concentration of urea liquid is
2-3mol/l, urea liquid are 1 with the mass ratio of sulfuric acid alum and the mixed solution of chromium sulfate:0.5-0.6.
The mass ratio of sodium borohydride and cladding material in step (2) is 0.3-0.35 in the step (3)：0.8-1.1, it is passed through
The quality of hydrogen expects 0.1-0.2 times of quality for cladding.
The mass ratio of paraffin and organic solvent is 1 in the step (4):1-2, the organic solvent are thiacyclohexane, washing
The mass ratio of sample afterwards and paraffin and the solution of organic solvent composition 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, up to 100-
120nm, reaction efficiency is high, using urea homogeneous coprecipitation sulfuric acid alum and chromium sulfate, it is possible to achieve the uniform cladding of alum and chromium, add
Enter cobalt ions as activator, reduce cost, while improve the consistency of cladding, while the micro addition of cobalt, do not influence
The performance of neodymium iron boron, using high pressure hydrogen reduction, the primary particle of reduction neodymium iron boron can be refined, while alum and chromium can be realized
Uniformly cladding and fine and close growth.Using oxidation of the neodymium iron boron in sintering process can be avoided by the way of adding wax, reduce simultaneously
The airborne dust of neodymium iron boron, the loss of neodymium iron boron is reduced, oxide-film and phosphorus can be realized in the concentrated sulfuric acid and potassium phosphate,monobasic mixed liquor
Change the dual layer passivation of film, it is simple to operate.
(2) by refining the primary particle of 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 improves corrosion resistance plus oxide-film and the dual layer passivation of phosphating coat.
(3) reduce while add boron using sodium borohydride, it is possible to achieve the addition of the other boron of molecular level, more uniformly,
The performance of neodymium iron boron is more preferable.
Brief description of the drawings
The invention will be further described with reference to the accompanying drawings and examples.
Fig. 1 is the structural representation of reactor of the present invention.
Fig. 2 is the top view of reactor of the present invention.
Embodiment
Below with reference to accompanying 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, it comprises the following steps：
(1) mixture of ferrous sulfate, neodymium chloride, sodium carbonate and sodium hydroxide is configured to solution, be respectively put into
In the container of sealing, then conveyed outward using compressed gas as power, while be mixed together and added in reactor with oxygen, reaction
Temperature is 50-55 DEG C, and second residence time 5-10 of material in the reactor, course of reaction maintains pH1.5-2.0, after obtaining reaction
Slurry.
(2) will be washed after slurries filtration, according to mass ratio 1 after washing:5 add 15-20mg/l CoCl2Solution, then
Add polyethylene glycol and be dispersed with stirring 30-35min, the mixed solution with Sulphuric acid alum and chromium sulfate, urea liquid is added, in 120-
125 DEG C of 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, reacts 2-3 at 25-35 DEG C
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 into paraffin with the solution of organic solvent composition, being 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
Outside, then by compressing and sintering, the mixed solution that the material after sintering is formed in the concentrated sulfuric acid and potassium phosphate,monobasic
The middle immersion 30-50 seconds, temperature during immersion is 5-15 DEG C, in then being eluted with 5-15 DEG C of sodium bicarbonate solution and being to wash water
Property, produce.
The ferrous sulfate, neodymium chloride, sodium carbonate and the mixture of sodium hydroxide, the mol ratio of oxygen are 6.8-6.9:
0.9-1.0：7-12：18-20, the mol ratio of the sodium carbonate and sodium hydroxide is 3:1-1.2, when adding reactor, sulfuric acid
Ferrous iron solution, neodymium chloride solution, the flow velocity of mixture solution of sodium carbonate and sodium hydroxide are 20-25m/s, and the flow velocity of oxygen is
30-50m/s。
Cyclic structure 1 is provided with the reactor, ferrous sulfate feed pipe 2 is provided with cyclic structure 1, neodymium chloride enters
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 discharging opening 6 is provided with cyclic structure 1, the axle center of cyclic structure 1, ferrous sulfate feed pipe 2, chlorination
The mixture feed pipe 4 and oxygen feeding pipe 5 of neodymium feed pipe 3, sodium carbonate and sodium hydroxide connect with discharging opening 6, and sulfuric acid is sub-
Iron feed pipe 2, neodymium chloride feed pipe 3, sodium carbonate and the mixture feed pipe 4 of sodium hydroxide and the bore of oxygen feeding pipe 5
For 0.5-2mm, the bore of discharging opening 6 is 2-5mm, and the length of discharging opening 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 mol ratio of sulfuric acid alum and chromium sulfate is 50-60 in the mixed solution of chromium:0.7-0.8:1.0-1.2 the concentration of urea liquid is
2-3mol/l, urea liquid are 1 with the mass ratio of sulfuric acid alum and the mixed solution of chromium sulfate:0.5-0.6.
The mass ratio of sodium borohydride and cladding material in step (2) is 0.3-0.35 in the step (3)：0.8-1.1, it is passed through
The quality of hydrogen expects 0.1-0.2 times of quality for cladding.
The mass ratio of paraffin and organic solvent is 1 in the step (4):1-2, the organic solvent are thiacyclohexane, washing
The mass ratio of sample afterwards and paraffin and the solution of organic solvent composition 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, it comprises the following steps：
(1) mixture of ferrous sulfate, neodymium chloride, sodium carbonate and sodium hydroxide is configured to solution, be respectively put into
In the container of sealing, then conveyed outward using compressed gas as power, while be mixed together and added in reactor with oxygen, reaction
Temperature is 52 DEG C, and 8 seconds residence times in the reactor of material, course of reaction maintains pH1.65, obtains reacted slurry.
(2) will be washed after slurries filtration, according to mass ratio 1 after washing:5 add 17.5mg/l CoCl2Solution, Ran Houjia
Enter polyethylene glycol and be dispersed with stirring 32.5min, the mixed solution with Sulphuric acid alum and chromium sulfate, add urea liquid, it is anti-at 122 DEG C
Answer 2.3 hours, filtration washing, obtain cladding material.
(3) will cladding material plus pure water pulp after, pH be 5.95 time addition sodium borohydrides, 29 DEG C reaction 2.3 hours, so
It 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 into paraffin with the solution of organic solvent composition, being 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
Face, then by compressing and sintering, by the material after sintering in the mixed solution that the concentrated sulfuric acid and potassium phosphate,monobasic form
Immersion 39 seconds, temperature during immersion are 12.5 DEG C, and it is neutral then to be eluted with 12.5 DEG C of sodium bicarbonate solution to wash water, i.e.,
.
The ferrous sulfate, neodymium chloride, sodium carbonate and the mixture of sodium hydroxide, the mol ratio of oxygen are 6.85:0.95：
8：19, the mol ratio of the sodium carbonate and sodium hydroxide is 3:1.1, when adding reactor, copperas 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 with the reactor, ferrous sulfate feed pipe 2 is provided with cyclic structure 1, neodymium chloride enters
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 discharging opening 6 is provided with cyclic structure 1, the axle center of cyclic structure 1, ferrous sulfate feed pipe 2, chlorination
The mixture feed pipe 4 and oxygen feeding pipe 5 of neodymium feed pipe 3, sodium carbonate and sodium hydroxide connect with discharging opening 6, and sulfuric acid is sub-
Iron feed pipe 2, neodymium chloride feed pipe 3, sodium carbonate and the mixture feed pipe 4 of sodium hydroxide and the bore of oxygen feeding pipe 5
For 0.95mm, the bore of discharging opening 6 is 3.5mm, and the length of discharging opening is 80cm.
The mass fraction of step (2) polyglycol solution is 0.015%, ferrous sulfate and sulfuric acid alum and chromium sulfate
The mol ratio of sulfuric acid alum and chromium sulfate is 55 in mixed solution:0.78:1.15, the concentration of urea liquid is 2.1mol/l, urea
Solution is 1 with the mass ratio of sulfuric acid alum and the mixed solution of chromium sulfate:0.56.
The mass ratio of sodium borohydride and cladding material in step (2) is 0.33 in the step (3)：0.95, it is passed through hydrogen
Quality expects 0.15 times of quality for cladding.
The mass ratio of paraffin and organic solvent is 1 in the step (4):1.1, the organic solvent is thiacyclohexane, washing
The mass ratio of sample afterwards and paraffin and the solution of organic solvent composition 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, it comprises the following steps：
(1) mixture of ferrous sulfate, neodymium chloride, sodium carbonate and sodium hydroxide is configured to solution, be respectively put into
In the container of sealing, then conveyed outward using compressed gas as power, while be mixed together and added in reactor with oxygen, reaction
Temperature is 52 DEG C, and 8 seconds residence times in the reactor of material, course of reaction maintains pH1.65, obtains reacted slurry.
(2) will be washed after slurries filtration, according to mass ratio 1 after washing:5 add 18.5mg/l CoCl2Solution, Ran Houjia
Enter polyethylene glycol and be dispersed with stirring 32min, the mixed solution with Sulphuric acid alum and chromium sulfate, add urea liquid, in 122 DEG C of reactions
2.3 hours, filtration washing, obtain cladding material.
(3) will cladding material plus pure water pulp after, pH be 5.95 time addition sodium borohydrides, 29 DEG C reaction 2.3 hours, so
It 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 into paraffin with the solution of organic solvent composition, being 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
Face, then by compressing and sintering, by the material after sintering in the mixed solution that the concentrated sulfuric acid and potassium phosphate,monobasic form
Immersion 36 seconds, temperature during immersion are 12.5 DEG C, and it is neutral then to be eluted with 12.5 DEG C of sodium bicarbonate solution to wash water, i.e.,
.
The ferrous sulfate, neodymium chloride, sodium carbonate and the mixture of sodium hydroxide, the mol ratio of oxygen are 6.85:0.95：
8：18, the mol ratio of the sodium carbonate and sodium hydroxide is 3:1.1, when adding reactor, copperas 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 with the reactor, ferrous sulfate feed pipe 2 is provided with cyclic structure 1, neodymium chloride enters
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 discharging opening 6 is provided with cyclic structure 1, the axle center of cyclic structure 1, ferrous sulfate feed pipe 2, chlorination
The mixture feed pipe 4 and oxygen feeding pipe 5 of neodymium feed pipe 3, sodium carbonate and sodium hydroxide connect with discharging opening 6, and sulfuric acid is sub-
Iron feed pipe 2, neodymium chloride feed pipe 3, sodium carbonate and the mixture feed pipe 4 of sodium hydroxide and the bore of oxygen feeding pipe 5
For 0.95mm, the bore of discharging opening 6 is 3.5mm, and the length of discharging opening is 90cm.
The mass fraction of step (2) polyglycol solution is 0.015%, ferrous sulfate and sulfuric acid alum and chromium sulfate
The mol ratio of sulfuric acid alum and chromium sulfate is 55 in mixed solution：0.78:1.12, the concentration of urea liquid is 2.1mol/l, urea
Solution is 1 with the mass ratio of sulfuric acid alum and the mixed solution of chromium sulfate:0.56.
The mass ratio of sodium borohydride and cladding material in step (2) is 0.33 in the step (3)：0.95, it is passed through hydrogen
Quality expects 0.15 times of quality for cladding.
The mass ratio of paraffin and organic solvent is 1 in the step (4):1.11, the organic solvent is thiacyclohexane, washing
The mass ratio of sample afterwards and paraffin and the solution of organic solvent composition 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, it comprises the following steps：
(1) mixture of ferrous sulfate, neodymium chloride, sodium carbonate and sodium hydroxide is configured to solution, be respectively put into
In the container of sealing, then conveyed outward using compressed gas as power, while be mixed together and added in reactor with oxygen, reaction
Temperature is 52 DEG C, and 8 seconds residence times in the reactor of material, course of reaction maintains pH1.6, obtains reacted slurry.
(2) will be washed after slurries filtration, according to mass ratio 1 after washing:5 add 16.5mg/l CoCl2Solution, Ran Houjia
Enter polyethylene glycol and be dispersed with stirring 31min, the mixed solution with Sulphuric acid alum and chromium sulfate, add urea liquid, in 123 DEG C of reactions
2.3 hours, filtration washing, obtain cladding material.
(3) will cladding material plus pure water pulp after, pH be 5.95 time addition sodium borohydrides, 29 DEG C reaction 2.3 hours, so
It 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 into paraffin with the solution of organic solvent composition, being 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
Face, then by compressing and sintering, by the material after sintering in the mixed solution that the concentrated sulfuric acid and potassium phosphate,monobasic form
Immersion 36 seconds, temperature during immersion are 13.5 DEG C, and it is neutral then to be eluted with 12.5 DEG C of sodium bicarbonate solution to wash water, i.e.,
.
The ferrous sulfate, neodymium chloride, sodium carbonate and the mixture of sodium hydroxide, the mol ratio of oxygen are 6.85:0.95：
8：18, the mol ratio of the sodium carbonate and sodium hydroxide is 3:1.1, when adding reactor, copperas 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 with the reactor, ferrous sulfate feed pipe 2 is provided with cyclic structure 1, neodymium chloride enters
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 discharging opening 6 is provided with cyclic structure 1, the axle center of cyclic structure 1, ferrous sulfate feed pipe 2, chlorination
The mixture feed pipe 4 and oxygen feeding pipe 5 of neodymium feed pipe 3, sodium carbonate and sodium hydroxide connect with discharging opening 6, and sulfuric acid is sub-
Iron feed pipe 2, neodymium chloride feed pipe 3, sodium carbonate and the mixture feed pipe 4 of sodium hydroxide and the bore of oxygen feeding pipe 5
For 0.95mm, the bore of discharging opening 6 is 3.5mm, and the length of discharging opening is 90cm.
The mass fraction of step (2) polyglycol solution is 0.015%, ferrous sulfate and sulfuric acid alum and chromium sulfate
The mol ratio of sulfuric acid alum and chromium sulfate is 55 in mixed solution：0.76:1.12, the concentration of urea liquid is 2.1mol/l, urea
Solution is 1 with the mass ratio of sulfuric acid alum and the mixed solution of chromium sulfate:0.56.
The mass ratio of sodium borohydride and cladding material in step (2) is 0.33 in the step (3)：0.95, it is passed through hydrogen
Quality expects 0.15 times of quality for cladding.
The mass ratio of paraffin and organic solvent is 1 in the step (4):1.11, the organic solvent is thiacyclohexane, washing
The mass ratio of sample afterwards and paraffin and the solution of organic solvent composition 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 illustrate, the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although with reference to compared with
The present invention is described in detail good embodiment, it will be understood by those within the art that, can be to the skill of the present invention
Art scheme is modified or equivalent substitution, and without departing from the objective and scope of technical solution of the present invention, it all should cover at this
Among the right of invention.
Claims (6)
1. a kind of preparation method of Nd-Fe-B permanent magnet, it is characterised in that comprise 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 add reactor in, reaction temperature
For 50-55 DEG C, second residence time 5-10 in the reactor, course of reaction maintains pH1.5-2.0, obtains reacted slurry.
(2) washed after the slurries filtration for obtaining step (1), according to mass ratio 1 after washing:5 add 15-20mg/l CoCl2It is molten
Liquid, then add polyethylene glycol and be dispersed with stirring 30-35min, the mixed solution with Sulphuric acid alum and chromium sulfate, it is molten to add urea
Liquid, reacted 2-2.5 hours at 120-125 DEG C, filtration washing, obtain cladding material.
(3) after the cladding material that step (2) obtains being added into 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 hours, are then 210-230 DEG C in temperature, pressure is to be passed through hydrogen under 5-7Mpa, reacts 3-3.5 hours, simultaneously
Mixing speed is 300-350r/min, then filtration washing.
(4) sample after step (3) is washed adds paraffin with the solution of organic solvent composition, being 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 by compressing and sintering, the mixing that the material after sintering is formed in the concentrated sulfuric acid and potassium phosphate,monobasic
The 30-50 seconds are soaked in solution, temperature during immersion is 5-15 DEG C, is then eluted with 5-15 DEG C of sodium bicarbonate solution to wash water and is
Neutrality, produce.
A kind of 2. 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, the mol ratio of oxygen are 6.8-6.9:0.9-1.0：7-12：18-20, it is described
The mol ratio of sodium carbonate and sodium hydroxide is 3:1-1.2, when adding reactor, copperas 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.
A kind of 3. 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 with 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 in cyclic structure (1) and same
In plane, and discharging opening (6), ferrous sulfate feed pipe are provided with cyclic structure (1), 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), the mixture feed pipe (4) of sodium carbonate and sodium hydroxide
Bore with oxygen feeding pipe (5) is 0.5-2mm, and the bore of discharging opening (6) is 2-5mm, and the length of discharging opening is 20-
100cm。
A kind of 4. 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 0.01-0.02%, ferrous sulfate and sulfuric acid alum in the mixed solution of sulfuric acid alum and chromium sulfate
Mol ratio with chromium sulfate is 50-60:0.7-0.8:1.0-1.2, 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.
A kind of 5. 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 sodium borohydride and cladding material in step (2) is 0.3-0.35：0.8-1.1, the quality for being passed through hydrogen are cladding material matter
0.1-0.2 times of amount.
A kind of 6. 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, the organic solvent are thiacyclohexane, the sample after washing and paraffin and organic solvent
The mass ratio of the solution of composition 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。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110202324A (en) * | 2019-06-05 | 2019-09-06 | 浙江鑫盛永磁科技有限公司 | Ndfeb magnet manufacturing process |
| CN113827867A (en) * | 2020-06-23 | 2021-12-24 | 和也健康科技有限公司 | Physiotherapy bed with flexible bonding neodymium iron boron magnetism body |
| CN113838656A (en) * | 2020-06-23 | 2021-12-24 | 和也健康科技有限公司 | Preparation method of flexible bonded neodymium-iron-boron magnet and product and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110202324A (en) * | 2019-06-05 | 2019-09-06 | 浙江鑫盛永磁科技有限公司 | Ndfeb magnet manufacturing process |
| CN113827867A (en) * | 2020-06-23 | 2021-12-24 | 和也健康科技有限公司 | Physiotherapy bed with flexible bonding neodymium iron boron magnetism body |
| CN113838656A (en) * | 2020-06-23 | 2021-12-24 | 和也健康科技有限公司 | Preparation method of flexible bonded neodymium-iron-boron magnet and 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 |
| 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 |
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