CN103736995A - Method for preparing composite magnet from surface tinned magnetic powder through hot embossing - Google Patents
Method for preparing composite magnet from surface tinned magnetic powder through hot embossing Download PDFInfo
- Publication number
- CN103736995A CN103736995A CN201410031912.5A CN201410031912A CN103736995A CN 103736995 A CN103736995 A CN 103736995A CN 201410031912 A CN201410031912 A CN 201410031912A CN 103736995 A CN103736995 A CN 103736995A
- Authority
- CN
- China
- Prior art keywords
- magnetic
- tin
- magnet
- solution
- hot moulding
- 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.)
- Granted
Links
Landscapes
- Manufacturing Cores, Coils, And Magnets (AREA)
- Chemically Coating (AREA)
Abstract
The invention discloses a method for preparing a composite magnet from a surface tinned magnetic powder through hot embossing. The method includes the steps of covering the magnetic powder unoiled and activated previously with a low-melting-point metal tin coating by an electroplating technique or chemical plating technique method in a plating tank in which an alkaline plating solution containing tin ions is held, and then obtaining the magnetic powder covered with the tin coating through separating, washing and purifying, and preparing the tinned magnetic power into the composite magnet by the way of hot embossing. Due to the adoption of the method, the problems of easy aging, easy shrinking, easy water absorption and poor organic solvent resisting capability of the composite magnetic with a thermosetting resin as an adhesive are effectively improved; the tin coating is enabled to cover the particles of the magnetic powder in advance; the distribution uniformity of the magnetic powder and the metal tin is effectively promoted; when the composite magnet is prepared, the proportion of the adhesive in the magnetic is effectively reduced while the same mechanical strength in the prior art is achieved; and therefore, the magnetic performance of the composite magnet is improved.
Description
Technical field
The invention belongs to powder surface treatment technology and magnet preparing technical field, relate in particular to a kind ofly at magnetic coating surface low-melting-point metal tin, and the method for built-up magnet is prepared in mold pressing at a certain temperature.
Background technology
After mold pressing is prepared built-up magnet and is referred to the macromolecular compounds such as magnetic and binding agent, coupling agent are evenly mixed, the adhesive composite magnet preparing by compression-moulding methods.In recent years, the product such as electronic apparatus, instrument develops rapidly to microminiaturized, complex-shapedization, this is also for the performance of magnetic material and processing are had higher requirement, adhesive composite magnet is simple because have production technology, product size precision is high, high conformity, the plurality of advantages such as the form free degree is large, so adhesive composite magnet acquisition is extensively carried out.
Current, mold pressing prepare built-up magnet binding agent used normally thermosetting resin as epoxy resin, phenolic resins etc.Yet, also there are some shortcomings in this class binding agent, such as: the low use field of having limited magnet of mechanical strength, the lower serviceability temperature that limits magnet of softening temperature, easy aging service life of limiting magnet, easily shrinkage affects the accuracy to size of magnet, and easily water suction causes magnetic oxidation and corrosion, organic solvent-resistant ability etc.In order to change thermosetting resin as the inferior position of binding agent, there is researcher to propose improvement method, as patent, CN200810052612.X proposes a kind of Agglutinate neodymium-iron-boron magnet and preparation method thereof, it is characterized in that adding in NdFeB magnetic powder and thermosetting resin mixed process nano silicon as reinforcing agent to improve the intensity of built-up magnet.Patent CN201210458728.X proposes a kind of high magnetic mechanical strength bonding neodymium iron boron permanent magnet and preparation method thereof, also mentions and in NdFeB magnetic powder and epoxy resin, adds metallocene macromolecule ferromagnetic powder and stainless steel powder to improve mechanical strength and magnetic property.Above-mentioned these methods still be take thermosetting resin as main binding agent; and utilize the low-melting-point metals such as tin can effectively solve as binding agent the inferior position that thermosetting resin brings as binding agent; meanwhile, the electric conductivity of metal adhesive is also for the follow-up surface of built-up magnet is carried out the anti-corrosion treatment such as electrophoretic painting or electro-cladding and provided convenience.As the method for patent CN03115679.7 proposition binding neodymium-iron-borou rare-earth permanent magnetic material by metal tin, adopt metallic tin powder and make metallic tin binding Nd-Fe-B permanent magnetic material through the NdFeB magnetic powder of passivation method of reducing parcel, to improve the high-temperature oxidation resistance of magnetic, the neodymium iron boron binding magnet of excellent.But the method that this patent is mentioned is to suppress the also technique of hot briquetting after metal powder with low melting point and magnetic are simply mixed, inevitably there is metallic tin powder and magnetic skewness, problem that glass putty proportion is too high in this, causes the low even phenomenon of waste of utilization ratio of binding agent; In addition, the magnetic property of magnet reduces along with the decline of magnetic proportion, thereby too much binding agent also can affect magnetic property.
Summary of the invention
For solving the inferior position that in prior art, thermosetting resin exists as binding agent, and low-melting-point metal tin powder is as binding agent skewness and the excessive deficiency of proportion around magnetic, the invention provides a kind of method of preparing built-up magnet with the magnetic hot moulding of electroplating surfaces with tin, the ductility that the method has greatly been improved binding agent distributing homogeneity, reduced binding agent percentage composition, fully applied metal tin is good and non-oxidizability, raising built-up magnet combination property.
The present invention reaches the technical scheme that goal of the invention adopts to be: in the coating bath filling containing the alkali plating solution of tin ion, by electroless plating technology or electroplating technology, make the coated upper metallic tin coating in magnetic surface of crossing through oil removing activation processing, then through separated, washing purification step, obtain being coated with the magnetic of tin coating, and by the mode of hot moulding, magnetic is made to built-up magnet.
Described magnetic is one of following: 1. neodymium iron boron (Nd-Fe-B), 2. samarium iron nitrogen (Sm-Fe-N).
For making metallic tin in the coated with uniform of magnetic, the bottom land of coating bath applies vicissitudinous magnetic field, and magnetic can be rolled in the process of the coated tin in surface, and the magnetic field of variation can be realized by the ferromagnetic sintered NdFeB magnetic stripe that moves around.
Described magnetic oil removing, activation pre-treatment step are: (1) oil removing: with containing 5 g/L～20 g/L NaOH, 5 g/L～20 g/L Na
2cO
3, 5 g/L～10 g/L Na
3pO
4, 0.008 g/L～0.05g/L neopelex the thorough oil removing of solution; (2) surface active: activate with dilute acid soln, the hydrochloric acid solution that conventional mass concentration is 3% activates.
Described purification procedures is: magnetic is taken out with distilled water and cleaned, then with absolute ethyl alcohol, do solvent extraction dehydration, vacuum drying under 20 ℃～100 ℃ conditions, obtains finally by hydrogen reducing the magnetic that surface is coated with metallic tin coating.
The described alkali plating solution containing tin ion comprises the electric depositing solution that employing electroplating technology is used and adopts electroless plating technology chemical plating stannum solution used.Wherein electric depositing solution formula is:
Sodium stannate (Na
2snO
3) 75 g/L～90 g/L
NaOH (NaOH) 5 g/L～12 g/L
Described electroplating technology method is carried out as follows:
(1) get the pre-treatment that magnetic carries out oil removing in 5 minutes, clear water rinsing, 1 minute surface active, clear water rinsing process;
(2) by formula, measure Na
2snO
3and NaOH, water dissolving is mixed with electric depositing solution and packs in groove, corrosion resistant plate is positioned over bottom land and is connected as negative electrode with the negative pole of constant voltage dc source by lead-in wire, and metal sheet tin hangs in electric depositing solution as anode, and ratio of cathodic to anodic area is 1: 2～4;
(3) magnetic after processing is put into groove, through precipitating after a while, magnetic is laid on corrosion resistant plate, at 60 ℃～85 ℃, cathode-current density 1 A/dm
2～1.5 A/dm
2condition under electrodeposit metals tin layer, in electrodeposition process, at bottom land, apply vicissitudinous magnetic field;
(4) after deposition 1-30min, close D.C. regulated power supply, magnetic is taken out and cleaned with distilled water, then with absolute ethyl alcohol, do solvent extraction dehydration, use permanent magnet from solvent, to take out magnetic, put into vacuum drying chamber vacuum drying under 60 ℃ of conditions, finally by hydrogen reducing, can obtain the magnetic that surface is coated with metallic tin layer.
Described electroless plating technology deposit tin comprises disproportionated reaction chemical plating stannum and reduction reaction chemical plating stannum.Wherein the solution formula of disproportionated reaction chemical plating stannum is:
Stannous chloride (SnCl
22H
2o) 50 g/L～100 g/L
NaOH (NaOH) 100 g/L～200 g/L
Sodium hypophosphite (NaH
2pO
2h
2o) 50 g/L～100 g/L
Natrium citricum (Na
2c
6h
5o
72H
2o) 150 g/L～210 g/L
Control 70～80 ℃ of solution temperatures
The solution formula of reduction reaction chemical plating stannum is:
Stannous chloride (SnCl
22H
2o) 10 g/L～80 g/L
Natrium citricum (Na
2c
6h
5o
72H
2o) 80 g/L～120 g/L
Disodium ethylene diamine tetraacetate (Na
2eDTA) 10 g/L～50 g/L
Aminotriacetic acid N (CH
2cOOH)
320 g/L～50 g/L
Reducing agent titanium trichloride (TiCl
3) 3 g/L～15 g/L
With ammoniacal liquor, adjust pH=9
Control 70～80 ℃ of solution temperatures
Described electroless plating technology method is carried out as follows:
(1) get the pre-treatment that magnetic carries out oil removing in 5 minutes, clear water rinsing, 1 minute surface active, clear water rinsing process;
(2) by solution formula separately, measure corresponding chemical reagent, water dissolves and is mixed with solution and packs in coating bath;
(3) magnetic after processing is put into groove, through precipitating after a while, magnetic is laid in bottom land, and temperature is 70 ℃～80 ℃, and magnetic applies vicissitudinous magnetic field at bottom land in the process of the coated tin in surface;
(4) after deposition 1-30min, magnetic is taken out with distilled water and cleaned, then with absolute ethyl alcohol, do solvent extraction dehydration, use permanent magnet from solvent, to take out magnetic, put into vacuum drying chamber vacuum drying under 60 ℃ of conditions, finally by hydrogen reducing, can obtain being coated with the magnetic of metallic tin layer.
The magnetic of the coated tin coating in surface is filled in mould, utilize forcing press to carry out hot moulding mold heated after uniform temperature, the condition of magnet hot moulding is: holding temperature is 200 ℃～300 ℃, and the pressure applying on mould is 20 ~ 60 KN/cm
2.
The beneficial effect that the method for built-up magnet is prepared in magnetic hot moulding with electroplating surfaces with tin of the present invention is mainly reflected in:
(1) on magnetic surface, be directly coated the metallic tin of low melting point, effectively promoted the distributing homogeneity of magnetic and metallic tin, when preparing built-up magnet, hot moulding improves the relative amount of magnetic, thereby improve magnetic property and the mechanical property of built-up magnet, also can improve the non-oxidizability of magnetic in hot moulding process simultaneously;
(2) utilize electroplating technology or electroless plating technology clad metal tin coating, technique is simple, and metallic tin thickness of coating can arbitrarily be controlled according to the time of metal deposition.
(3) according to the characteristic of magnetic polar repulsion, at the bottom land of coating bath, apply vicissitudinous magnetic field, can impel magnetic can roll in the process of metal deposition, prevent that magnetic can not be coated because of overlapping, or because of mechanical agitation broken.
(4) no matter electroplating solution or chemical plating solution, all adopt alkaline system, can prevent that like this magnetic from metal deposition process, chemical attack occurring for a long time.
The specific embodiment
Below in conjunction with specific embodiment, the present invention is described further, but method related in scheme and technical parameter can not be interpreted as to limitation of the present invention.
Embodiment 1: the coated tin layer of NdFeB magnetic powder electroplating technology deposition, and built-up magnet is prepared in hot moulding
Electroplating solution formula: Na
2snO
380g/L, NaOH 8g/L.
Technique is as follows: take respectively Na
2snO
340 g, NaOH 4g, water dissolves and is mixed with the electric depositing solution of 500 milliliters and packs in groove, contains solution tank and makes of lucite.Corrosion resistant plate is placed on bottom land and is connected as negative electrode with the negative pole of power supply by lead-in wire, and sheet tin is suspended in electric depositing solution as anode, and ratio of cathodic to anodic area is 1:2.Then the fast quenching NdFeB magnetic powder that takes the 50g trade mark and be MQP13-9 is through the pre-treatment of oil removing in 5 minutes, clear water rinsing, 1 minute surface active, clear water rinsing process, NdFeB magnetic powder after pre-treatment is put into galvanic deposition cell, through the magnet adsorption of bottom land, NdFeB magnetic powder is laid on corrosion resistant plate.At 65 ℃, 1.0A/dm
2condition under electro-deposition clad metal tin layer.In electrodeposition process, with sintered NdFeB permanent magnet iron, at bottom land, move, make NdFeB magnetic powder can paste corrosion resistant plate and constantly roll.After 50 minutes, close D.C. regulated power supply, take out and clean magnetic with distilled water, clean later with anhydrous ethanol solvent extraction dehydration, through suction filtration, put into vacuum drying chamber dry at 60 ℃, finally by hydrogen reducing, obtaining the NdFeB magnetic powder of the coated tin coating in surface, is 6.5% through energy dispersion type Xray fluorescence spectrometer (EDX-GP) test tin coating weight ratio content.The magnetic of the coated tin coating in surface is filled in mould, then mould is placed in to stove and is heated to 250 ℃, taking-up is placed in forcing press and carries out hot moulding, exerts pressure as 30KN/cm
2, pressurize 2min, then takes out mould room temperature cooling, and moves back mould and take out sample.The density of built-up magnet is 6.5g/cm after tested
3, magnet performance is Br 0.890T, Hcj 735 KA/m, (BH) m 121.2 KJ/m
3, compression strength is 91MPa.
Embodiment 2: the coated tin layer of NdFeB magnetic powder electroless plating technology deposition, and built-up magnet is prepared in hot moulding
Chemical plating solution formula: SnCl
22H
2o 80 g/L, NaOH 150g/L, NaH
2pO
2h
2o 90 g/L, Na
2c
6h
5o
72H
2o 200 g/L.
Technique is as follows: take respectively SnCl
22H
2o 40 g, NaOH 75 g, NaH
2pO
2h
2o 45 g, Na
2c
6h
5o
72H
2o 100 g.Water dissolves and is mixed with the chemical plating solution of 500 milliliters and packs in groove, contains solution tank and makes of lucite.Then the fast quenching NdFeB magnetic powder that takes the 40g trade mark and be MQP13-9 is through the pre-treatment of oil removing in 5 minutes, clear water rinsing, 1 minute surface active, clear water rinsing process, samarium iron nitrogen magnetic after pre-treatment is put into chemical plating solution, through the magnet adsorption of bottom land, on samarium iron nitrogen magnetic is laid at the bottom of electroless plating tank.Under the condition that control solution temperature is 75 ℃, deposit clad metal tin layer.After 30 minutes, take out magnetic and clean with distilled water, clean later with anhydrous ethanol solvent extraction dehydration, through suction filtration, put into vacuum drying chamber dry at 60 ℃, finally by hydrogen reducing, obtaining the samarium iron nitrogen magnetic of the coated tin coating in surface, is 7.8 % through energy dispersion type Xray fluorescence spectrometer (EDX-GP) test tin coating weight ratio content.The magnetic of the coated tin coating in surface is filled in mould, then mould is placed in to stove and is heated to 250 ℃, taking-up is placed in forcing press and carries out hot moulding, exerts pressure as 30KN/cm
2, pressurize 2min, then takes out mould room temperature cooling, and moves back mould and take out sample.The density of built-up magnet is 6.7g/cm after tested
3, magnet performance is Br 0.840T, Hcj 716 KA/m, (BH) m 118.7 KJ/m
3, compression strength is 94 MPa.
Embodiment 3: the coated tin layer of samarium iron nitrogen magnetic electroless plating technology deposition, and built-up magnet is prepared in hot moulding
Chemical plating solution formula: SnCl
22H
2o 75 g/L, NaOH 150g/L, NaH
2pO
2h
2o 80 g/L, Na
2c
6h
5o
72H
2o 190 g/L.
Technique is as follows: take respectively SnCl
22H
2o 37.5 g, NaOH 75 g, NaH
2pO
2h
2o 40 g, Na
2c
6h
5o
72H
2o 95 g.Water dissolves and is mixed with the chemical plating solution of 500 milliliters and packs in groove, contains solution tank and makes of lucite.Then take 35g samarium iron nitrogen magnetic through the pre-treatment of oil removing in 5 minutes, clear water rinsing, 1 minute surface active, clear water rinsing process, samarium iron nitrogen magnetic after pre-treatment is put into chemical plating solution, through the magnet adsorption of bottom land, on samarium iron nitrogen magnetic is laid at the bottom of electroless plating tank.Under the condition that control solution temperature is 75 ℃, deposit clad metal tin layer.After 30 minutes, take out magnetic and clean with distilled water, clean later with anhydrous ethanol solvent extraction dehydration, through suction filtration, put into vacuum drying chamber dry at 60 ℃, finally by hydrogen reducing, obtaining the samarium iron nitrogen magnetic of the coated tin coating in surface, is 8.1 % through energy dispersion type Xray fluorescence spectrometer (EDX-GP) test tin coating weight ratio content.The magnetic of the coated tin coating in surface is filled in mould, then mould is placed in to stove and is heated to 250 ℃, taking-up is placed in forcing press and carries out hot moulding, exerts pressure as 30KN/cm
2, pressurize 2min, then takes out mould room temperature cooling, and moves back mould and take out sample.The density of built-up magnet is 6.6g/cm after tested
3, magnet performance is Br 0.780T, Hcj 1200 KA/m, (BH) m 150.2 KJ/m
3, compression strength is 96 MPa.
Embodiment 4: the coated tin layer of samarium iron nitrogen magnetic electroless plating technology deposition, and built-up magnet is prepared in hot moulding
Chemical plating solution formula: SnCl
22H
2o 60 g/L, Na
2c
6h
5o
72H
2o 100g/L, Na
2eDTA 30 g/L, N (CH
2cOOH)
335 g/L, TiCl
35 g/L.
Technique is as follows: take respectively SnCl
22H
2o 60 g/L, Na
2c
6h
5o
72H
2o 100g/L, Na
2eDTA 30 g/L, N (CH
2cOOH)
335 g/L, TiCl
35 g/L.Water dissolves and is mixed with the chemical plating solution of 500 milliliters and packs in groove, contains solution tank and makes of lucite.Then take 35g samarium iron nitrogen magnetic through the pre-treatment of oil removing in 5 minutes, clear water rinsing, 1 minute surface active, clear water rinsing process, samarium iron nitrogen magnetic after pre-treatment is put into chemical plating solution, through the magnet adsorption of bottom land, on samarium iron nitrogen magnetic is laid at the bottom of electroless plating tank.Under the condition that control solution temperature is 70 ℃, deposit clad metal tin layer.After 30 minutes, take out magnetic and clean with distilled water, clean later with anhydrous ethanol solvent extraction dehydration, through suction filtration, put into vacuum drying chamber dry at 60 ℃, finally by hydrogen reducing, obtaining the samarium iron nitrogen magnetic of the coated tin coating in surface, is 8.6 % through energy dispersion type Xray fluorescence spectrometer (EDX-GP) test tin coating weight ratio content.The magnetic of the coated tin coating in surface is filled in mould, then mould is placed in to stove and is heated to 250 ℃, taking-up is placed in forcing press and carries out hot moulding, exerts pressure as 30KN/cm
2, pressurize 2min, then takes out mould room temperature cooling, and moves back mould and take out sample.The density of built-up magnet is 6.8g/cm after tested
3, magnet performance is Br 0.740T, Hcj 1180KA/m, (BH) m 145.6 KJ/m
3, compression strength is 98 MPa.
Embodiment 5: the coated tin layer of NdFeB magnetic powder electroplating technology deposition, and built-up magnet is prepared in hot moulding
Electroplating solution formula: Na
2snO
375 g/L, NaOH 12 g/L.
Technique is as follows: take respectively Na
2snO
337.5 g, NaOH 6 g, water dissolves and is mixed with the electric depositing solution of 500 milliliters and packs in groove, contains solution tank and makes of lucite.Corrosion resistant plate is placed on bottom land and is connected as negative electrode with the negative pole of power supply by lead-in wire, and sheet tin is suspended in electric depositing solution as anode, and ratio of cathodic to anodic area is 1:4.Then the fast quenching NdFeB magnetic powder that takes the 50g trade mark and be MQP13-9 is through the pre-treatment of oil removing in 5 minutes, clear water rinsing, 1 minute surface active, clear water rinsing process, NdFeB magnetic powder after pre-treatment is put into galvanic deposition cell, through the magnet adsorption of bottom land, NdFeB magnetic powder is laid on corrosion resistant plate.At 85 ℃, 1.5 A/dm
2condition under electro-deposition clad metal tin layer.In electrodeposition process, with sintered NdFeB permanent magnet iron, at bottom land, move, make NdFeB magnetic powder can paste corrosion resistant plate and constantly roll.After 30 minutes, close D.C. regulated power supply, take out and clean magnetic with distilled water, clean later with anhydrous ethanol solvent extraction dehydration, through suction filtration, put into vacuum drying chamber and be dried at 60 ℃, finally by hydrogen reducing, obtain the NdFeB magnetic powder of the coated tin coating in surface.The magnetic of the coated tin coating in surface is filled in mould, then mould is placed in to stove and is heated to 200 ℃, taking-up is placed in forcing press and carries out hot moulding, exerts pressure as 20KN/cm
2, pressurize 2min, then takes out mould room temperature cooling, and moves back mould and take out sample.
Embodiment 6: the coated tin layer of NdFeB magnetic powder electroplating technology deposition, and built-up magnet is prepared in hot moulding
Electroplating solution formula: Na
2snO
390g/L, NaOH 5g/L.
Technique is as follows: take respectively Na
2snO
345 g, NaOH 2.5g, water dissolves and is mixed with the electric depositing solution of 500 milliliters and packs in groove, contains solution tank and makes of lucite.Corrosion resistant plate is placed on bottom land and is connected as negative electrode with the negative pole of power supply by lead-in wire, and sheet tin is suspended in electric depositing solution as anode, and ratio of cathodic to anodic area is 1:2.Then the fast quenching NdFeB magnetic powder that takes the 50g trade mark and be MQP13-9 is through the pre-treatment of oil removing in 5 minutes, clear water rinsing, 1 minute surface active, clear water rinsing process, NdFeB magnetic powder after pre-treatment is put into galvanic deposition cell, through the magnet adsorption of bottom land, NdFeB magnetic powder is laid on corrosion resistant plate.At 60 ℃, 1.0A/dm
2condition under electro-deposition clad metal tin layer.In electrodeposition process, with sintered NdFeB permanent magnet iron, at bottom land, move, make NdFeB magnetic powder can paste corrosion resistant plate and constantly roll.After 1 minute, close D.C. regulated power supply, take out and clean magnetic with distilled water, clean later with anhydrous ethanol solvent extraction dehydration, through suction filtration, put into vacuum drying chamber and be dried at 60 ℃, finally by hydrogen reducing, obtain the NdFeB magnetic powder of the coated tin coating in surface.The magnetic of the coated tin coating in surface is filled in mould, then mould is placed in to stove and is heated to 250 ℃, taking-up is placed in forcing press and carries out hot moulding, exerts pressure as 60KN/cm
2, pressurize 2min, then takes out mould room temperature cooling, and moves back mould and take out sample.
Embodiment 7: the coated tin layer of NdFeB magnetic powder electroless plating technology deposition, and built-up magnet is prepared in hot moulding
Chemical plating solution formula: SnCl
22H
2o 50 g/L, NaOH 100g/L, NaH
2pO
2h
2o 50 g/L, Na
2c
6h
5o
72H
2o 150 g/L.
Technique is as follows: take respectively SnCl
22H
2o 25 g, NaOH 50 g, NaH
2pO
2h
2o 25 g, Na
2c
6h
5o
72H
2o 75 g.Water dissolves and is mixed with the chemical plating solution of 500 milliliters and packs in groove, contains solution tank and makes of lucite.Then the fast quenching NdFeB magnetic powder that takes the 40g trade mark and be MQP13-9 is through the pre-treatment of oil removing in 5 minutes, clear water rinsing, 1 minute surface active, clear water rinsing process, samarium iron nitrogen magnetic after pre-treatment is put into chemical plating solution, through the magnet adsorption of bottom land, on samarium iron nitrogen magnetic is laid at the bottom of electroless plating tank.Under the condition that control solution temperature is 70 ℃, deposit clad metal tin layer.After 30 minutes, take out magnetic and with distilled water cleaning, clean later and extract dehydration with anhydrous ethanol solvent, through suction filtration, put into vacuum drying chamber and be dried at 60 ℃, finally by hydrogen reducing, obtain the samarium iron nitrogen magnetic of the coated tin coating in surface.The magnetic of the coated tin coating in surface is filled in mould, then mould is placed in to stove and is heated to 200 ℃, taking-up is placed in forcing press and carries out hot moulding, exerts pressure as 60KN/cm
2, pressurize 2min, then takes out mould room temperature cooling, and moves back mould and take out sample.
Embodiment 8: the coated tin layer of NdFeB magnetic powder electroless plating technology deposition, and built-up magnet is prepared in hot moulding
Chemical plating solution formula: SnCl
22H
2o 100 g/L, NaOH 200g/L, NaH
2pO
2h
2o 100 g/L, Na
2c
6h
5o
72H
2o 210 g/L.
Technique is as follows: take respectively SnCl
22H
2o 50 g, NaOH 100 g, NaH
2pO
2h
2o 50 g, Na
2c
6h
5o
72H
2o 105 g.Water dissolves and is mixed with the chemical plating solution of 500 milliliters and packs in groove, contains solution tank and makes of lucite.Then the fast quenching NdFeB magnetic powder that takes the 40g trade mark and be MQP13-9 is through the pre-treatment of oil removing in 5 minutes, clear water rinsing, 1 minute surface active, clear water rinsing process, samarium iron nitrogen magnetic after pre-treatment is put into chemical plating solution, through the magnet adsorption of bottom land, on samarium iron nitrogen magnetic is laid at the bottom of electroless plating tank.Under the condition that control solution temperature is 80 ℃, deposit clad metal tin layer.After 1 minute, take out magnetic and with distilled water cleaning, clean later and extract dehydration with anhydrous ethanol solvent, through suction filtration, put into vacuum drying chamber and be dried at 60 ℃, finally by hydrogen reducing, obtain the samarium iron nitrogen magnetic of the coated tin coating in surface.The magnetic of the coated tin coating in surface is filled in mould, then mould is placed in to stove and is heated to 300 ℃, taking-up is placed in forcing press and carries out hot moulding, exerts pressure as 20KN/cm
2, pressurize 2min, then takes out mould room temperature cooling, and moves back mould and take out sample.
Embodiment 9: the coated tin layer of samarium iron nitrogen magnetic electroless plating technology deposition, and built-up magnet is prepared in hot moulding
Chemical plating solution formula: SnCl
22H
2o 10 g/L, Na
2c
6h
5o
72H
2o 80g/L, Na
2eDTA 10 g/L, N (CH
2cOOH)
320 g/L, TiCl
33 g/L.
Technique is as follows: take respectively SnCl
22H
2o 5 g, Na
2c
6h
5o
72H
2o 40g, Na
2eDTA 5 g, N (CH
2cOOH)
310 g, TiCl
31.5 g.Water dissolves and is mixed with the chemical plating solution of 500 milliliters and packs in groove, contains solution tank and makes of lucite.Then take 35g samarium iron nitrogen magnetic through the pre-treatment of oil removing in 5 minutes, clear water rinsing, 1 minute surface active, clear water rinsing process, samarium iron nitrogen magnetic after pre-treatment is put into chemical plating solution, through the magnet adsorption of bottom land, on samarium iron nitrogen magnetic is laid at the bottom of electroless plating tank.Under the condition that control solution temperature is 70 ℃, deposit clad metal tin layer.After 30 minutes, take out magnetic and with distilled water cleaning, clean later and extract dehydration with anhydrous ethanol solvent, through suction filtration, put into vacuum drying chamber and be dried at 60 ℃, finally by hydrogen reducing, obtain the samarium iron nitrogen magnetic of the coated tin coating in surface.The magnetic of the coated tin coating in surface is filled in mould, then mould is placed in to stove and is heated to 200 ℃, taking-up is placed in forcing press and carries out hot moulding, exerts pressure as 60KN/cm
2, pressurize 2min, then takes out mould room temperature cooling, and moves back mould and take out sample.
Embodiment 10: the coated tin layer of samarium iron nitrogen magnetic electroless plating technology deposition, and built-up magnet is prepared in hot moulding
Chemical plating solution formula: SnCl
22H
2o 80 g/L, Na
2c
6h
5o
72H
2o 120g/L, Na
2eDTA 50 g/L, N (CH
2cOOH)
350 g/L, TiCl
315 g/L.
Technique is as follows: take respectively SnCl
22H
2o 40g, Na
2c
6h
5o
72H
2o 60g, Na
2eDTA 25 g, N (CH
2cOOH)
325 g, TiCl
37.5 g.Water dissolves and is mixed with the chemical plating solution of 500 milliliters and packs in groove, contains solution tank and makes of lucite.Then take 35g samarium iron nitrogen magnetic through the pre-treatment of oil removing in 5 minutes, clear water rinsing, 1 minute surface active, clear water rinsing process, samarium iron nitrogen magnetic after pre-treatment is put into chemical plating solution, through the magnet adsorption of bottom land, on samarium iron nitrogen magnetic is laid at the bottom of electroless plating tank.Under the condition that control solution temperature is 70 ℃, deposit clad metal tin layer.After 1 minute, take out magnetic and with distilled water cleaning, clean later and extract dehydration with anhydrous ethanol solvent, through suction filtration, put into vacuum drying chamber and be dried at 60 ℃, finally by hydrogen reducing, obtain the samarium iron nitrogen magnetic of the coated tin coating in surface.The magnetic of the coated tin coating in surface is filled in mould, then mould is placed in to stove and is heated to 300 ℃, taking-up is placed in forcing press and carries out hot moulding, exerts pressure as 20KN/cm
2, pressurize 2min, then takes out mould room temperature cooling, and moves back mould and take out sample.
Above-described embodiment is used for the present invention that explains, rather than limits the invention, and in the protection domain of spirit of the present invention and claim, any modification and change that the present invention is made, all fall into protection scope of the present invention.
Claims (9)
1. a method of preparing built-up magnet with the magnetic hot moulding of electroplating surfaces with tin, it is characterized in that, described method is: in the coating bath filling containing the alkali plating solution of tin ion, method by electroplating technology or electroless plating technology makes the coated upper metallic tin layer in magnetic surface of crossing through oil removing activation processing, then through separated, washing purification step, obtain the magnetic that surface is coated with tin coating, and by the mode of hot moulding, the magnetic after coated is prepared into built-up magnet.
2. the method for preparing built-up magnet with the magnetic hot moulding of electroplating surfaces with tin as claimed in claim 1, is characterized in that, the bottom land of described coating bath applies vicissitudinous magnetic field, and the magnetic field of variation can be realized by the sintered NdFeB magnetic stripe that moves around.
3. the method for preparing built-up magnet with the magnetic hot moulding of electroplating surfaces with tin as claimed in claim 1, is characterized in that described magnetic is neodymium iron boron or samarium iron nitrogen.
4. the method for preparing built-up magnet with the magnetic hot moulding of electroplating surfaces with tin as claimed in claim 1, is characterized in that described oil removing activation processing process are specially:
(1) oil removing: with containing 5g/L～20g/L NaOH, 5g/L～20g/L Na
2cO
3, 5g/L～10g/L Na
3pO
4, 0.008g/L～0.05g/L neopelex the thorough oil removing of the aqueous solution;
(2) surface active: activate with dilute acid soln, the hydrochloric acid solution that conventional mass concentration is 3% activates.
5. the method for preparing built-up magnet with the magnetic hot moulding of electroplating surfaces with tin as claimed in claim 1, it is characterized in that described separation, washing purification step are specially: magnetic is taken out and cleaned with distilled water, then with absolute ethyl alcohol, do solvent extraction dehydration, vacuum drying under 20 ℃～100 ℃ conditions, obtains finally by hydrogen reducing the magnetic that surface is coated with metallic tin coating.
6. the method for preparing built-up magnet with the magnetic hot moulding of electroplating surfaces with tin as claimed in claim 1, is characterized in that, the described alkali plating solution containing tin ion comprises electroplating solution and the electroless plating technology chemical plating solution used that electroplating technology is used.
7. as claim 1 and the method for preparing built-up magnet with the magnetic hot moulding of electroplating surfaces with tin claimed in claim 6, it is characterized in that, the described basic plating solution formula containing tin ion is:
Sodium stannate (Na
2snO
3) 75 g/L～90 g/L,
NaOH (NaOH) 5 g/L～12 g/L,
Solvent is water;
Described electroplating technology method is carried out as follows:
(1) get the pre-treatment that magnetic carries out oil removing in 5 minutes, clear water rinsing, 1 minute surface active, clear water rinsing process;
(2) by formula, measure Na
2snO
3and NaOH, water dissolving is mixed with electric depositing solution and packs in groove, corrosion resistant plate is positioned over bottom land and is connected as negative electrode with the negative pole of constant voltage dc source by lead-in wire, and metal sheet tin hangs in electric depositing solution as anode, and ratio of cathodic to anodic area is 1: 2～4;
(3) magnetic after step 1 processing is put into groove, precipitation, magnetic is laid on corrosion resistant plate, at 60 ℃～85 ℃, cathode-current density 1 A/dm
2～1.5 A/dm
2condition under electrodeposit metals tin layer, in electrodeposition process, at bottom land, apply vicissitudinous magnetic field;
(4) after deposition 1-30min, close D.C. regulated power supply, magnetic is taken out and cleaned with distilled water, then with absolute ethyl alcohol, do solvent extraction dehydration, use permanent magnet from solvent, to take out magnetic, put into vacuum drying chamber vacuum drying under 60 ℃ of conditions, finally by hydrogen reducing, can obtain the magnetic that surface is coated with metallic tin layer.
8. as claim 1 and the method for preparing built-up magnet with the magnetic hot moulding of electroplating surfaces with tin claimed in claim 6, it is characterized in that, the described alkali electroless plating liquor containing tin ion comprises disproportionated reaction chemical plating stannum solution and reduction reaction chemical plating stannum solution, wherein, the solution formula of disproportionated reaction chemical plating stannum is:
Stannous chloride (SnCl
22H
2o) 50 g/L～100 g/L,
NaOH (NaOH) 100 g/L～200 g/L,
Sodium hypophosphite (NaH
2pO
2h
2o) 50 g/L～100 g/L,
Natrium citricum (Na
2c
6h
5o
72H
2o) 150 g/L～210 g/L,
Solvent is water,
Control 70～80 ℃ of solution temperatures;
The solution formula of reduction reaction chemical plating stannum is:
Stannous chloride (SnCl
22H
2o) 10 g/L～80 g/L,
Natrium citricum (Na
2c
6h
5o
72H
2o) 80 g/L～120 g/L,
Disodium ethylene diamine tetraacetate (Na
2eDTA) 10 g/L～50 g/L,
Aminotriacetic acid N (CH
2cOOH)
320 g/L～50 g/L,
Reducing agent titanium trichloride (TiCl
3) 3 g/L～15 g/L,
Solvent is water,
With ammoniacal liquor, adjust pH=9,
Control 70～80 ℃ of solution temperatures;
Described electroless plating technology method is carried out as follows:
(1) get the pre-treatment that magnetic carries out oil removing in 5 minutes, clear water rinsing, 1 minute surface active, clear water rinsing process;
(2) by solution formula separately, measure corresponding chemical reagent, water dissolves and is mixed with solution and packs in coating bath;
(3) magnetic after step 1 processing is put into groove, precipitation, magnetic is laid in bottom land, and temperature is 70 ℃～80 ℃, and magnetic applies vicissitudinous magnetic field at bottom land in the process of the coated tin in surface;
(4) after deposition 1-30min, magnetic is taken out with distilled water and cleaned, then with absolute ethyl alcohol, do solvent extraction dehydration, use permanent magnet from solvent, to take out magnetic, put into vacuum drying chamber vacuum drying under 60 ℃ of conditions, finally by hydrogen reducing, can obtain being coated with the magnetic of metallic tin layer.
9. the method for preparing built-up magnet with the magnetic hot moulding of electroplating surfaces with tin as claimed in claim 1, it is characterized in that, the method of described hot moulding is specially: the magnetic of the coated tin coating in surface is filled in mould, by after mold heated to 200 ℃～300 ℃, utilize forcing press to carry out hot moulding, the pressure applying on mould is 20 ~ 60 KN/cm
2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410031912.5A CN103736995B (en) | 2014-01-24 | 2014-01-24 | The magnetic heat-die compaction of a kind of electroplating surfaces with tin is for the method for built-up magnet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410031912.5A CN103736995B (en) | 2014-01-24 | 2014-01-24 | The magnetic heat-die compaction of a kind of electroplating surfaces with tin is for the method for built-up magnet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103736995A true CN103736995A (en) | 2014-04-23 |
| CN103736995B CN103736995B (en) | 2016-07-06 |
Family
ID=50494102
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410031912.5A Active CN103736995B (en) | 2014-01-24 | 2014-01-24 | The magnetic heat-die compaction of a kind of electroplating surfaces with tin is for the method for built-up magnet |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103736995B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106654298A (en) * | 2016-11-11 | 2017-05-10 | 攀钢集团攀枝花钢铁研究院有限公司 | Negative electrode material with Sn-containing electrocatalyst of vanadium redox flow battery and preparation method for negative electrode material |
| CN118098808A (en) * | 2024-04-09 | 2024-05-28 | 安徽大学 | Low-temperature metal bonding preparation method of high-performance samarium-iron-nitrogen composite magnet |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02232902A (en) * | 1989-03-07 | 1990-09-14 | Ishihara Sangyo Kaisha Ltd | Manufacture of magnetic metal powder for magnetic recording |
| CN1438659A (en) * | 2003-03-06 | 2003-08-27 | 上海交通大学 | Method of binding neodymium-iron-borou rare-earth permanent magnetic material by metal tin |
| CN1690255A (en) * | 2004-04-21 | 2005-11-02 | 浙江工业大学 | Method for preparing neodymium-iron-boron magnetic powder coated with metal layer by electrochemical deposition |
| CN1901322A (en) * | 2006-07-24 | 2007-01-24 | 广州金南磁塑有限公司 | Moulding press composite adhesive magnetic tile and its preparing method |
| CN101157779A (en) * | 2007-09-27 | 2008-04-09 | 广州金南磁塑有限公司 | Novel rubber magnet and method for making same |
| CN101325108A (en) * | 2008-04-03 | 2008-12-17 | 麦格昆磁（天津）有限公司 | Agglutinate neodymium-iron-boron magnet and preparation method thereof |
| CN103406541A (en) * | 2013-08-17 | 2013-11-27 | 张家港保税区金企鹅贸易有限公司 | Method for coating metal material on surface of non-metallic material |
-
2014
- 2014-01-24 CN CN201410031912.5A patent/CN103736995B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02232902A (en) * | 1989-03-07 | 1990-09-14 | Ishihara Sangyo Kaisha Ltd | Manufacture of magnetic metal powder for magnetic recording |
| CN1438659A (en) * | 2003-03-06 | 2003-08-27 | 上海交通大学 | Method of binding neodymium-iron-borou rare-earth permanent magnetic material by metal tin |
| CN1690255A (en) * | 2004-04-21 | 2005-11-02 | 浙江工业大学 | Method for preparing neodymium-iron-boron magnetic powder coated with metal layer by electrochemical deposition |
| CN1901322A (en) * | 2006-07-24 | 2007-01-24 | 广州金南磁塑有限公司 | Moulding press composite adhesive magnetic tile and its preparing method |
| CN101157779A (en) * | 2007-09-27 | 2008-04-09 | 广州金南磁塑有限公司 | Novel rubber magnet and method for making same |
| CN101325108A (en) * | 2008-04-03 | 2008-12-17 | 麦格昆磁（天津）有限公司 | Agglutinate neodymium-iron-boron magnet and preparation method thereof |
| CN103406541A (en) * | 2013-08-17 | 2013-11-27 | 张家港保税区金企鹅贸易有限公司 | Method for coating metal material on surface of non-metallic material |
Non-Patent Citations (2)
| Title |
|---|
| 姜晓霞等: "《化学镀理论及实践》", 31 December 2000, 国防工业出版社 * |
| 赵杰等: "化学镀锡反应历程的研究进展", 《电镀与涂饰》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106654298A (en) * | 2016-11-11 | 2017-05-10 | 攀钢集团攀枝花钢铁研究院有限公司 | Negative electrode material with Sn-containing electrocatalyst of vanadium redox flow battery and preparation method for negative electrode material |
| CN118098808A (en) * | 2024-04-09 | 2024-05-28 | 安徽大学 | Low-temperature metal bonding preparation method of high-performance samarium-iron-nitrogen composite magnet |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103736995B (en) | 2016-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101665965B (en) | Electroplating device of copper plating of graphite powder and technique | |
| CN102776547B (en) | Method for preparing rare earth permanent magnetic material | |
| CN102108511A (en) | Electroplating and chemical plating composite protecting process for NdFeB permanent magnet and NdFeB permanent magnet with composite protective layer | |
| CN103668369A (en) | Electric plating method capable of improving anti-corrosion performance of metal element | |
| CN101575723A (en) | Anode oxidation method | |
| CN104109885A (en) | Weak-alkalinity pyrophosphate solution and technology for electroplating bright tin | |
| CN100414003C (en) | Method for preparing neodymium-iron-boron magnetic powder coated with metal layer by electrochemical deposition | |
| KR101096531B1 (en) | Manufacturing process of high conductive carbon fibers by metal electroplating method | |
| CN103014787A (en) | Copper-electroplating solution and electroplating process thereof | |
| CN103219523B (en) | Negative plate of lead-acid storage battery and preparation method of negative plate | |
| CN104480499A (en) | Nickel electroplating method adopting ionic liquid | |
| CN103736995A (en) | Method for preparing composite magnet from surface tinned magnetic powder through hot embossing | |
| CN104790000A (en) | Manganese-bismuth-iron-phosphor permanent magnetic alloy plating solution and preparation method thereof | |
| CN101550570A (en) | Non-cyanide electro cooper plating bath of EDTA system and use method thereof | |
| CN204174295U (en) | Be configured with bianode Acidic zinc-nickel alloy electroplanting device | |
| CN205874527U (en) | A anchor clamps for sintered ndfeb magnet surface physical vapor deposition | |
| CN100484666C (en) | Nd-Fe-B magnet inorganic sealing hole adhesion and cathode electrophoresis composite surface protection technique | |
| CN104388992B (en) | The method of Al Zn alloy layers is co-deposited in ion liquid system | |
| CN105274582B (en) | Trivalent chromium plating method based on eutectic solvent | |
| CN104928734B (en) | The method of steel and iron parts cyanideless electro-plating tin bronze | |
| CN104099658A (en) | Auxiliary anode for use in acid zinc-nickel alloy electroplating | |
| CN107083559B (en) | The method of high-quality nickel is chemically electrolysed out in nickel-plating waste water | |
| CN100570013C (en) | A kind of gold plating liquid and gold plating method thereof | |
| CN102828209B (en) | Preparation method of alkaline zincate zinc-plating brightener | |
| CN105420768A (en) | Method for adjusting bivalent tin ion concentration |
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 |