CN101894648B - Bonded ferrite magnetic powder, preparation method thereof and bonded permanent magnet - Google Patents
Bonded ferrite magnetic powder, preparation method thereof and bonded permanent magnet Download PDFInfo
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Abstract
The invention discloses bonded ferrite magnetic powder, a preparation method thereof and a bonded permanent magnet, which belong to the technical field of magnetic materials. The magnetic powder comprises a principal phase with the molecular formula of (M1-xLax)O.n(Fe1-yZnyBiz)2O3, wherein M denotes at least one of strontium and barium; x, y, z and n denote mole ratios, and meets x=2mn(y+z); x is 0.01 to 0.40; z/y is more than or equal to 0.01 and less than or equal to 0.3; n is 5.50 to 6.40; and m is 0.90 to 1.10. The invention also provides the preparation method for the bonded ferrite magnetic powder, and the bonded permanent magnet. Bismuth oxide is added in certain proportion in a material mixing process, and chloride is added in certain proportion as a fluxing agent in the material mixing process, so the reduction of pre-burning temperature and control over the growth of crystal grains and the grain size distribution of the magnetic powder are realized, and the prepared magnetic powder is endowed with the advantages of high Br and high jHc.
Description
Technical field
The present invention relates to technical field of magnetic materials, particularly relate to a kind of bonded ferrite magnetic powder and preparation method thereof and bonded permanent magnet.
Background technology
Therefore permanent-magnet ferrite material comprises barium ferrite and two kinds of materials of strontium ferrite, because it has raw material wide material sources and advantages such as low price, cost performance height, is used widely in industry such as motor, automobile, household electrical appliances and sphere of life.So far permanent-magnet ferrite material is still the highest permanent magnetic material of output.
According to the difference of molding mode, the permanent-magnet ferrite magnet mainly is divided into ferrite sintered body and bonded ferrite.Ferrite sintered body need pass through operations such as double sintering and mill processing; Bonded ferrite then is that magnetic and binding agent are composited.Compare ferrite sintered body, bonded ferrite has advantages such as dimensional accuracy height, plasticity be good, but also has shortcomings such as magnetic property is lower.
The magnetic property index of bonded ferrite product mainly contains residual magnetic flux density Br, HCJ jHc, maximum magnetic energy product (BH) max etc.Along with the miniaturization development of electronic devices and components, the volume of magnet is more and more littler, so the performance of magnet must develop towards high performance.The magnetic property of bonded ferrite is by the magnetic filling rate in the magnet, the magnetic degree of orientation and the decision of magnetic intrinsic the subject of knowledge and the object of knowledge; The influencing factor of residual magnetic flux density is shown below; Br ∝ 4 π Ms*Nc*X; Wherein 4 π Ms represent the saturation magnetization of magnetic, and Nc represents the degree of orientation of magnetic, and X represents the filling rate of magnetic.Obtain the product of high remanent magnetism, just must use the magnetic of high Ms, improve the filling rate of magnetic and improve the degree of orientation of magnetic as far as possible as far as possible.
Under traditional process conditions, the magnetic powder material of high Ms is generally through adopting high-purity raw, strict control production technology and magnetic powder particle shape to obtain.The high fill-ratio of magnetic and high-orientation then with pressed density, dispersiveness and the particle size distribution of magnetic, and the processing technology of magnet is relevant.Through the control of production technology, can the filling rate of magnetic be brought up to 92wt.%, but be difficult to improve again at present, because will worsen the shaping characteristic and the degree of orientation that reduces magnetic of magnet along with the raising of magnetic filling rate.At present, through the improvement of traditional preparation process technology, the performance that further improve bonded permanent magnet has become very difficult.
Publication number is that the patent application of CN1256785A discloses the ferrite powder that a kind of binding magnet is used, and has basic magnetic lead-acid type crystalline texture, has following basic composition: (A
1-xR
x) On [(Fe
1-yM
y)
2O
3], wherein A is strontium and/or barium; R is at least a element that comprises in the rare earth element of Y, must contain La, and M is at least a element that is selected among Co, Ma, Ni, the Zn; X, y and n satisfy respectively: 0.01≤X≤0.4, [x/ (2.6n)]≤y≤[x/ (1.6n)] and 5≤n≤6.As showing that when the particle mean size of magnetic reached 1.65 μ m, its jHc had only 24800e (197kA/m) among the embodiment 5 of this patent application.Because described bonded permanent magnet of this patent application and magnetic roller adopt injection molding, this molding mode requires magnetic must have big particle mean size (＞1.5 μ m) and higher pressed density (＞3.25g/cm
3), otherwise be difficult to obtain high fill-ratio and high Br.The inventor discovers, by the ferrite powder of the disclosed preparation method's preparation of this patent application, is difficult to obtain simultaneously to have high Br and high jHc (Br >=285mT for example, jHc >=210kA/m).The inventor furthers investigate discovery, and the interpolation of independent La and Zn element substitutes, and along with Zn substitutes the increase of measuring, magnetic jHc is on a declining curve.
Summary of the invention
The purpose of the embodiment of the invention provides a kind of bonded ferrite magnetic powder and preparation method thereof and bonded permanent magnet; Compare with common Sr/Ba ferrite; Under same magnetic filling rate, have higher Br and higher jHc, can guarantee performance with the bonded magnet of this magnetic powders.
The objective of the invention is to realize through following technical proposals:
The embodiment of the invention provides a kind of bonded ferrite magnetic powder, and this magnetic has the principal phase of following molecular formula:
(M
1-xLa
x)O·n(Fe
1-yZn
yBi
z)
2O
3
Wherein, M represents at least a element in strontium, the barium; X, y, z, n representes mol ratio, satisfies x=2mn (y+z), and x=0.01～0.40,0.01≤z/y≤0.3, n=5.50～6.40, m=0.90～1.10.
The embodiment of the invention also provides a kind of preparation method of bonded ferrite magnetic powder, may further comprise the steps:
(1) any in the compound of the compound of employing strontium or barium and the oxide of iron, the oxide of lanthanum, the oxide of zinc and the oxide of bismuth are raw material, and each raw material all adopts Powdered, according to molecular formula (M
1-xLa
x) On (Fe
1-yZn
yBi
z)
2O
3Batching, M represents at least one middle element in strontium, the barium; X in the molecular formula, y, z, n representes mol ratio, satisfies x=2mn (y+z), and x=0.01～0.40,0.01≤z/y≤0.3, n=5.50～6.40, m=0.90～1.10;
(2) each raw material of weighing in proportion is with obtaining compound after each raw materials mix;
(3) when said compound is carried out batch mixing, in compound, add chloride as flux;
(4) under 1050～1280 ℃ temperature, carry out pre-burning, obtain the pre-burning material;
(5) said pre-burning material is carried out coarse crushing and obtain meal;
(6) to the further fine grinding of said meal, obtain fine powder;
(7) under 850～980 ℃ of temperature, said fine powder is annealed, the lattice defect through annealing in process elimination magnetic promptly obtains bonded ferrite magnetic powder after the annealing in process.
The embodiment of the invention further provides a kind of bonded permanent magnet, and this bonded permanent magnet is the bonded permanent magnet that raw material is processed with moulding process for adopting above-mentioned magnetic.
Technical scheme through the embodiment of the invention provides can be found out; In the embodiment of the invention through adding a certain proportion of bismuth oxide in the batch mixing process; And add a certain proportion of chloride as flux in the batch mixing process; Thereby realized reducing growing up and control the granularity of magnet powder distribution of calcined temperature, control crystal grain, made the magnetic that makes have the advantage of high Br and high jHc.Therefore, the present invention has molecular formula (M
1-xLa
x) On (Fe
1-yZn
yBi
z)
2O
3Ferromagnetic oxide powder, compare with common Sr/Ba ferrite, under same magnetic filling rate, have higher Br and higher jHc; And the bonded permanent magnet of processing thus.
Embodiment
The embodiment of the invention provides a kind of bonded ferrite magnetic powder, is used to prepare the magnetic of making bonded permanent magnet, makes the bonded permanent magnet that makes have higher Br and higher jHc, and this magnetic has the principal phase of following molecular formula:
(M
1-xLa
x)O·n(Fe
1-yZn
yBi
z)
2O
3
Wherein, M represents at least a element in strontium, the barium; X, y, z, n representes mol ratio, satisfies x=2mn (y+z), and x=0.01～0.40,0.01≤z/y≤0.3, n=5.50～6.40, m=0.90～1.10.
The pressed density of above-mentioned magnetic is 2.8～3.7g/cm
3, the particle mean size of magnetic is 0.9～3.0 μ m.
Above-mentioned bonded ferrite magnetic powder prepares through following step, specifically comprises:
(1) any in the compound of the compound of employing strontium or barium and the oxide of iron, the oxide of lanthanum, the oxide of zinc and the oxide of bismuth are raw material, and each raw material all adopts Powdered shape, according to molecular formula (M
1-xLa
x) On (Fe
1-yZn
yBi
z)
2O
3Batching, M represents at least one middle element in strontium, the barium; X in the molecular formula, y, z, n representes mol ratio, satisfies x=2mn (y+z), and x=0.01～0.40,0.01≤z/y≤0.3, n=5.50～6.40, m=0.90～1.10;
In the above-mentioned steps (1), the compound of said strontium adopts any in strontium carbonate, the strontium sulfate; The compound of said barium adopts any in brium carbonate, the barium sulfate;
The oxide of said iron adopts any in iron scale powder, iron oxide red powder or the fine ore, and its purity range is 97.5～99.5%;
The oxide raw material of said lanthanum adopts the oxide of pulverous lanthanum, as: lanthana, its purity range are technical grade;
The oxide raw material of said zinc adopts the oxide of pulverous zinc, as: zinc oxide, its purity range are technical grade;
The oxide raw material of said bismuth adopts the oxide of pulverous bismuth, as: bismuth oxide, its purity range are technical grade.
(2) each raw material of weighing in proportion is with obtaining compound after each raw materials mix;
(3) when said compound is carried out batch mixing, add a certain proportion of chloride as flux, muriatic consumption accounts for 0.1～10% of compound total weight; Chloride can adopt sodium chloride nacl, potassium chloride (KCl), magnesium chloride Mg Cl
2, calcium chloride CaCl
2, strontium oxide strontia SrCl
2, barium chloride BaCl
2In any or any several kinds;
(4) under 1050～1280 ℃ temperature, carry out pre-burning, the pre-burning time is X～Y hour, obtains the pre-burning material;
(5) said pre-burning material is carried out coarse crushing and obtain meal;
(6) to the further fine grinding of said meal, obtain fine powder;
(7) under 850～980 ℃ of temperature, said fine powder is carried out annealing in process, the lattice defect through annealing in process elimination magnetic promptly obtains bonded ferrite magnetic powder after the annealing in process.
In the above-mentioned preparation magnetic method; Associating element substitution through La, Zn and Bi; Add a certain proportion of chloride simultaneously as flux, can effectively control the distribution of sizes with crystal grain of growing up of crystal grain, thereby effectively control the jHc and the grain shape of improving magnetic of magnetic.
Utilize above-mentioned magnetic to be prepared into bonded permanent magnet, specifically can adopt any moulding process in injection moulding, extrusion molding, the calendering formation through moulding process.
The inventor discovers, adds a certain proportion of bismuth oxide in the batch mixing process, can play the effect that suppresses grain growth, effectively improves granularity of magnet powder and distributes, and makes the size distribution narrow of magnetic, therefore improves the jHc of magnetic.Muriatic fusing point generally between 850～980 ℃, is lower than calcined temperature of the present invention.The inventor discovers simultaneously; When adding certain bismuth oxide; In the batch mixing process, in compound, add a certain proportion of chloride as flux; Can effectively reduce calcined temperature, avoid growing up unusually of crystal grain, well improve growing up and grain shape of granularity of magnet powder distribution and control crystal grain.
The inventor finds, through adding a certain proportion of La, Zn element, adds a certain proportion of Bi element simultaneously, and in batch mixing, adds a certain proportion of chloride as flux, can obtain to possess the magnetic of high Br and high jHc.
Below in conjunction with specific embodiment the present invention is described further.
Embodiment 1
Present embodiment provides a kind of preparation method of bonded ferrite magnetic powder, specifically comprises:
Weighing 1420g purity is that 98.5% iron oxide red, 205g purity are that 98% strontium carbonate, 24.4g purity are that 98.5% lanthana, 12 gram purity are 99.2% zinc oxide; 2 gram purity are 99.5% bismuth oxide; Adopt wet ball mill to mix 3 hours, oven dry obtains compound then;
The above-mentioned compound of weighing 1500 grams, and add 15 gram strontium chloride SrCl
2,, obtain the pre-burning material 1200 ℃ of following sintering 1 hour; It is slightly broken to adopt dry ball that the pre-burning pellet is carried out, and adopts wet ball mill to carry out fine grinding 3 hours subsequently, obtains the fine grinding powder after the oven dry;
The fine grinding powder was annealed 1 hour down at 940 ℃, and carry out dispersion treatment, obtain the magnetic that bonds.
Utilize above-mentioned bonding magnetic to utilize moulding process can prepare bonded magnet, specific as follows:
Weighing 1000g bonding magnetic, the relevant auxiliary agent with 20g of 110g nylon 6 (silane coupler and lubricant TAF) after mixing, adopt double screw extruder to carry out mixing and granulation, and melting temperature is 270 ℃;
Pellet is added vertical type injection molding machine, be heated to 250 ℃, injection moulding obtains the cylinder magnetic patch of Φ 10 * 10mm, and process of injection molding applies the magnetic field intensity of 10000Oe.
Can adopt the B-H tester to measure the magnetic hysteresis loop of the above-mentioned cylinder magnetic patch that makes, obtain magnet performance.
Can adopt WLP-202 model particle mean size tester that the above-mentioned bonded magnetic powder that makes is averaged granularity Detection.
Embodiment 2
Present embodiment provides a kind of preparation method of bonded ferrite magnetic powder, specifically comprises:
Weighing 1405g purity is that 98.5% iron oxide red, 183g purity are that 98% strontium carbonate, 49g purity are that 98.5% lanthana, 23.9 gram purity are 99.2% zinc oxide; 3.5 being 99.5% bismuth oxide, gram purity adopt wet ball mill to mix 3 hours; Oven dry obtains compound then;
The above-mentioned compound that makes of weighing 1500 gram, and add 15 gram strontium chlorides 1200 ℃ of following sintering 1 hour, obtains the pre-burning material.It is slightly broken to adopt dry ball that the pre-burning pellet is carried out, and adopts wet ball mill to carry out fine grinding 3 hours subsequently, obtains the fine grinding powder after the oven dry;
The fine grinding powder was annealed 1 hour down at 940 ℃, and carry out dispersion treatment, obtain the magnetic that bonds.
Utilize above-mentioned bonding magnetic to utilize moulding process can prepare bonded magnet, specific as follows:
Weighing 1000g bonding magnetic, the relevant auxiliary agent with 20g of 110g nylon 6 (silane coupler and lubricant TAF) after mixing, adopt double screw extruder to carry out mixing and granulation, and melting temperature is 270 ℃;
Pellet is added vertical type injection molding machine, be heated to 250 ℃, injection moulding obtains the cylinder magnetic patch of Φ 10 * 10mm, and process of injection molding applies the magnetic field intensity of 10000Oe.
Can adopt the B-H tester to measure the magnetic hysteresis loop of the above-mentioned cylinder magnetic patch that makes, obtain magnet performance.
Can adopt WLP-202 model particle mean size tester that the above-mentioned bonded magnetic powder that makes is averaged granularity Detection.
Embodiment 3
Present embodiment provides a kind of preparation method of bonded ferrite magnetic powder, specifically comprises:
Weighing 1395g purity is that 98.5% iron oxide red, 161g purity are that 98% strontium carbonate, 73.3g purity are that 98.5% lanthana, 35.9 gram purity are 99.2% zinc oxide; 5 gram purity are 99.5% bismuth oxide; Wet ball mill mixed 3 hours, and oven dry obtains compound then.
Weighing 1500 gram compounds, and add 15 gram strontium chlorides 1200 ℃ of following sintering 1 hour, obtain the pre-burning material.It is slightly broken to adopt dry ball that the pre-burning pellet is carried out, and adopts wet ball mill to carry out fine grinding 3 hours subsequently, obtains the fine grinding powder after the oven dry.
The fine grinding powder was annealed 1 hour down at 940 ℃, and carry out dispersion treatment, obtain the magnetic that bonds.
Weighing 1000g bonding magnetic, the relevant auxiliary agent with 20g of 110g nylon 6 (silane coupler and lubricant TAF) after mixing, adopt double screw extruder to carry out mixing and granulation, and melting temperature is 270 ℃;
Pellet is added vertical type injection molding machine, be heated to 250 ℃, injection moulding obtains the cylinder magnetic patch of Φ 10 * 10mm, and process of injection molding applies the magnetic field intensity of 10000Oe.
Can adopt the B-H tester to measure the magnetic hysteresis loop of the above-mentioned cylinder magnetic patch that makes, obtain magnet performance.
Can adopt WLP-202 model particle mean size tester that the above-mentioned bonded magnetic powder that makes is averaged granularity Detection.
Embodiment 4
Present embodiment provides a kind of preparation method of bonded ferrite magnetic powder, specifically comprises:
Weighing 1383g purity is that 98.5% iron oxide red, 139g purity are that 98% strontium carbonate, 97.9g purity are that 98.5% lanthana, 48.8 gram purity are 99.2% zinc oxide; 6 gram purity are 99.5% bismuth oxide; Adopt wet ball mill to mix 3 hours, oven dry obtains compound then.
Weighing 1500 gram compounds, and add 15 gram strontium chlorides 1200 ℃ of following sintering 1 hour, obtain the pre-burning material.It is slightly broken to adopt dry ball that the pre-burning pellet is carried out, and adopts wet ball mill to carry out fine grinding 3 hours subsequently, obtains the fine grinding powder after the oven dry.
The fine grinding powder was annealed 1 hour down at 940 ℃, and carry out dispersion treatment, obtain the magnetic that bonds.
Weighing 1000g bonding magnetic, the relevant auxiliary agent with 20g of 110g nylon 6 (silane coupler and lubricant TAF) after mixing, adopt double screw extruder to carry out mixing and granulation, and melting temperature is 270 ℃;
Pellet is added vertical type injection molding machine, be heated to 250 ℃, injection moulding obtains the cylinder magnetic patch of Φ 10 * 10mm, and process of injection molding applies the magnetic field intensity of 10000Oe.
Can adopt the B-H tester to measure the magnetic hysteresis loop of the above-mentioned cylinder magnetic patch that makes, obtain magnet performance.
Can adopt WLP-202 model particle mean size tester that the above-mentioned bonded magnetic powder that makes is averaged granularity Detection.
Embodiment 5
Present embodiment provides a kind of preparation method of bonded ferrite magnetic powder, specifically comprises:
Weighing 1420g purity is that 98.5% iron oxide red, 213g purity are that 98% strontium carbonate, 25.4g purity are that 98.5% lanthana, 12.5 gram purity are 99.2% zinc oxide; 2 gram purity are 99.5% bismuth oxide; Adopt wet ball mill to mix 3 hours, oven dry obtains compound then.
Weighing 1500 gram compounds, and add 130 gram strontium chlorides 1100 ℃ of following sintering 1 hour, obtain the pre-burning material.It is slightly broken to adopt dry ball that the pre-burning pellet is carried out, and adopts wet ball mill to carry out fine grinding 3 hours subsequently, obtains the fine grinding powder after the oven dry.
The fine grinding powder was annealed 1 hour down at 960 ℃, and carry out dispersion treatment, obtain the magnetic that bonds.
Weighing 460g bonding magnetic, 32gCPE and other auxiliary agent of 11g (titanate coupling agent and as the stearic acid of lubricant), calendering formation in two rollers of running in opposite directions, forming temperature is 85 ℃, obtains the film that thickness is 2.1mm;
Photographic film stamping is gone out the cylindrical film of Φ 25, and 6 cylindrical films are superimposed, obtain a cylinder magnetic patch.
Can adopt the B-H tester to measure the magnetic hysteresis loop of the above-mentioned cylinder magnetic patch that makes, obtain magnet performance.
Can adopt WLP-202 model particle mean size tester that the above-mentioned bonded magnetic powder that makes is averaged granularity Detection.
Embodiment 6
Present embodiment provides a kind of preparation method of bonded ferrite magnetic powder, specifically comprises:
Weighing 1405g purity is that 98.5% iron oxide red, 190g purity are that 98% strontium carbonate, 50.9g purity are that 98.5% lanthana, 25 gram purity are 99.2% zinc oxide; 3 gram purity are that 99.5% bismuth oxide adopts wet ball mill to mix 3 hours; Oven dry obtains compound then.
Weighing 1500 gram compounds, and add 130 gram strontium chlorides 1100 ℃ of following sintering 1 hour, obtain the pre-burning material.It is slightly broken to adopt dry ball that the pre-burning pellet is carried out, and adopts wet ball mill to carry out fine grinding 3 hours subsequently, obtains the fine grinding powder after the oven dry.
The fine grinding powder was annealed 1 hour down at 960 ℃, and carry out dispersion treatment, obtain the magnetic that bonds.
Weighing 460g bonding magnetic, 32gCPE and other auxiliary agent of 11g (titanate coupling agent and as the stearic acid of lubricant), calendering formation in two rollers of running in opposite directions, forming temperature is 85 ℃, obtains the film that thickness is 2.1mm;
Photographic film stamping is gone out the cylindrical film of Φ 25, and 6 cylindrical films are superimposed, obtain a cylinder magnetic patch.
Can adopt the B-H tester to measure the magnetic hysteresis loop of the above-mentioned cylinder magnetic patch that makes, obtain magnet performance.
Can adopt WLP-202 model particle mean size tester that the above-mentioned bonded magnetic powder that makes is averaged granularity Detection.
Comparative Examples 1
The preparation bonded magnetic powder, specific as follows:
Weighing 1430g purity is that 98.5% iron oxide red, 230g purity are 98% strontium carbonate, adopts wet ball mill to mix 3 hours, and oven dry obtains compound then;
Compound 1250 ℃ of following sintering 1 hour, is obtained the pre-burning material.It is slightly broken to adopt dry ball that the pre-burning pellet is carried out, and adopts wet ball mill to carry out fine grinding 3 hours subsequently, obtains the fine grinding powder after the oven dry;
The fine grinding powder was annealed 1 hour down at 940 ℃, and carry out dispersion treatment, obtain the magnetic that bonds.
With the above-mentioned magnetic powders bonded magnet that makes, specific as follows:
Weighing 1000g bonding magnetic, the relevant auxiliary agent with 20g of 110g nylon 6 (silane coupler and lubricant TAF) after mixing, adopt double screw extruder to carry out mixing and granulation, and melting temperature is 270 ℃; Pellet is added vertical type injection molding machine, be heated to 250 ℃, injection moulding obtains the cylinder magnetic patch of Φ 10 * 10mm, and process of injection molding applies the magnetic field intensity of 10000Oe.
Adopt the B-H tester to measure the magnetic hysteresis loop of the above-mentioned cylinder magnetic patch that makes, obtain magnet performance.
Adopt WLP-202 model particle mean size tester that the above-mentioned magnetic that makes is averaged granularity Detection.
Comparative Examples 2
The preparation bonded magnetic powder, specific as follows:
Weighing 1430g purity is that 98.5% iron oxide red, 230g purity are 98% strontium carbonate, adopts wet ball mill to mix 3 hours, and oven dry obtains compound then;
Compound 1250 ℃ of following sintering 1 hour, is obtained the pre-burning material; It is slightly broken to adopt dry ball that the pre-burning pellet is carried out, and adopts wet ball mill to carry out fine grinding 3 hours subsequently, obtains the fine grinding powder after the oven dry;
The fine grinding powder was annealed 1 hour down at 940 ℃, and carry out dispersion treatment, obtain the magnetic that bonds.
With the above-mentioned magnetic powders bonded magnet that makes, specific as follows:
Weighing 1000g bonding magnetic, the relevant auxiliary agent with 20g of 100g nylon 6 (silane coupler and lubricant TAF) after mixing, adopt double screw extruder to carry out mixing and granulation, and melting temperature is 270 ℃; Pellet is added vertical type injection molding machine, be heated to 250 ℃, injection moulding obtains the cylinder magnetic patch of Φ 10 * 10mm, and process of injection molding applies the magnetic field intensity of 10000Oe.
Adopt the B-H tester to measure the magnetic hysteresis loop of the above-mentioned cylinder magnetic patch that makes, obtain magnet performance.
Adopt WLP-202 model particle mean size tester that the above-mentioned magnetic that makes is averaged granularity Detection.
Comparative Examples 3
The preparation bonded magnetic powder, specific as follows:
Weighing 1430g purity is that 98.5% iron oxide red, 230g purity are 98% strontium carbonate, adopts wet ball mill to mix 3 hours, and oven dry obtains compound then;
Compound 1200 ℃ of following sintering 1 hour, is obtained the pre-burning material.It is slightly broken to adopt dry ball that the pre-burning pellet is carried out, and adopts wet ball mill to carry out fine grinding 3 hours subsequently, obtains the fine grinding powder after the oven dry;
The fine grinding powder was annealed 1 hour down at 940 ℃, and carry out dispersion treatment, obtain the magnetic that bonds.
With the above-mentioned magnetic powders bonded magnet that makes, specific as follows:
Weighing 1000g bonding magnetic, the relevant auxiliary agent with 20g of 110g nylon 6 (silane coupler and lubricant TAF) after mixing, adopt double screw extruder to carry out mixing and granulation, and melting temperature is 270 ℃; Pellet is added vertical type injection molding machine, be heated to 250 ℃, injection moulding obtains the cylinder magnetic patch of Φ 10 * 10mm, and process of injection molding applies the magnetic field intensity of 10000Oe.
Adopt the B-H tester to measure the magnetic hysteresis loop of the above-mentioned cylinder magnetic patch that makes, obtain magnet performance.
Adopt WLP-202 model particle mean size tester that the above-mentioned magnetic that makes is averaged granularity Detection.
Comparative Examples 4
The preparation bonded magnetic powder, specific as follows:
Weighing 1420g purity is that 98.5% iron oxide red, 205g purity are that 98% strontium carbonate, 24.4g purity are that 98.5% lanthana, 12 gram purity are 99.2% zinc oxide, adopts wet ball mill to mix 3 hours, and oven dry obtains compound then;
Compound 1250 ℃ of following sintering 1 hour, is obtained the pre-burning material.It is slightly broken to adopt dry ball that the pre-burning pellet is carried out, and adopts wet ball mill to carry out fine grinding 3 hours subsequently, obtains the fine grinding powder after the oven dry;
The fine grinding powder was annealed 1 hour down at 940 ℃, and carry out dispersion treatment, obtain the magnetic that bonds.
With the above-mentioned magnetic powders bonded magnet that makes, specific as follows:
Weighing 1000g bonding magnetic, the relevant auxiliary agent with 20g of 110g nylon 6 (silane coupler and lubricant TAF) after mixing, adopt double screw extruder to carry out mixing and granulation, and melting temperature is 270 ℃; Pellet is added vertical type injection molding machine, be heated to 250 ℃, injection moulding obtains the cylinder magnetic patch of Φ 10 * 10mm, and process of injection molding applies the magnetic field intensity of 10000Oe.
Adopt the B-H tester to measure the magnetic hysteresis loop of the above-mentioned cylinder magnetic patch that makes, obtain magnet performance.
Adopt WLP-202 model particle mean size tester that the above-mentioned magnetic that makes is averaged granularity Detection.
Comparative Examples 5
The preparation bonded magnetic powder, specific as follows:
Weighing 1430g purity is that 98.5% iron oxide red, 236g purity are 98% strontium carbonate, adopts wet ball mill to mix 3 hours, and oven dry obtains compound then;
Compound 1100 ℃ of following sintering 1 hour, is obtained the pre-burning material.It is slightly broken to adopt dry ball that the pre-burning pellet is carried out, and adopts wet ball mill to carry out fine grinding 3 hours subsequently, obtains the fine grinding powder after the oven dry;
The fine grinding powder was annealed 1 hour down at 960 ℃, and carry out dispersion treatment, obtain the magnetic that bonds.
With the above-mentioned magnetic powders bonded magnet that makes, specific as follows:
Weighing 460g bonding magnetic, 32gCPE and other auxiliary agent of 11g (titanate coupling agent and as the stearic acid of lubricant), calendering formation in two rollers of running in opposite directions, forming temperature is 85 ℃, obtains the film that thickness is 2.1mm; Photographic film stamping is gone out the cylindrical film of Φ 25, and 6 cylindrical films are superimposed, obtain a cylinder magnetic patch.
Adopt the B-H tester to measure the magnetic hysteresis loop of the above-mentioned cylinder magnetic patch that makes, obtain magnet performance.
Adopt WLP-202 model particle mean size tester that the above-mentioned magnetic that makes is averaged granularity Detection.
The magnetic patch performance that magnetic patch performance that the foregoing description 1～4 is made and Comparative Examples 1～4 make compares its result such as table 2:
Table 1 embodiment of the invention and comparative example's contrast table
Magnetic patch performance and powder characteristics after table 2 injection moulding
Through the comparing result of above-mentioned table 2, can find out that the Br of the embodiment of the invention compares with Comparative Examples 2 with comparative example 1, under equal powder containing quantity condition, have the high advantage of magnet Br; The magnet jHc of the embodiment of the invention compares with Comparative Examples 4, has the high and high advantage of jHc of magnet Br.
The magnetic patch performance that magnetic patch performance that the foregoing description 5,6 is made and Comparative Examples 5 make compares its result such as table 3:
Magnetic patch performance and powder characteristics behind table 3 calendering formation
Through the comparing result of above-mentioned table 3, can find out that the Br of the embodiment of the invention compares with Comparative Examples 5, have the high advantage of Br.
In sum, through adding a certain proportion of bismuth oxide, can play the effect that suppresses grain growth in the embodiment of the invention, effectively improve granularity of magnet powder and distribute, make the size distribution narrow of magnetic, therefore improve the jHc of magnetic in the batch mixing process.Through when adding certain bismuth oxide; And when batch mixing, add a certain proportion of chloride as flux; Can effectively reduce calcined temperature, avoid growing up unusually of crystal grain, well improve growing up and grain shape of granularity of magnet powder distribution and control crystal grain.In sum, the present invention adds a certain proportion of Bi element simultaneously, and in batch mixing, adds a certain proportion of chloride as flux through adding a certain proportion of La, Zn element, can obtain to possess the magnetic of high Br and high jHc.
The above; Be merely the preferable embodiment of the present invention, but protection scope of the present invention is not limited thereto, any technical staff who is familiar with the present technique field is in the technical scope that the present invention discloses; The variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection range of claims.
Claims (8)
1. a bonded ferrite magnetic powder is characterized in that, this magnetic has the principal phase of following molecular formula:
(M
1-xLa
x)O·n(Fe
1-yZn
yBi
z)
2O
3
Wherein, M represents at least a element in strontium, the barium; X, y, z, n representes mol ratio, satisfies x=2mn (y+z), and x=0.01～0.40, z/y=0.30, n=5.50～6.40, m=0.90～1.10; The pressed density of said magnetic is 3.05～3.7g/cm
3, the particle mean size of magnetic is 0.9～3.0 μ m.
2. the preparation method of a bonded ferrite magnetic powder is characterized in that, may further comprise the steps:
(1) any in the compound of the compound of employing strontium or barium and the oxide of iron, the oxide of lanthanum, the oxide of zinc and the oxide of bismuth are raw material, and each raw material all adopts Powdered, according to molecular formula (M
1-xLa
x) On (Fe
1-yZn
yBi
z)
2O
3Batching, M represents at least a element in strontium, the barium; X in the molecular formula, y, z, n representes mol ratio, satisfies x=2mn (y+z), and x=0.01～0.40, z/y=0.30, n=5.50～6.40, m=0.90～1.10;
(2) each raw material of weighing in proportion is with obtaining compound after each raw materials mix;
(3 when carrying out batch mixing to said compound, in compound, adds chloride as flux;
(4) under 1050～1280 ℃ temperature, carry out pre-burning, obtain the pre-burning material;
(5) said pre-burning material is carried out coarse crushing and obtain meal;
(6) to the further fine grinding of said meal, obtain fine powder;
(7) under 850～980 ℃ of temperature, said fine powder is annealed, through the lattice defect of annealing in process elimination magnetic, promptly obtaining pressed density after the annealing in process is 3.05～3.7g/cm
3, particle mean size is the bonded ferrite magnetic powder of 0.9～3.0 μ m;
The compound of said strontium adopts any in strontium carbonate, the strontium sulfate; The compound of said barium adopts any in brium carbonate, the barium sulfate;
The oxide of said iron adopts any in iron scale powder, iron oxide red powder or the fine ore, and its purity range is 97.5～99.5%;
The oxide raw material of said lanthanum adopts pulverous lanthana, and its purity range is a technical grade;
The oxide raw material of said zinc adopts pulverous zinc oxide, and its purity range is a technical grade;
The oxide raw material of said bismuth adopts pulverous bismuth oxide, and its purity range is a technical grade.
3. according to the preparation method of the said bonded ferrite magnetic powder of claim 2; It is characterized in that a certain proportion of chloride of adding as flux is in the said method step (3): the chloride that adding accounts for compound total weight 0.1～10% in compound is as flux.
4. according to the preparation method of the said bonded ferrite magnetic powder of claim 3, it is characterized in that said chloride comprises: any in sodium chloride, potassium chloride, magnesium chloride, calcium chloride, strontium oxide strontia, the barium chloride or any several kinds.
5. according to the preparation method of the said bonded ferrite magnetic powder of claim 2, it is characterized in that the pre-burning time of under 1050～1280 ℃ temperature, carrying out pre-burning in the said method step (4) is 0.01～5 hour.
6. according to the preparation method of the said bonded ferrite magnetic powder of claim 2, it is characterized in that the annealing time of under 850～980 ℃ of temperature, said fine powder being annealed in the said method step (7) is 0.01～3 hour.
7. a bonded permanent magnet is characterized in that, this bonded permanent magnet is the bonded permanent magnet that raw material is processed with moulding process for adopting aforesaid right to require 1 described magnetic.
8. bonded permanent magnet according to claim 7 is characterized in that, said moulding skill adopts: any in injection moulding, extrusion molding, the calendering formation.
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| CN102351525A (en) * | 2011-07-19 | 2012-02-15 | 吕佳佳 | Manufacture method of permanent magnet ferrite material powder for injection molding |
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| CN102992744A (en) * | 2011-09-13 | 2013-03-27 | 张连墩 | M-type strontium ferrite powder for injection molding bonded permanent magnet and preparation process of M-type strontium ferrite powder |
| KR102269998B1 (en) * | 2013-10-02 | 2021-06-25 | 도다 고교 가부시끼가이샤 | Ferrite particle powder for bonded magnet, resin composition for bonded magnet, and molded article using ferrite particle powder and resin composition |
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| CN104616882B (en) * | 2015-01-17 | 2017-07-04 | 浙江和也健康科技有限公司 | A kind of anisotropic bonded magnet and its production technology |
| CN104844187A (en) * | 2015-04-29 | 2015-08-19 | 安徽中磁高科有限公司 | Permanent magnetic ferrite material containing rare earth and preparation method thereof |
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| CN106673637A (en) * | 2016-12-14 | 2017-05-17 | 湖南航天磁电有限责任公司 | Permanent magnetic ferrite preparation method with improved formula materials |
| CN107399964B (en) * | 2017-08-21 | 2021-07-20 | 北矿磁材科技有限公司 | Preparation method of bonded ferrite magnetic powder |
| CN114464387A (en) * | 2021-08-10 | 2022-05-10 | 浙江安特磁材股份有限公司 | Rolled permanent magnetic ferrite magnetic powder and rubber product thereof |
| CN115784732B (en) * | 2022-11-25 | 2023-09-05 | 中国科学院宁波材料技术与工程研究所 | Ce-Mn doped strontium ferrite and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0758786A1 (en) * | 1995-08-11 | 1997-02-19 | TDK Corporation | Magnet powder, sintered magnet, bonded magnet, and magnetic recording medium |
| CN1724461A (en) * | 2004-07-23 | 2006-01-25 | 佛山市顺德区霸菱磁电有限公司 | Process for mfg. ferrite rubber-plastic magnetic powder |
| EP2136379A1 (en) * | 2007-03-14 | 2009-12-23 | Toda Kogyo Corporation | Ferrite powder for bonded magnet, resin composition for bonded magnet, and molded body made of those |
| CN101656135A (en) * | 2009-08-21 | 2010-02-24 | 北矿磁材科技股份有限公司 | Ferromagnetic oxide powder for magnetic recording and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001335361A (en) * | 2000-05-23 | 2001-12-04 | Sumitomo Special Metals Co Ltd | Ferrite material powder and method for manufacturing ferrite magnet |
| EP1667176B1 (en) * | 2003-09-12 | 2016-03-23 | Hitachi Metals, Ltd. | Ferrite sintered magnet |
-
2010
- 2010-07-02 CN CN2010102250094A patent/CN101894648B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0758786A1 (en) * | 1995-08-11 | 1997-02-19 | TDK Corporation | Magnet powder, sintered magnet, bonded magnet, and magnetic recording medium |
| CN1724461A (en) * | 2004-07-23 | 2006-01-25 | 佛山市顺德区霸菱磁电有限公司 | Process for mfg. ferrite rubber-plastic magnetic powder |
| EP2136379A1 (en) * | 2007-03-14 | 2009-12-23 | Toda Kogyo Corporation | Ferrite powder for bonded magnet, resin composition for bonded magnet, and molded body made of those |
| CN101656135A (en) * | 2009-08-21 | 2010-02-24 | 北矿磁材科技股份有限公司 | Ferromagnetic oxide powder for magnetic recording and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2001-335361A 2001.12.04 |
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