WO2017222212A1 - 페라이트 자성재료 및 페라이트 소결자석 - Google Patents

페라이트 자성재료 및 페라이트 소결자석 Download PDF

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WO2017222212A1
WO2017222212A1 PCT/KR2017/005878 KR2017005878W WO2017222212A1 WO 2017222212 A1 WO2017222212 A1 WO 2017222212A1 KR 2017005878 W KR2017005878 W KR 2017005878W WO 2017222212 A1 WO2017222212 A1 WO 2017222212A1
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Prior art keywords
ferrite
magnetic
magnetic material
sintered magnet
maximum
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PCT/KR2017/005878
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English (en)
French (fr)
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김민호
이동영
이정환
정은선
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쌍용머티리얼 주식회사
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Priority to EP17815625.3A priority Critical patent/EP3473606B1/en
Priority to PL17815625.3T priority patent/PL3473606T3/pl
Priority to MX2018015263A priority patent/MX2018015263A/es
Priority to BR112018076409-4A priority patent/BR112018076409B1/pt
Priority to CN201780038058.7A priority patent/CN109311762A/zh
Priority to US16/308,163 priority patent/US20190252100A1/en
Publication of WO2017222212A1 publication Critical patent/WO2017222212A1/ko

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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/606—Drying
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/76—Crystal structural characteristics, e.g. symmetry
    • C04B2235/767—Hexagonal symmetry, e.g. beta-Si3N4, beta-Sialon, alpha-SiC or hexa-ferrites
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/64—Electric machine technologies in electromobility

Definitions

  • the present invention relates to a ferrite magnetic material and a ferrite sintered magnet using the same, which are inexpensive and can provide a high maximum magnetic energy ((BH) max ) compared to conventional ferrite sintered magnets.
  • Ferrite has a hexagonal magneto-plumbite (M) crystal structure, and its magnetic properties do not change easily depending on the direction and size of the magnetic field. In general, it is used as a material for permanent magnets, such as motors for automotive electronics and rotary machines for electric appliances. Ferrite is made of low cost strontium carbonate and iron oxide as a raw material, and is manufactured by a general ceramic manufacturing process.
  • M hexagonal magneto-plumbite
  • Representative magnetic properties of permanent magnets include residual magnetic flux density (Br), intrinsic coercive force (iHc), maximum magnetic energy ((BH) max )), and angular ratio (Hknie / iHc). Have a relationship.
  • the residual magnetic flux density (Br) is proportional to the saturation magnetization, density, and degree of orientation, which is the sum of the magnetic spin moments of the composition. Density and orientation can be achieved at about 95% of the theoretical value by process optimization with the properties obtained in the process after pulverization of the ferrite manufacturing process.
  • the intrinsic coercive force (iHc) is proportional to the ratio of the anisotropic magnetic field and the terminal sphere volume.
  • the theoretical anisotropic magnetic field value of the terminal sphere Sr-ferrite is 20,000 Oe and the terminal sphere crystal size is about 1 ⁇ m.
  • a high coercivity value can be obtained by increasing the volume ratio of the terminal sphere size.
  • Sr-ferrite is the size of a terminal sphere, it is possible to achieve about 40% (7,700 Oe) of the theoretical value by the internal semi-magnetic field, and higher anisotropic magnetic field by substituting Fe ions with Co, Cr, Al, etc. You can get the value.
  • the maximum magnetic energy product ((BH) max ) is a product of the magnetic flux density (B) provided by the magnet and the magnetic field (H) acting on the magnet at each operating point in the BH curve, and the energy accumulated inside the magnet. Means.
  • the point at which the product of B and H is the maximum on each demagnetization curve is the maximum magneto-energy.
  • permanent magnets with high Br, iHc and angular ratios have high maximum magnetic energy, and motors employing the permanent magnets are less likely to generate potatoes due to high power and external magnetic fields.
  • the maximum magnetic energy level is a representative performance index of permanent magnets.
  • Patent Document 1 U. S. Patent No. 5,846, 449 (Patent Document 1) has improved saturation magnetization compared to the conventional composition in which a part of Fe is replaced with Co when a part of Fe is replaced with Zn and a part of Sr is replaced with La. It is disclosed that a ferrite magnet having can be obtained.
  • a part of Fe is replaced with Zn as described above, there is a problem in that the maximum magnetic energy is lowered to 5.14 MGOe due to the rapid decrease in the anisotropic magnetic field.
  • Patent Document 2 discloses to improve the residual magnetic flux density and intrinsic coercive force by substituting a part of Ca with rare earth elements such as La and a part of Fe with Co, This results in a maximum magnetic energy of 42.0 kJ / m 3 (about 5.28 MGOe).
  • Patent Document 1 discloses to improve the residual magnetic flux density and intrinsic coercive force by substituting a part of Ca with rare earth elements such as La and a part of Fe with Co, This results in a maximum magnetic energy of 42.0 kJ / m 3 (about 5.28 MGOe).
  • Patent Document 1 discloses to improve the residual magnetic flux density and intrinsic coercive force by substituting a part of Ca with rare earth elements such as La and a part of Fe with Co, This results in a maximum magnetic energy of 42.0 kJ / m 3 (about 5.28 MGOe).
  • Patent Document 2 discloses to improve the residual magnetic flux density and intrinsic coercive force by substituting a part of Ca with rare earth elements such as La and a part
  • Patent Document 3 obtains high residual magnetic flux density, intrinsic coercive force, and square ratio by substituting part of Ca with Sr, Ba and La and substituting part of Fe with Co and Cr. Although the method is described, the maximum magnetic energy of the magnet obtained by this method is 5.29 MGOe, which is not sufficiently high compared with the conventional Sr ferrite magnet (Patent Document 1).
  • Korean Patent No. 10-0910048 discloses that in order to obtain the maximum magnetic energy of 5.28 MGOe, La of 0.3 and Co of 0.5 are required as the content ratio
  • Korean Patent No. 10-1082389 discloses that in order to obtain a maximum magnetic energy product of 5.29 MGOe, La of 0.415 and Co of 0.316 are required as content ratios.
  • La and Co are expensive raw materials ranging from tens of times to about 100 times of iron oxide, which is the main component of ferrite sintered magnets, and as the content thereof increases, the production cost of ferrite sintered magnets increases considerably.
  • ferrite magnetic materials of known composition are expensive and still unsatisfactory with respect to the price required by the market, and development of magnetic materials having lower magnetic properties and superior magnetic properties than existing magnetic materials is required.
  • the present inventors conducted continuous research to achieve the above object, and as a result, each of the saturation magnetization and anisotropic magnetic field can be simultaneously improved in a ferrite composition containing La as less than 0.4 and Co as less than 0.3.
  • the present invention has been completed by finding a ferrite magnetic material which is inexpensive compared to the prior art and can provide high maximum magnetic energy due to high saturation magnetization and anisotropic magnetic field.
  • an object of the present invention is to provide a ferrite magnetic material capable of providing high maximum magnetic energy with low cost by lowering the content of La and Co, and a ferrite sintered magnet obtained by sintering the same.
  • the present invention provides a ferrite magnetic material, characterized in that the magneto plumbite phase having a hexagonal structure as a main phase, the element constituting the main phase comprises a composition of the formula (1):
  • the ferrite sintered magnet obtained from the ferrite magnetic material according to the present invention is cheaper than the conventional magnetic material and has a high maximum magnetic energy ((BH) max ), thereby meeting high efficiency and miniaturization of a recently required motor. have.
  • FIG. 1 is a graph showing the change of maximum magnetic energy ((BH) max ) according to the change of the Co content (m) of the ferrite sintered magnet obtained in Preparation Example 1.
  • FIG. 1 is a graph showing the change of maximum magnetic energy ((BH) max ) according to the change of the Co content (m) of the ferrite sintered magnet obtained in Preparation Example 1.
  • FIG. 2 is a graph showing the change of maximum magnetic energy ((BH) max ) according to the change of La content (y) of the ferrite sintered magnet obtained in Preparation Example 2.
  • FIG. 2 is a graph showing the change of maximum magnetic energy ((BH) max ) according to the change of La content (y) of the ferrite sintered magnet obtained in Preparation Example 2.
  • the ferrite magnetic material of the present invention has a magneto plumbite phase having a hexagonal structure as a main phase, and the elements constituting the main phase include a composition of Formula 1 below:
  • the content (y) of La is in the range of 0.32 to 0.394, high saturation magnetization and anisotropic magnetic field are obtained, whereby high maximum magnetic energy product can be obtained. More preferred La content is in the range of 0.35 to 0.394. If the La content (y) is within the above range, it is possible to prevent an increase in cost and to prevent a problem in that a nonmagnetic phase is generated to simultaneously reduce saturation magnetization and anisotropic magnetic field or decrease the high capacity to obtain a high maximum magnetic energy product.
  • the Co content (m) When the Co content (m) is in the range of 0.251 to 0.29, a high maximum magnetic energy product can be obtained. If the Co content (m) is within the above range, the increase in cost is prevented, the substitutional solid solution amount is decreased, and the saturation magnetization and anisotropic magnetic field are simultaneously decreased, or the phase magnetic instability is reduced according to the sintering temperature, thereby reducing the maximum magnetic energy. Can be prevented.
  • the Ca content (1-x-y) is in the range of 0.42 to 0.52, a high maximum magnetic energy product can be obtained. More preferred Ca content is in the range of 0.44 to 0.50.
  • the phase is unstable depending on the sintering temperature, thereby preventing the problem of decreasing the maximum magnetic energy amount or reducing the maximum magnetic energy amount by reducing the substitutional solid solution amount.
  • 2n is a value representing the content of (Fe + Co) / (Ca + Sr + La), and when 2n is in the range of 9.0 to 10.0, a high maximum magnetic energy product can be obtained.
  • the Ca, Sr, and La weight ratios are relatively increased, so that nonmagnetic due to the excess of the high capacity is generated, thereby reducing the maximum magnetic energy or unreacted ⁇ -Fe 2 O 3 , thereby reducing the maximum magnetic energy.
  • Ferrite magnetic material and a sintered magnet manufacturing method according to an embodiment of the present invention is as follows.
  • the weight is converted into% by weight from a predetermined ratio of each element with respect to the starting material and then weighed.
  • the mixing equipment is wet mixed with a starting material using a wet-type ball mill or a wet-type attritor, wherein the wet ball mill is based on 5 to 10 hours and the wet attire is 2 to 10 hours. Mix well and uniformly for 4 hours.
  • starting materials SrCO 3 , CaCO 3 , La 2 O 3 , Fe 2 O 3 , Co 3 O 4 , and the like, which form ferrite sintered magnets, may be used.
  • impurities such as Al 2 O 3 , Cr 2 O 3 , NiO, MnO, ZnO, SiO 2 , MgO, BaO, P, and S may be included in an amount of 0.1 to 1.0 wt%.
  • H 3 BO 3 0.05 to 0.2 parts by weight of H 3 BO 3 based on 100 parts by weight of the starting material may be further mixed with the starting material.
  • the calcining process is a process of calcining the raw materials of the composition mixed and blended in the previous process to form a plastic body having a M (magnet plumbite) structure with ferritic reaction, and calcining is usually performed in an oxidizing atmosphere in air.
  • the calcining is preferably performed for 30 minutes to 2 hours in the range of 1,150 to 1,250 ° C.
  • the longer the plasticization time the higher the proportion of the M phase, but this leads to an increase in the manufacturing cost.
  • 90% or more of the ratio of M phase which is a main phase of a plastic body is preferable, and it is preferable that the particle size in a structure shall be 2-4 micrometers.
  • the grinding means may be a dry vibration mill or a dry ball mill, and the like, and preferably, a dry vibration mill is used.
  • the average particle diameter of the powder after coarse grinding ie, coarse grinding powder
  • the average particle diameter of the fine powder is 0.6 to 0.8 mu m.
  • the orientation is degraded due to particle aggregation between the ferrite magnetic powders, the magnetic properties are deteriorated, and the leakage of slurry occurs during molding, or the dehydration time is increased to increase manufacturing costs; And multi-spheres are generated, the coercive force is drastically reduced and much heat energy is required to secure sufficient sintering density, thereby preventing a problem of rising manufacturing costs.
  • Grinding means can be pulverized using a wet ball mill or a wet attritor, the grinding time is inversely proportional to the pulverization energy and the time varies depending on the type of the pulverizer can be adjusted according to the pulverizer and the target particle diameter.
  • SiO 2 , CaCO 3 or a mixture thereof may be added as an additive during pulverization, promoting the substitution effect during sintering and the growth of the particles.
  • Fe 2 O 3 , La 2 O 3 , SrCO 3 , Co 3 O 4 or the like may be added as an additive. At this time, if the addition amount of the additive is too small, the effect is insignificant, and if too much of the negative effect occurs, it can be added in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the pulverized powder, respectively.
  • dispersing agents may be added to improve the fluidity of the slurry, decrease the viscosity, and increase the orientation effect during molding in a magnetic field.
  • a dispersing agent both an aqueous dispersant and a non-aqueous dispersant may be used.
  • Dispersants can be used.
  • the aqueous dispersant an organic compound having a hydroxyl group and a carboxyl group, sorbitol, calcium gluconate, or the like can be used.
  • the dispersant may be added in an amount of 0.1 to 1.0 parts by weight based on 100 parts by weight of the coarsely pulverized powder. When the amount of the dispersant added is within the above range, dehydration may be reduced to prevent a problem of causing cracks during drying and sintering of the molded body.
  • the molding process may be performed by a wet anisotropic molding method, and the molding is performed by applying a magnetic field during molding, thereby obtaining a molded body of an anisotropic sintered magnet.
  • the slurry is dehydrated and concentrated to carry out molding in a magnetic field while maintaining a predetermined concentration.
  • Dehydration and concentration may be performed using a centrifugal separator or a filter press, wherein the slurry concentration may be 60 to 66% by weight, the molding pressure is 0.3 to 0.5 ton / cm 2, and the applied magnetic field may be 10 to 20 kOe.
  • residual moisture is present in the range of about 10 to 15% by weight, and if it is sintered as it is, it may cause cracks during dehydration during heating, so that it is naturally dried or low temperature in air (50 to 100 ° C.) to prevent this. After drying, it may be sintered.
  • a ferrite sintered magnet is obtained by continuously drying and sintering a shaped body in an oxidizing atmosphere in the atmosphere. Dehydration and degreasing can be carried out at 50 to 100 ° C. for removal of water remaining in the molded body and degreasing of the dispersant.
  • the magnetic properties of ferrite sintered magnets can be improved by controlling the sintering conditions such as temperature rising rate, maximum temperature, maximum temperature holding time, and cooling rate. For example, depending on the sintering conditions (sintering time, temperature increase rate, maximum temperature, holding time), the concentration of substitution element solid solution in the grains of the ferrite sintered magnet is increased, the grain growth is controlled, the grain size is uniformly maintained, and the density and orientation of the sintered magnet are controlled. Magnetic properties can be controlled.
  • It can be sintered for 30 minutes to 2 hours at a temperature increase time of 1 to 10 ° C./min, sintering maximum temperature of 1,200 to 1,250 ° C., and cooled to a cooling time of 1 to 10 ° C./min.
  • the magneto plumbite-type ferrite sintered magnet of the present invention obtained by sintering the ferrite magnetic material has a maximum magnetic energy when the saturation magnetization (4 ⁇ Is) is 4.8 kG or more and the anisotropic magnetic field (H A ) is 26 kOe or more.
  • ((BH) max ) has magnetic properties of 5.5 MGOe or more.
  • the 4 ⁇ I-H curve is related to magnetization, which refers to an operation in which a magnetic field is applied to a magnetic body to generate a magnetic moment and magnetic polarization.
  • the present invention provides a permanent magnet such as segment type or block type derived from a ferrite magnetic material.
  • the permanent magnet of the present invention can be used in a rotor, a sensor and a bond magnet used in automobiles, electric appliances, home appliances.
  • the maximum magnetic energy ((BH) max ) of the ferrite sintered magnet prepared in the following Preparation Example was measured using a BH Curve Tracer having a maximum applied field of 25 kOe (1,990 kA / m) in an atmosphere of 20 ° C.
  • the ferrite sintered magnet was cut into a width of 5 mm and a thickness of 5 mm, followed by saturation magnetization (4 ⁇ Is) and anisotropic magnetic field (H A ) in one quadrant of the 4 ⁇ I-H curve for the plane parallel to the plane perpendicular to the alignment plane. The value was measured, and the density of the ferrite magnet was measured by the Archimedes method.
  • Iron oxides Fe 2 O 3 , purity 99% or more
  • strontium carbonate SrCO 3
  • calcium carbonate CaCO 3
  • lanthanum oxide La 2 O 3
  • cobalt oxide Co 3 O 4
  • To this starting material is a composition satisfying Ca (1-xy) ferrite sintered magnet of Sr x La y Fe (2n- m) Co m O 19 , which, as described in Table 1 were blended so obtained.
  • 0.1 wt% of H 3 BO 3 was added to the total weight of the blended raw material.
  • the blended raw materials were mixed with water to a concentration of 40% by weight and then wet circulated for 2 hours.
  • the raw material thus made was dried at 130 ° C. for 24 hours.
  • Preparation Example 1-1 The powder dried in Preparation Example 1-1 was calcined in air at 1,200 ° C. for 1 hour to obtain a plastic body.
  • the plastic body of Production Example 1-2 obtained a coarse pulverized powder having an average particle diameter of 4 ⁇ m using a dry vibration mill.
  • the coarsely pulverized powder is added to the circulating attritor so that the coarse pulverized powder has a concentration of 40 wt%, and the coarsely pulverized powder and water are added to the coarsely pulverized powder, and 1.0 wt% CaCO 3 , 0.40 wt% SiO 2 and 0.6 wt% of calcium gluconate was added (based on the total content of the coarse pulverized powder) to obtain a sintered body composition as shown in Table 1 above.
  • the average particle diameter of the powder after pulverization was set to 0.65 mu m.
  • the slurry which is a mixture of the finely divided powder and water obtained in Production Example 1-3, was dewatered to have a concentration of 63% by weight of the finely divided powder, and then a disk type (40 mm in diameter) was formed using a wet magnetic field machine in which the magnetic field direction was parallel to the pressing direction. A molded sample of X thickness 11 mm) was produced.
  • the magnetic field strength was set to 10 kOe (796 kA / m) and the molding pressure was set to 0.4 Ton / cm 2.
  • the molded body obtained in Production Example 1-4 was sintered at 1,210 ° C. for 1 hour, and the obtained sintered body was processed to a thickness of 7 mm using a double-sided thickness processing machine to obtain a ferrite sintered magnet.
  • the magnetic properties and density of the obtained ferrite sintered magnet was measured and shown in Table 1 below.
  • the change of maximum magnetic energy ((BH) max ) according to the change of Co content (m) of the obtained ferrite sintered magnet was also illustrated. 1 is shown.
  • the maximum magnetic energy product ((BH) max ) was found to be 5.5 MGOe or more, which was significantly higher than the comparative example in which the Co content was outside the above range.
  • Ferrite sintered magnets were prepared in the same manner as in Preparation Example 1 except that the overall sintered compact composition ratio including La content (y) was changed as shown in Table 2 below. It is shown in Table 2 below.
  • Table 2 the change of the maximum magnetic energy product ((BH) max ) according to the change of La content (y) of the obtained ferrite sintered magnet is shown in FIG.
  • the maximum magnetic energy product of 5.5 MGOe or more was obtained.
  • the La content is more than 0.394, La not dissolved in the ferrite main phase generates orthoferrite, which is a nonmagnetic phase, and the maximum magnetic energy is decreased.
  • the La content is less than 0.32, the substitution capacity of La is not sufficient and 4 ⁇ Is is reduced. The maximum magnetic energy product required in the present invention could not be obtained.
  • a ferrite sintered magnet was manufactured in the same manner as in Preparation Example 1, except that the Ca content (1-x-y) was changed as shown in Table 3 below.
  • the magnetic properties and density of the obtained ferrite sintered magnet were measured and shown in Table 3 below.
  • Samples 15 and 22 correspond to Comparative Examples of the present invention
  • Samples 16 to 21 are examples of the present invention.
  • a ferrite sintered magnet was manufactured in the same manner as in Preparation Example 1, except that 2n was changed as shown in Table 4, and the magnetic properties and density of the obtained ferrite sintered magnet were measured and shown in Table 4 below.
  • Samples 23 and 28 correspond to Comparative Examples of the present invention
  • Samples 24 to 27 are examples of the present invention.

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Abstract

본 발명은 La 및 Co를 저첨가함으로써 가격이 저렴하면서도 높은 포화자화 및 높은 이방성 자계를 유도하여 종래 페라이트 자성재료보다 현저히 높은 최대자기에너지적((BH)max)을 제공할 수 있는 페라이트 자성재료를 제공한다.

Description

페라이트 자성재료 및 페라이트 소결자석
본 발명은 종래의 페라이트 소결자석에 비교하여 가격이 저렴하면서도 높은 최대자기에너지적((BH)max)을 제공할 수 있는 페라이트 자성 재료 및 이를 이용한 페라이트 소결자석에 관한 것이다.
페라이트는 육방정의 마그네토플럼바이트(Magneto-plumbite, M)형 결정구조를 가지며, 재료의 자기적 특성이 자장의 방향과 크기에 따라 쉽게 변화되지 않는 재료이다. 통상적으로 자동차 전장용 모터 및 전기기구용 회전기 등 영구자석의 재료로 사용되고 있다. 페라이트는 영구자석 재료 중 가격이 저렴한 스트론튬 탄산염과 산화철을 원료로 하고 일반적인 세라믹 제조공정으로 제조되어 가격이 저렴하다는 특징을 갖는다.
한편, 최근 환경 문제와 이에 따른 에너지 절약과 관련된 여러 가지 법 규제로 인하여 모터의 소형화와 고효율화가 요구되고 있으며 영구자석에도 고성능화가 요구되고 있다.
영구자석의 대표적인 자기특성으로 잔류자속밀도(Br), 고유보자력(iHc), 최대자기에너지적((BH)max)), 각형비(Hknie/iHc)가 있으며, 잔류자속밀도 및 고유보자력은 하기 관계식을 갖는다.
Br = 4πIs x ρ x f (Is: 포화자화, ρ: 밀도, f: 배향도)
iHc = HA x fc (HA: 이방성 자계, fc: 단자구 체적 비율)
잔류자속밀도(Br)는 조성의 자기 스핀 모멘트 합인 포화자화, 밀도, 배향도에 비례한다. 밀도와 배향도는 페라이트 제조공정의 미분쇄 이후 공정에서 얻어지는 물성으로 공정 최적화에 의해 이론값의 약 95% 정도로 달성할 수 있다. 상온에서 스트론튬 페라이트(하기 "Sr-페라이트"로 기재함)의 이론 포화자화는 74 emu/g(4πIs = 4,760 G: 밀도와 배향도가 각각 100% 일 때 값)으로 알려져 있으며, 치환된 페라이트 조성에서 스핀 자기 모멘트 증가에 의해 포화자화가 증가된다.
고유보자력(iHc)은 이방성 자계와 단자구 체적 비율에 비례하며, 단자구 Sr-페라이트의 이론 이방성 자계값은 20,000 Oe 이며, 단자구 결정 크기는 약 1 ㎛로 알려져 있다. 페라이트 제조공정의 미분쇄 이후 공정 최적화에 의해 단자구 크기의 체적 비율을 높여 높은 보자력 값을 얻을 수 있다. Sr-페라이트가 단자구 크기일 때 내부 반자장에 의해 이론값의 약 40% (7,700 Oe) 달성 가능하며, Fe 이온을 자기 이방성이 큰 원소인 Co, Cr, Al 등으로 치환함으로써 더 높은 이방성 자계값을 얻을 수 있다.
한편, 최대자기에너지적((BH)max)은 B-H 곡선에서의 각각의 동작점에서 자석이 제공하는 자속밀도(B)와 자석에 작용하는 자장(H)의 곱으로서, 자석 내부에 축적된 에너지를 의미한다. 각각의 감자(demagnetization)곡선 상에서 B와 H의 곱이 최대인 지점이 최대자기에너지적이 된다. 일반적으로 Br, iHc와 각형비가 모두 높은 영구자석이 높은 최대자기에너지적을 가지며, 그 영구자석을 채용한 모터는 높은 출력과 외부자계에 의한 감자 발생이 적다. 결과적으로 최대자기에너지적은 영구자석의 대표적인 성능지표라고 할 수 있다.
예컨대, 미국 등록특허 제 5,846,449 호(특허문헌 1)는 Fe의 일부를 Zn으로 치환하고 Sr의 일부를 La로 치환할 경우, Fe의 일부를 Co로 치환하는 종래의 조성에 비해, 향상된 포화자화를 갖는 페라이트 자석을 얻을 수 있음을 개시하고 있다. 그러나 이와 같이 Fe의 일부를 Zn으로 치환할 경우, 이방성 자계의 급격한 감소에 의해 최대자기에너지적이 5.14 MGOe로 낮아지는 문제가 있다.
또한, 대한민국 등록특허 제 10-0910048 호(특허문헌 2)는 Ca의 일부를 La 등의 희토류 원소로 치환하고 Fe의 일부를 Co로 치환하여 잔류자속밀도와 고유보자력을 향상시키는 것을 개시하고 있으며, 이를 통해 42.0 kJ/m3 (약 5.28 MGOe)의 최대자기에너지적을 얻고 있다. 그러나, 특허문헌 2로부터 얻어지는 자석의 자기특성은 종래의 Sr계 페라이트 자석(특허문헌 1)의 자기특성에 비해 충분히 높지 않은 문제가 있다.
나아가, 대한민국 등록특허 제 10-1082389 호(특허문헌 3)는 Ca의 일부를 Sr, Ba와 La으로 치환하고 Fe의 일부를 Co와 Cr으로 치환하여 높은 잔류자속밀도, 고유보자력, 각형비를 얻는 방법을 기재하고 있으나, 이 방법에 의해 얻어지는 자석의 최대자기에너지적이 5.29 MGOe로 종래의 Sr계 페라이트 자석(특허문헌 1)에 비해 충분히 높지 않다.
또한, 대한민국 등록특허 제 10-0910048 호(특허문헌 2)는 5.28 MGOe의 최대자기에너지적을 얻기 위해서는 함량비로서 0.5의 La와 0.3의 Co가 필요함을 개시하고 있으며, 대한민국 등록특허 제 10-1082389 호(특허문헌 3)는 5.29 MGOe의 최대자기에너지적을 얻기 위해서는 함량비로서 0.415의 La와 0.316의 Co가 필요함을 개시하고 있다. 그러나, La과 Co는 페라이트 소결자석의 주성분인 산화철의 수십 배에서 약 100 배에 해당하는 고가의 원료이어서, 그 함유량이 증가할수록 페라이트 소결자석의 제조비용의 상당한 상승을 초래한다.
이와 같이, 기존에 알려진 조성의 페라이트 자성재료는 시장에서 요구하는 가격에 비해 고가이고 여전히 불만족스러운 자기특성을 가져, 기존 자성재료보다 저가이면서 우수한 자기특성을 갖는 자성재료의 개발이 요구된다.
이에, 본 발명자들은 상기 목적을 달성하기 위하여 지속적인 연구를 수행한 결과, 함량비로서 La를 0.4 미만으로, 그리고 Co를 0.3 미만으로 포함하는 페라이트 조성에서 포화자화와 이방성 자계를 동시에 향상시킬 수 있는 각 원소들의 조합을 연구함으로써, 종래 기술 대비 가격이 저렴하면서도 높은 포화자화 및 이방성 자계로 인해 높은 최대자기에너지적을 제공할 수 있는 페라이트 자성재료를 발견하여 본 발명을 완성하였다.
따라서, 본 발명의 목적은 La와 Co 각각의 함유량을 낮추어 가격이 저렴하면서도 높은 최대자기에너지적을 제공할 수 있는 페라이트 자성재료, 및 이를 소결하여 얻은 페라이트 소결자석을 제공하는 것에 있다.
상기의 목적을 달성하기 위하여, 본 발명은 육방정계 구조를 갖는 마그네토플럼바이트상을 주상으로 하고, 주상을 구성하는 원소가 하기 화학식 1의 조성을 포함하는 것을 특징으로 하는 페라이트 자성재료를 제공한다:
[화학식 1]
Ca(1-x-y)SrxLayFe(2n-m)ComO19
상기 식에서,
0.32 ≤ y ≤ 0.394 이고,
0.251 ≤ m ≤ 0.29 이고,
0.42 ≤ 1-x-y ≤ 0.52 이고,
9.0 ≤ 2n ≤ 10.0 이다.
이와 같이, 본 발명에 따른 페라이트 자성재료로부터 얻어진 페라이트 소결자석은 종래의 자성재료보다 가격이 저렴하면서도 높은 최대자기에너지적((BH)max)을 가져 최근 요구되는 모터의 고효율화 및 소형화에 부합할 수 있다.
도 1은 제조예 1에서 수득한 페라이트 소결자석의 Co 함유량(m)의 변화에 따른 최대자기에너지적((BH)max)의 변화 그래프이다.
도 2는 제조예 2에서 수득한 페라이트 소결자석의 La 함유량(y)의 변화에 따른 최대자기에너지적((BH)max)의 변화 그래프이다.
본 발명의 페라이트 자성재료는 육방정계 구조를 갖는 마그네토플럼바이트상을 주상으로 하고, 주상을 구성하는 원소가 하기 화학식 1의 조성을 포함한다:
[화학식 1]
Ca(1-x-y)SrxLayFe(2n-m)ComO19
La의 함유량(y)이 0.32 내지 0.394의 범위일 때 높은 포화자화 및 이방성 자계가 얻어지고, 이로 인해 높은 최대자기에너지적을 얻을 수 있다. 보다 바람직한 La 함유량은 0.35 내지 0.394 범위이다. La 함유량(y)이 상기 범위 내이면, 비용의 상승을 막고, 비자성상이 생성되어 포화자화와 이방성 자계가 동시에 감소하거나 고용량이 감소되어 높은 최대자기에너지적을 얻을 수 없는 문제를 방지할 수 있다.
Co 함유량(m)이 0.251 내지 0.29의 범위일 때 높은 최대자기에너지적을 얻을 수 있다. Co 함유량(m)이 상기 범위 내이면, 비용의 상승을 막고, 치환 고용량이 감소되어 포화자화 및 이방성 자계가 동시에 감소하거나 소결온도에 따라 상(phase)이 불안정성을 띠어 최대자기에너지적이 감소하는 문제를 방지할 수 있다.
Ca의 함유량(1-x-y)이 0.42 내지 0.52 범위일 때 높은 최대자기에너지적을 얻을 수 있다. 보다 바람직한 Ca 함유량은 0.44 내지 0.50 범위이다. Ca 함유량(1-x-y)이 상기 범위 내이면, 소결온도에 따라 상(phase)이 불안정성을 띠어 최대자기에너지적이 감소하거나 치환 고용량이 감소되어 최대자기에너지적이 감소하는 문제를 방지할 수 있다.
2n은 (Fe+Co)/(Ca+Sr+La)의 함유량을 나타내는 값으로, 2n이 9.0 내지 10.0 범위 내일 때 높은 최대자기에너지적을 얻을 수 있다. 2n이 상기 범위 내이면, 상대적으로 Ca, Sr, La 중량비가 많아져 고용량 초과에 의한 비자성이 생성되어 최대자기에너지적이 감소하거나 미반응된 α-Fe2O3가 생성되어 최대자기에너지적이 감소하는 문제를 방지할 수 있다.
본 발명의 실시예에 따른 페라이트 자성재료 및 소결자석의 제조방법은 하기와 같다.
<혼합 공정>
먼저, 출발원료에 대하여 각 원소의 소정의 비율로부터 중량 %로 환산한 후 이를 칭량한다. 통상적으로 혼합 설비로는 습식 볼밀(wet-type ball mill) 또는 습식 아트라이터(wet-type attritor)를 사용하여 출발원료를 습식 혼합하는데, 이때 습식 볼밀 기준 5 내지 10 시간, 습식 아트라이터 기준 2 내지 4 시간 동안 균일하게 충분히 혼합하여야 한다. 출발원료로는 페라이트 소결자석을 구성하는 SrCO3, CaCO3, La2O3, Fe2O3, Co3O4 등을 사용할 수 있다. 출발원료의 순도에 따라 Al2O3, Cr2O3, NiO, MnO, ZnO, SiO2, MgO, BaO, P, S 등의 불순물이 0.1 내지 1.0 중량%까지 포함될 수 있다.
가소 시 낮은 가소 온도에서 페라이트 반응을 촉진시키고 입자의 성장을 균일하게 하기 위하여, 출발원료에 출발원료 100 중량부 기준 0.05 내지 0.2 중량부의 H3BO3를 추가로 혼합할 수 있다.
<가소 공정>
가소 공정은 이전 공정에서 혼합 및 배합된 조성물의 원료를 가소하여 페라이트화 반응과 함께 M(마그네토플럼바이트)상 구조를 갖는 가소체를 만드는 공정으로, 통상적으로 가소는 공기 중 산화분위기에서 행한다. 가소는 1,150 내지 1,250 ℃의 범위에서 30분 내지 2시간 동안 수행하는 것이 바람직하다. 가소 시간이 길수록 M상의 비율이 높아질 수 있으나, 이는 제조비용의 상승을 초래한다. 가소체의 주상인 M상의 비율은 90% 이상이 좋으며, 조직 내의 입자 크기는 2 내지 4 ㎛로 하는 것이 바람직하다.
<조분쇄 공정>
가소 후의 가소체 상태는 일반적으로 과립이거나 클링커(clinker) 상태이기 때문에 조(粗)분쇄할 수 있다. 분쇄수단은 건식 진동밀 또는 건식 볼밀 등을 사용할 수 있는데, 건식 진동밀을 사용하는 것이 바람직하다. 조분쇄 후 분말(즉, 조분쇄 분말)의 평균 입경은 2 내지 4 ㎛일 수 있다.
<미분쇄 공정>
미분쇄 공정에서 미분의 평균 입경이 0.6 내지 0.8 ㎛일 때 충분한 자기특성을 얻을 수 있다. 미분 평균 입도가 상기 범위 내이면, 페라이트 자성 분말 간의 입자 응집에 의해 배향성이 저하되어 자기특성이 열화되며 성형 시 슬러리의 누설이 발생되거나 탈수 시간이 증가되어 제조비용이 상승하는 문제; 및 다자구가 생성되어 보자력이 급격히 감소되며 충분한 소결밀도를 확보하는데 많은 열에너지가 필요하게 되어 제조비용이 상승하는 문제를 방지할 수 있다.
미분쇄 수단으로는 습식 볼밀 또는 습식 아트라이터를 사용하여 분쇄할 수 있으며, 분쇄시간은 분쇄에너지에 반비례하고 분쇄기 종류에 따라 시간이 달라지므로 분쇄기와 목표 입경에 따라 분쇄시간을 조정할 수 있다.
또한, 소결시 입자의 성장 및 억제를 조절하고 결정 입경의 크기를 조절하기 위하여 미분쇄시 첨가제로서 SiO2, CaCO3 또는 이들의 혼합물을 첨가할 수 있고, 소결시 치환효과를 촉진하고 입자의 성장을 조절하기 위하여 미분쇄 시 첨가제로서 Fe2O3, La2O3, SrCO3, Co3O4 등을 첨가할 수도 있다. 이때, 상기 첨가제의 첨가량이 너무 적으면 효과가 미미하고 너무 많이 넣으면 부의 효과가 일어나기 때문에, 분쇄 분말 100 중량부에 대하여 각각 0.1 내지 10 중량부의 양으로 첨가할 수 있다.
또한, 자장 중 성형 시 슬러리의 유동성 향상과 점도 저하, 배향 효과를 높이기 위해 분산제를 첨가할 수 있는데, 분산제로는 수계 분산제 및 비수계 분산제 모두 사용가능 하지만, 제조공정 중 환경적 측면을 감안하여 수계 분산제를 사용할 수 있다. 수계 분산제로는 수산기 및 카르복실기를 갖는 유기화합물, 솔비톨, 글루콘산칼슘 등을 사용할 수 있다. 분산제는 조분쇄 분말 100 중량부에 대하여 0.1 내지 1.0 중량부의 함량으로 첨가할 수 있다. 분산제 첨가량이 상기 범위 내이면, 탈수성이 저하되어 성형체의 건조 및 소결 시 크랙(crack)이 유발되는 문제를 방지할 수 있다.
<성형 공정>
성형 공정은 습식 이방성 성형방식으로 수행할 수 있으며, 성형 시 자장을 인가하면서 가압 성형하고, 이로 인해 이방성 소결자석의 성형체가 얻어진다.
습식 이방성 성형의 예를 들면, 미분쇄 후 슬러리를 탈수, 농축하여 소정의 농도를 유지하면서 자장 중 성형을 수행한다. 탈수 및 농축은 원심분리장치나 필터 프레스를 이용할 수 있으며, 이때 슬러리 농도는 60 내지 66 중량%, 성형압력은 0.3 내지 0.5 ton/㎠, 인가 자장은 10 내지 20 kOe 일 수 있다.
이렇게 가압성형한 성형체에는 잔류수분이 10 내지 15 중량% 정도 존재하고, 이것을 그대로 소결하면, 승온 시 탈수과정에서 균열을 유발할 수 있으므로, 이를 방지하기 위해 자연건조나 대기 중 저온(50 내지 100 ℃)건조를 수행한 후 소결할 수 있다.
<건조 및 소결 공정>
일반적으로, 대기 중 산화분위기에서 성형체를 연속적으로 건조 및 소결함으로써 페라이트 소결자석을 얻는다. 성형체에 잔류하는 수분의 제거 및 분산제의 탈지를 위해 50 내지 100 ℃에서 탈수 및 탈지를 수행할 수 있다.
소결 공정에서 승온 속도, 최고 온도, 최고 온도 유지시간, 냉각 속도 등의 소결조건을 조절함으로써 페라이트 소결자석의 자기특성을 고성능화시킬 수 있다. 예컨대, 소결 조건(소결 시간, 승온 속도, 최고 온도, 유지시간)에 따라 페라이트 소결자석의 결정입 내의 치환원소 고용농도 증대, 입자 결정 성장 조절, 입자크기 균일 유지 및 소결자석의 밀도와 배향도를 조절하여 자기특성을 제어할 수 있다. 승온 시간 1 내지 10 ℃/분, 소결 최고 온도 1,200 내지 1,250 ℃에서 30분 내지 2시간 동안 소결하고, 냉각 시간 1 내지 10 ℃/분으로 냉각할 수 있다.
상술한 바와 같이, 상기 페라이트 자성재료를 소결시켜 얻어진 본 발명의 마그네토플럼바이트형 페라이트 소결자석은 포화자화(4πIs)가 4.8 kG 이상이면서 이방성 자계(HA)가 26 kOe 이상일 때, 최대자기에너지적((BH)max)이 5.5 MGOe 이상의 자기특성을 갖는다. 4πI-H 곡선은 자성체에 자장을 걸어 자기모멘트와 자기분극을 생기게 하는 조작을 의미하는 자화(磁化)와 관계된 것으로서, 자석내부(자석고유)의 특성을 나타낸다.
또한, 본 발명은 페라이트 자성재료로부터 유도된 세그멘트형 또는 블록형 등의 영구자석을 제공한다.
나아가, 본 발명의 영구자석은 자동차, 전기기구, 가전기기에 사용되는 회전기, 센서 및 본드자석 등에 사용될 수 있다.
이하, 본 발명을 하기 실시예에 의거하여 좀 더 상세하게 설명하고자 한다. 단, 하기 실시예는 본 발명을 예시하기 위한 것일 뿐, 본 발명의 범위가 이들만으로 제한되는 것은 아니다.
[실시예]
참조예. 자기특성 및 밀도 측정
하기 제조예에서 제조한 페라이트 소결자석에 대해 20 ℃의 대기 분위기에서 최대 인가자장 25 kOe(1,990 kA/m)의 B-H Curve Tracer를 사용하여 최대자기에너지적((BH)max)을 측정하였다. 또한, 페라이트 소결자석을 폭 5 mm, 두께 5 mm로 절단한 후 배향면의 수직한 면과 평행한 면에 대해 각각 4πI-H 곡선 1 사분면에서의 포화자화(4πIs) 및 이방성 자계(HA) 값을 측정하였고, 페라이트 자석의 밀도는 아르키메데스법에 의해 측정하였다.
제조예 1.
제조예 1-1: 혼합 공정
출발원료로서 산화철(Fe2O3, 순도 99% 이상), 탄산스트론튬(SrCO3), 탄산칼슘(CaCO3), 산화란탄(La2O3) 및 산화코발트(Co3O4)를 사용하였다. 이러한 출발원료를 하기 표 1에 기재된 바와 같은 조성을 만족하는 Ca(1-x-y)SrxLayFe(2n-m)ComO19의 페라이트 소결자석이 얻어지도록 배합하였다. 배합원료에 페라이트 반응 촉진을 위하여, 배합원료 총 중량 대비 0.1 중량%의 H3BO3을 첨가하였다. 배합된 원료를 물과 혼합하여 농도 40 중량%로 만든 후 2 시간 동안 습식 순환 혼합하였다. 이렇게 만든 원료를 130 ℃에서 24시간 동안 건조하였다.
제조예 1-2: 가소 공정
상기 제조예 1-1에서 건조된 분말을 1,200 ℃에서 1시간 동안 대기 중에서 가소하여 가소체를 얻었다.
제조예 1-3: 조분쇄 및 미분쇄 공정
제조예 1-2의 가소체는 건식 진동밀을 이용하여 평균 입경 4 ㎛의 조분쇄 분말을 얻었다. 조분쇄된 분말은 미분쇄하기 위해 순환식 아트라이터에 조분쇄 분말의 농도가 40 중량%가 되도록 조분쇄 분말과 물을 넣고, 조분쇄 분말에 대하여 CaCO3 1.0 중량%, SiO2 0.40 중량% 및 글루콘산칼슘 0.6 중량%를 첨가하여(조분쇄 분말 총 함량을 기준으로 첨가), 상기 표 1과 같은 소결체 조성이 얻어지도록 하였다. 미분쇄 후 분말의 평균 입경은 0.65 ㎛가 되도록 하였다.
제조예 1-4: 성형 공정
제조예 1-3에서 얻어진 미분쇄 분말 및 물의 혼합물인 슬러리를 미분쇄 분말의 농도가 63 중량%가 되도록 탈수한 후 자장 방향이 가압방향과 평행한 습식 자장 성형기를 이용하여 디스크형(직경 40 mm X 두께 11 mm)의 성형체 샘플을 제작하였다. 이때 자계강도는 10 kOe(796 kA/m), 성형압력은 0.4 Ton/㎠으로 설정하였다.
제조예 1-5: 소결 공정
제조예 1-4에서 얻어진 성형체를 1,210 ℃에서 1 시간 동안 소결하고, 얻어진 소결체는 양면 두께 가공기를 이용하여 7 ㎜ 두께로 가공하여 페라이트 소결자석을 수득하였다. 또한, 수득한 페라이트 소결자석의 자기특성 및 밀도를 측정하여 하기 표 1에 나타냈고, 수득한 페라이트 소결자석의 Co 함유량(m) 변화에 따른 최대자기에너지적((BH)max)의 변화를 도 1에 나타냈다.
시료No. Sr(x) Fe(2n-m) La(y) Ca(1-x-y) Co(m) 2n 소결밀도(g/cm3) 4πIs(kG) HA (kOe) (BH)max(MGOe)
1 0.170 9.355 0.385 0.445 0.303 9.66 5.094 4.75 27.0 5.21
2 0.170 9.367 0.385 0.445 0.290 9.66 5.103 4.82 26.8 5.53
3 0.170 9.381 0.385 0.445 0.279 9.66 5.105 4.85 26.6 5.55
4 0.170 9.390 0.385 0.445 0.267 9.66 5.098 4.84 26.4 5.53
5 0.170 9.411 0.385 0.445 0.251 9.66 5.108 4.82 26.3 5.52
6 0.170 9.420 0.385 0.445 0.240 9.66 5.099 4.77 25.5 5.30
7 0.170 9.435 0.385 0.445 0.220 9.66 5.098 4.72 24.8 5.11
표 1에서 보는 바와 같이, 시료 1, 6 및 7은 본 발명의 비교예에 해당되고, 시료 2 내지 5은 본 발명의 실시예가 된다.
Co의 함유량(m)이 0.251 내지 0.29일 때 최대자기에너지적((BH)max))이 5.5 MGOe 이상으로 나타났으며, 이는 Co 함유량이 상기 범위를 벗어나는 비교예에 비해 현저히 높은 값이었다.
제조예 2.
La의 함유량(y)을 비롯한 전체적인 소결체 조성비를 하기 표 2에 기재한 바와 같이 변화시킨 것 이외에는 제조예 1과 동일하게 페라이트 소결자석을 제조하였으며, 수득한 페라이트 소결자석의 자기특성 및 밀도를 측정하여 하기 표 2에 나타냈다. 또한, 수득한 페라이트 소결자석의 La 함유량(y) 변화에 따른 최대자기에너지적((BH)max)의 변화를 도 2에 나타냈다.
시료No. Sr(x) Fe(2n-m) La(y) Ca(1-x-y) Co(m) 2n 소결밀도(g/cm3) 4πIs(kG) HA(kOe) (BH)max(MGOe)
8 0.135 9.402 0.420 0.445 0.265 9.67 5.112 4.77 25.8 5.31
9 0.146 9.402 0.394 0.460 0.265 9.67 5.107 4.85 26.5 5.54
10 0.157 9.404 0.372 0.471 0.265 9.67 5.105 4.84 26.5 5.53
11 0.166 9.413 0.350 0.485 0.260 9.67 5.106 4.84 26.5 5.52
12 0.175 9.419 0.330 0.495 0.260 9.68 5.101 4.82 26.4 5.50
13 0.178 9.419 0.320 0.502 0.260 9.68 5.093 4.81 26.4 5.50
14 0.181 9.422 0.310 0.509 0.260 9.68 5.084 4.73 26.0 5.21
표 2에서 보는 바와 같이, 시료 8 및 14는 본 발명의 비교예에 해당되고, 시료 9 내지 13은 본 발명의 실시예가 된다.
La의 함유량(y)이 0.32 내지 0.394일 때 5.5 MGOe 이상의 최대자기에너지적을 얻을 수 있었다. La 함유량이 0.394를 초과할 경우 페라이트 주상에 고용되지 않은 La이 비자성상인 오르소페라이트(orthoferrite)를 생성시켜 최대자기에너지적이 감소되었고, 0.32 미만일 경우 La의 치환 고용량이 충분하지 않아 4πIs가 감소되어 본 발명에서 요구되는 최대자기에너지적을 얻을 수 없었다.
제조예 3.
Ca의 함유량(1-x-y)을 하기 표 3과 같이 변화시킨 것 이외에는 제조예 1과 동일하게 페라이트 소결자석을 제조하였으며, 수득한 페라이트 소결자석의 자기특성 및 밀도를 측정하여 하기 표 3에 나타냈다.
시료No. Sr(x) Fe(2n-m) La(y) Ca(1-x-y) Co(m) 2n 소결밀도(g/cm3) 4πIs(kG) HA(kOe) (BH)max(MGOe)
15 0.092 9.409 0.370 0.538 0.265 9.67 5.121 4.75 24.3 5.15
16 0.110 9.408 0.370 0.520 0.265 9.67 5.114 7.83 26.2 5.51
17 0.131 9.411 0.370 0.499 0.265 9.68 5.108 4.83 26.3 5.52
18 0.149 9.407 0.370 0.481 0.265 9.67 5.111 4.85 26.4 5.54
19 0.172 9.405 0.370 0.458 0.265 9.67 5.107 4.85 26.4 5.53
20 0.189 9.412 0.370 0.441 0.265 9.68 5.106 4.82 26.5 5.52
21 0.210 9.408 0.370 0.420 0.265 9.67 5.102 4.81 26.2 5.50
22 0.230 9.406 0.370 0.400 0.265 9.67 5.095 4.73 25.5 5.30
표 3에서 보는 바와 같이, 시료 15 및 22는 본 발명의 비교예에 해당되고, 시료 16 내지 21은 본 발명의 실시예가 된다.
Ca의 함유량(1-x-y)이 0.42 내지 0.52일 때 5.5 MGOe 이상의 최대자기에너지적을 얻을 수 있었다. Ca의 함유량이 0.42 미만일 경우, Ca의 치환 고용량 감소에 의한 포화자화 및 이방성 자계의 감소로 높은 최대자기에너지적을 얻을 수 없었다. 또한, Ca 함유량이 0.52를 초과할 경우, 급격한 입자성장에 의한 상(phase) 불안정성으로 이방성 자계(HA) 및 최대자기에너지적이 감소되었다.
제조예 4.
2n을 하기 표 4와 같이 변화시킨 것 이외에는 제조예 1과 동일하게 페라이트 소결자석을 제조하였으며, 수득한 페라이트 소결자석의 자기특성 및 밀도를 측정하여 하기 표 4에 나타냈다.
시료No. Sr(x) Fe(2n-m) La(y) Ca(1-x-y) Co(m) 2n 소결밀도(g/cm3) 4πIs(kG) HA(kOe) (BH)max(MGOe)
23 0.170 8.651 0.370 0.460 0.265 8.92 5.117 4.70 24.7 5.15
24 0.170 8.735 0.370 0.460 0.265 9.00 5.115 4.83 26.4 5.51
25 0.170 9.064 0.370 0.460 0.265 9.32 5.114 4.83 26.6 5.52
26 0.170 9.353 0.370 0.460 0.265 9.61 5.108 4.84 26.7 5.53
27 0.170 9.730 0.370 0.460 0.265 10.00 5.104 4.82 26.5 5.51
28 0.170 9.911 0.370 0.460 0.265 10.18 5.085 4.75 26.8 5.29
표 4에서 보는 바와 같이, 시료 23 및 28은 본 발명의 비교예에 해당되고, 시료 24 내지 27은 본 발명의 실시예가 된다.
2n이 9.0 내지 10.0일 때 5.5 MGOe 이상의 최대자기에너지적을 얻을 수 있었다. 2n이 9.0 미만이면 Fe를 제외한 모든 원소가 상대적으로 많아져 치환 고용량이 초과하고, 이로 인해 포화자화 및 이방성 자계가 감소되어 최대자기에너지적도 감소되었다. 또한, 2n이 10.0을 초과하면 미반응된 α-Fe2O3가 생성되어 포화자화 및 이방성 자계가 감소되고, 이로 인해 최대자기에너지적이 감소되었다.

Claims (4)

  1. 육방정계 구조를 갖는 마그네토플럼바이트상을 주상으로 하고, 주상을 구성하는 원소가 하기 화학식 1의 조성을 포함하는 것을 특징으로 하는 페라이트 자성재료:
    [화학식 1]
    Ca(1-x-y)SrxLayFe(2n-m)ComO19
    상기 식에서,
    0.32 ≤ y ≤ 0.394 이고,
    0.251 ≤ m ≤ 0.29 이고,
    0.42 ≤ 1-x-y ≤ 0.52 이고,
    9.0 ≤ 2n ≤ 10.0 이다.
  2. 제 1항에 있어서, 상기 y 값이 0.35 ≤ y ≤ 0.394 인 것을 특징으로 하는 페라이트 자성재료.
  3. 제 1항에 있어서, 상기 1-x-y 값이 0.44 ≤ 1-x-y ≤ 0.50 인 것을 특징으로 하는 페라이트 자성재료.
  4. 제1항 내지 제3항 중 어느 한 항의 페라이트 자성재료를 소결시켜 얻어지며,
    포화자화(4πIs)가 4.8 kG 이상이면서 이방성 자계(HA)가 26 kOe 이상일 때, 최대자기에너지적((BH)max)이 5.5 MGOe 이상인, 페라이트 소결자석.
PCT/KR2017/005878 2016-06-20 2017-06-07 페라이트 자성재료 및 페라이트 소결자석 WO2017222212A1 (ko)

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