Patent Grant
11972885
This application is the U.S. National Phase under 35 U.S.C. § 371 of International Application PCT/JP2012/050058, filed Jan. 5, 2012, which claims priority to Japanese Patent Applications No. 2011-184223, filed Aug. 26, 2011. The International Application was published under PCT Article 21(2) in a language other than English.
The present invention relates to a magnetic material that can be used primarily as a core of coil inductor, etc., as well as a coil component using the same.
Coil components such as inductors, choke coils, and transformers (so-called inductance components) have a magnetic material and a coil formed inside or on the surface of the magnetic material. For the magnetic material, Ni—Cu—Zn ferrite or other type of ferrite is generally used.
Coil components of this type have been facing a demand for larger current (higher rated current) in recent years. To meet this demand, proposals have been made to replace the material of the magnetic body from ferrite as had been traditionally used, to Fe—Cr—Si alloy, Fe—Al—Si alloy or other soft magnetic alloy, where these proposed alloys are characterized by their higher saturated magnetic flux density compared to ferrite. On the other hand, their volume resistivity is significantly lower than that of ferrite.
Patent Literature 1 discloses a complex magnetic material using grains of Fe—Al—Si alloy with alumina film formed around them. Patent Literature 2 discloses a complex magnetic body that contains metal magnetic powder and thermosetting resin, with the metal magnetic powder present at a specific fill ratio.
To expand the scope of application of magnetic materials using soft magnetic alloy, it is desired that compacts of soft magnetic alloy grains be made stronger. The object of the present invention is to provide a magnetic material comprising a compact of soft magnetic alloy grains and constituted in a manner achieving improved mechanical strength, as well as a coil component using such magnetic material.
After studying in earnest, the inventors of the present invention completed the invention relating to a magnetic material, the details of which are described below.
The magnetic material proposed by the present invention comprises a grain compact produced by compacting metal grains having oxide film. The metal grains are constituted by Fe—Si—M soft magnetic alloy (where M represents a metal element that oxidizes more easily than iron). Metal grains in the grain compact are mutually bonded with adjacent metal grains by means of inter-bonding of their oxide films. At least some of this bonding of oxide films takes the form of bonding of crystalline oxides, and preferably at least some of this bonding of crystalline oxides is based on continuous lattice bond. In the meantime, preferably the aforementioned inter-bonding of oxide films is generated by means of heat treatment. According to another embodiment of the present invention, various types of coil components using the aforementioned magnetic material are provided.
According to the present invention, metal grains are bonded together by means of bonding of crystalline oxides in the grain compact, so a magnetic material offering high strength can be obtained. In a favorable embodiment, the aforementioned bond has continuously lattice-bonded oxides, which improves the strength further.
The present invention is described in detail by referring to the drawings as appropriate. It should be noted, however, that the present invention is not at all limited to the illustrated embodiments and that, because the characteristic parts of the invention may be emphasized in the drawings, the scale of each part of the drawings is not necessarily accurate. According to the present invention, the magnetic material comprises a grain compact produced by compacting specific grains. Under the present invention, the magnetic material plays the role of a magnetic path in a coil inductor or other coil component, and typically takes the form of a core of a coil component, etc.
The oxide film 12 formed roughly all around individual metal grains 11 may be formed in the material grain stage before the grain compact 1 is formed. Or, the oxide film may be generated in the compacting process using material grains in which oxide film is absent or minimal. Presence of oxide film 12 can be recognized as a contrast (brightness) difference on an image captured with a scanning electron microscope (SEM) at around 3000 magnifications. Presence of oxide film 12 assures the insulation property of the magnetic material as a whole.
In the grain compact 1, inter-bonding of grains is primarily based on inter-bonding 22 of oxide films 12. Presence of inter-bonding 22 of oxide films 12 can be clearly determined by, for example, visually recognizing on a SEM image, etc., taken at around 3000 magnifications that the oxide films 12 of adjacent metal grains 11 have the same phase. Presence of inter-bonding 22 of oxide films 12 improves the mechanical strength and insulation property.
According to the present invention, at least some of the many bonds 22 present in the grain compact 1 are based on crystalline oxides. Because not all inter-bonds 22 of oxide films 12 are amorphous, but crystalline oxides are also present, the inter-bonding of metal grains 11 becomes stronger and the strength of the grain compact 1 improves as a result.
That the inter-bonding 22 of oxide film 12 is that of oxides having crystallinity can be verified by, for example, obtaining an X-ray diffraction pattern of the grain compact 1 and then checking whether or not there is a diffraction peak of the applicable crystalline oxide.
According to a favorable embodiment of the present invention, at least some of the many bonds 22 present in the grain compact 1 are based on continuously lattice-bonded crystalline oxides. In
According to the present invention, preferably the oxide films 12 of adjacent metal grains 11 are bonded together over the entire grain compact 1, but as long as they are bonded at least partially, considerable improvement in mechanical strength and insulation property can be achieved and this mode is also considered an embodiment of the present invention. Preferably inter-bonds 22 of oxide films 12 equal to or greater than the number of metal grains 11 contained in the grain compact 1 are present. Additionally, inter-bonds of metal grains 11 (not illustrated), which are not via inter-bonding of oxide films 12, may be present partially. Furthermore, a mode may be partially present where adjacent metal grains 11 are simply in contact with or in close proximity to each other physically, without inter-bonding of oxide films 12 or inter-bonding of metal grains 11.
Methods to generate inter-bonding 22 of oxide films 12 include, for example, applying heat treatment at a specified temperature as described later in an ambience where oxygen is present (such as in air), when the grain compact 1 is manufactured. Preferably, generating oxide film 12 through the heat treatment facilitates the formation by the oxide film 12 of a bond 22 having a continuous lattice bond. To be more specific, preferably oxide film 12 is formed as a result of oxidization, by the heat treatment, of the part that was metal in the material grain stage, as this facilitates the formation of a bond 22 having a continuous lattice bond.
According to the present invention, not only inter-bonding 22 of oxide films 12, but also inter-bonding of metal grains 11 (metal bonding) can be present in the grain compact 1. As is the case with the aforementioned inter-bonding 22 of oxide films 12, presence of metal bonding can be clearly determined by, for example, visually recognizing on a SEM image, etc., taken at around 3000 magnifications that the adjacent metal grains 11 have bonding points while maintaining the same phase. Presence of metal bonding improves the magnetic permeability further.
Methods to generate metal bonding include, for example, using grains with less oxide film as material grains, adjusting the temperature and partial oxygen pressure as described later during the heat treatment applied to manufacture the grain compact 1, and adjusting the compacting density when the grain compact 1 is obtained from the material grains.
The individual metal grains 11 are primarily constituted by specific soft magnetic alloy. Under the present invention, the metal grain 11 is constituted by Fe—Si—M soft magnetic alloy. Here, M is a metal element that oxidizes more easily than iron, and is typically chromium, aluminum, titanium, etc., and preferably chromium or aluminum. Particularly when chromium is used, the metal grain becomes relatively soft, which makes it possible to achieve a higher compacting density through deformation of grains. It also permits generation of many inter-bonds of oxide films.
The Si content in the Fe—Si—M soft magnetic alloy is preferably 0.5 to 7.0 percent by weight, or more preferably 2.0 to 5.0 percent by weight. A higher Si content is preferable in that it leads to high resistance and high magnetic permeability, while a lower Si content is associated with good compactibility.
If M above is chromium, the Cr content in the Fe—Si—M soft magnetic alloy is preferably 2.0 to 15 percent by weight, or more preferably 3.0 to 6.0 percent by weight. Presence of chromium lowers the magnetic characteristics before heat treatment that represent the physical properties of the material grain, but it suppresses excessive oxidization during heat treatment. This means that more Cr leads to a greater effect of raising the magnetic permeability through heat treatment, while lowering the specific resistance after heat treatment. The above preferable range is proposed in consideration of the foregoing.
If M above is aluminum, the Al content in the Fe—Si—M soft magnetic alloy is preferably 2.0 to 15 percent by weight, or more preferably 3.0 to 6.0 percent by weight. Presence of aluminum is preferable in that it leads to formation of a passive state to suppress excessive oxidization during heat treatment, while allowing for expression of strength and insulation resistance; on the other hand, however, less aluminum is preferable from the viewpoint of improving magnetic characteristics. The above preferable range is proposed in consideration of the foregoing. It should be noted that the preferable contents of each metal component in Fe—Si—M soft magnetic alloy as mentioned above assume that the total amount of all alloy component represents 100 percent by weight. In other words, oxide film composition is excluded in the calculations of preferable contents above.
Preferably the remainder of the Fe—Si—M soft magnetic alloy other than Si and metal M, except for unavoidable impurities, is iron. Metals that may be contained other than Fe, Si, and M include manganese, cobalt, nickel and copper.
The chemical composition of the alloy constituting each metal grain 11 in the grain compact 1 can be calculated, for example, by capturing a section of the grain compact 1 with a scanning electron microscope (SEM) and then analyzing the composition by energy dispersive X-ray spectroscopy (EDS) according to the ZAF method.
The size of each material grain is virtually equivalent to the size of the metal grain constituting the grain compact 1 in the magnetic material to be finally obtained. When the magnetic permeability and in-grain eddy current loss are considered, the size of the material grain based on d50 is preferably 2 to 30 μm, or more preferably 2 to 20 μm, or yet more preferably 3 to 13 μm. The d50 of the material grain can be measured using a laser diffraction/scattering measuring system.
The material grain is preferably a grain manufactured per the atomization method. As mentioned above, preferably the part that was metal in the material grain stage is oxidized through heat treatment when bonding 22 via oxide films 12 is formed in the grain compact 1. For this reason, it is better that oxide film is not present excessively in the material grain, although oxide film can be present. Means for reducing the oxide film in the material grain includes, among others, putting the material grain through heat treatment in a reducing ambience or through chemical or other treatment such as removing the surface oxide layer using acid.
For the aforementioned material grain, any known alloy grain manufacturing method may be adopted, or PF20-F by Epson Atmix, SFR-FeSiAl by Nippon Atomized Metal Powders or other commercial product may be used.
The method to obtain the compact from the material grain is not limited in any way, and any known means in the field of grain compact manufacturing can be incorporated as deemed appropriate. The following illustrates a typical manufacturing example based on a manufacturing method where the coil component is a laminated inductor. First, a doctor blade, die-coater, or other coating machine is used to coat the surface of a base film made of resin, etc., with a magnetic paste (slurry) prepared beforehand. The coated film is then dried with a hot-air dryer or other dryer to obtain a green sheet. The magnetic paste contains material grains 11 and, typically, polymer resin as a binder, and solvent.
Preferably the magnetic paste contains polymer resin as a binder. The type of polymer resin is not limited in any way and may be polyvinyl butyral (PVB) or other polyvinyl acetal resin, for example. The type of solvent in the magnetic paste is not limited in any way and butyl carbitol or other glycol ether can be used, for example. The blending ratio of soft magnetic alloy grains, polymer resin, solvent, etc., in the magnetic paste, among other conditions, can be adjusted as deemed appropriate, and the viscosity and other properties of the magnetic paste can also be set this way.
For the specific method to obtain a green sheet by coating and drying a magnetic paste, any prior art can be applied as deemed appropriate. The green sheet may be rolled, as well. Rolling can be done using a calendar roll, roll press, etc. Rolling is done by applying a load of 1800 kgf or more, or preferably 2000 kgf or more, or more preferably 2000 to 8000 kgf, for example, at a temperature of 60° C. or above, or preferably 60 to 90° C., for example.
Next, the green sheet is punched with a stamping machine, laser processing machine, or other punching machine to form through holes in a specific pattern. The pattern of through holes is set so that when multiple sheets, each prepared this way, are stacked on top of each other, a coil will be formed by the through holes filled with a conductor, and the conductor patterns. For the through hole patterns and conductor pattern shapes for forming a coil, any prior art can be applied as deemed appropriate, and a specific example is also explained in “Example” later by referring to the drawings.
Preferably a conductive paste is used to fill the through holes and print conductive patterns. The conductive paste contains conductive grains and, typically, polymer resin as a binder, and solvent.
For the conductive grains, silver grains, etc., can be used. The size of the conductive grain based on volume is such that preferably the d50 is 1 to 10 μm. The d50 of the conductive grain is measured with a grain size/granularity distribution measuring system applying the laser diffraction/scattering method (such as Microtrac by Nikkiso Co., Ltd., for example).
Preferably the conductive paste contains polymer resin as a binder. The type of polymer resin is not limited in any way and may be polyvinyl butyral (PVB) or other polyvinyl acetal resin, for example. The type of solvent in the conductive paste is not limited in any way and butyl carbitol or other glycol ether can be used, for example. The blending ratio of conductive grains, polymer resin, solvent, etc., in the conductive paste, among other conditions, can be adjusted as deemed appropriate, and the viscosity and other properties of the conductive paste can also be set this way.
Next, a screen printer, gravure printer, or other printing machine is used to print the conductive paste on the surface of each green sheet, after which the printed sheet is dried with a hot-air dryer or other dryer to form a conductive pattern corresponding to a coil. During printing, the aforementioned through hole is filled with some of the conductive paste. As a result, the conductive paste filling the through holes, and the printed conductive patterns will together constitute a coil shape.
Using a suction transfer machine and press, the printed green sheets are stacked on top of each other in a specified order and then thermally compressed to produce a laminate. Next, a dicer, laser processing machine, or other cutting machine is used to cut the laminate to the component body size to produce a chip before heat treatment.
A sintering furnace or other heating system is used to heat-treat the chip before heat treatment in an oxidizing ambience such as atmosphere. This heat treatment normally includes a binder removal process and oxide film forming process, where the binder removal process is implemented under the condition of heating for approx. 1 hour at a temperature around which the polymer resin used as the binder disappears, such as approx. 300° C., for example, while the oxide film forming process is implemented under the condition of approx. 750° C. for approx. 2 hours, for example.
In the chip before heat treatment, many fine gaps exist between individual metal grains 11, and normally these fine gaps are filled with a mixture of solvent and binder. The mixture disappears in the binder removal process, so once the binder removal process is completed, the fine gaps turn into pores. Also in the chip before heat treatment, many fine gaps also exist between conductive grains. These fine gaps are filled with a mixture of solvent and binder. This mixture also disappears in the binder removal process.
In the oxide film forming process following the binder removal process, the alloy grains 11 pack together closely to produce a grain compact 1 and, typically when this happens, the oxide films 12 on the surfaces of respective alloy grains 11 form bond 22 together, where at least some of these bonds 22 are constituted by crystalline oxides and preferably characterized by continuous lattice bonding. In this state, the conductive grains are sintered to form a coil. As a result, a laminated inductor is obtained.
Normally, external terminals are formed after the heat treatment. A dip coater, roller coater, or other coating machine is used to coat a conductive paste prepared beforehand on both longitudinal ends of the component body, and the coated component body is then baked using a sintering furnace or other heating system under the condition of approx. 600° C. for approx. 1 hour, for example, to form external terminals. For the conductive paste for external terminals, the aforementioned paste for printing conductive patterns or any similar paste can be used as deemed appropriate.
As another method for manufacturing a coil component using the magnetic material proposed by the present invention, a method whereby material grains are compacted under non-heating conditions and then put through heat treatment is explained.
When compacting the material grains under non-heating conditions, it is preferable to add organic resin as a binder. For the organic resin, it is preferable to use one constituted by acrylic resin, butyral resin, vinyl resin, or other resin whose thermal decomposition temperature is 500° C. or below, as less binder will remain after the heat treatment. Any known lubricant may be added at the time of compacting. The lubricant may be organic acid salt, etc., where specific examples include zinc stearate and calcium stearate. The amount of lubricant is preferably 0 to 1.5 parts by weight, or more preferably 0.1 to 1.0 parts by weight. When the amount of lubricant is zero, it means no lubricant is used. Material grains are agitated after adding a binder and/or lubricant as desired, and then the agitated material grains are compacted to a desired shape. Compacting is done by applying a pressure of 5 to 10 t/cm2, for example. In this stage, it is highly likely that neither inter-bonding 22 of oxide films nor metal bonding is generated.
A favorable embodiment of heat treatment is explained. Preferably heat treatment is performed in an oxidizing ambience. To be more specific, the oxygen concentration is preferably 1% or more during heating, as it promotes the generation of both bonds 22 that interconnect oxide films and the metal bonding. Although the upper limit of oxygen concentration is not specified in particular, the oxygen concentration in air (approx. 21%) may be used, for example, in consideration of manufacturing cost, etc. The heating temperature is preferably 600° C. or above from the viewpoint of generating oxide film 12 constituted by crystalline oxide to facilitate the generation of inter-bonding 22 of oxide films 12 having continuous lattice bonds, but it is also preferably 900° C. or below from the viewpoint of suppressing oxidization to an appropriate level to maintain the presence of metal bonding and thereby raise the magnetic permeability. More preferably the heating temperature is 700 to 800° C. The heating time is preferably 0.5 hour or more from the viewpoint of facilitating the formation of continuous lattice bonding by the inter-bonding 22 of oxide films 12. The heating time is preferably 0.5 to 3 hours from the viewpoint of facilitating not only the generation of inter-bonding 22 of oxide films 12, but also that of metal bonding.
Voids 30 may be present in the obtained grain compact 1. Polymer resin (not illustrated) may be impregnated in at least some of the voids 30 present in the grain compact 1. Means for impregnating polymer resin include, for example, soaking the grain compact 1 in a liquid of polymer resin such as liquefied polymer resin or a solution of polymer resin and then lowering the pressure of the manufacturing system, or coating the aforementioned liquid of polymer resin on the grain compact 1 and letting it seep into the voids 30 near the surface. Impregnating polymer resin in the voids 30 of the grain compact 1 provides advantages such as higher strength and suppressed hygroscopic property. Examples of polymer resin include, but are not limited to, epoxy resin, fluororesin, and other organic resins, as well as silicone resin.
The magnetic material constituted by the grain compact 1 thus obtained can be used as a constituent of various types of electronic components. For example, the magnetic material proposed by the present invention may be used as a core and insulating-sheathed conductive wires are wound around it to form a coil component. In addition to the above, the magnetic material proposed by the present invention may be used as an element body and a coil is formed on the interior or surface of the element body to obtain various coil components. The aforementioned laminated inductor is also an embodiment of coil component. The coil component may be of surface mounting type, through-hole mounting type or any of the various mounting patterns, and for the means for obtaining the coil component from the magnetic material, including the means for constituting the coil component of any of these mounting patterns, any known manufacturing method in the field of electronic components can be incorporated as deemed appropriate.
The present invention is explained specifically below using examples. It should be noted, however, that the present invention is not at all limited to the embodiments described in these examples.
[Specific Structure of Coil Component]
An example of specific structure of the coil component manufactured in this example is explained. The coil component is approx. 3.2 mm long, approx. 1.6 mm wide, and approx. 0.8 mm high, and forms a rectangular solid shape as a whole.
The coil 43 has a structure where a total of five coil segments CS1 to CS5 are spirally joined together with a total of four relay segments IS1 to IS4 connecting the coil segments CS1 to CS5, and is wound by approx. 3.5 times. This coil 43 is obtained primarily by heat-treating silver grains, where the volume-based size d50 of the silver grain used as the material is 5 μm.
The four coil segments CS1 to CS4 have a C shape, and the one coil segment CS5 has a band shape. The coil segments CS1 to CS5 each have a thickness of approx. 20 μm and width of approx. 0.2 mm. The top coil segment CS1 has, as a continuous part, an L-shaped leader part LS1 used to connect to the external terminal 44, while the bottom coil segment CS5 has, as a continuous part, an L-shaped leader part LS2 used to connect to the external terminal 45. The relay segments IS1 to IS4 each have a columnar shape penetrating the magnetic layers ML1 to ML4, and each has a bore of approx. 15 μm.
The external terminals 44, 45 each extend to each longitudinal end face of the component body 41 and the four side faces near the end face, and each has a thickness of approx. 20 μm. The one external terminal 44 connects to the edge of the leader part LS1 of the top coil segment CS1, while the other external terminal 45 connects to the edge of the leader part LS2 of the bottom coil segment CS5. These external terminals 44, 45 are obtained primarily by heat-treating silver grains whose volume-based size d50 is 5 μm.
[Manufacturing of Laminated Inductor]
A magnetic paste constituted by 85 percent by weight of the aforementioned Fe—Cr—Si alloy, 13 percent by weight of butyl carbitol (solvent), and 2 percent by weight of polyvinyl butyral (binder) was prepared. Using a doctor blade the magnetic paste was coated on the surface of a plastic base film, after which the coated film was dried with a hot-air dryer under the condition of approx. 80° C. for approx. 5 minutes. A green sheet was thus obtained on the base film. This base film and green sheet were rolled at approx. 70° C. under a load of 2000 kgf using a calendar roll. Thereafter, the green sheet was cut to obtain first through sixth sheets, respectively corresponding to the magnetic layers ML1 to ML6 (refer to
Next, a punching machine was used to punch the first sheet corresponding to the magnetic layer ML1, and a through hole corresponding to the relay segment IS1 was formed according to a specific pattern. Similarly, through holes corresponding to the relay segments IS2 to IS4 were formed, according to specific patterns, in the second through fourth sheets corresponding to the magnetic layers ML2 to ML4.
Next, a printing machine was used to print on the surface of the first sheet a conductive paste constituted by 85 percent by weight of the aforementioned Ag grains, 13 percent by weight of butyl carbitol (solvent), and 2 percent by weight of polyvinyl butyral (binder), after which the printed sheet was dried with a hot-air dryer under the condition of approx. 80° C. for approx. 5 minutes, and then a first printed layer corresponding to the coil segment CS1 was produced according to a specific pattern. Similarly, second through fifth printed layers corresponding to the coil segments CS2 to CS5 were produced according to specific patterns on the surfaces of the second through fifth sheet, respectively.
Since the through holes formed in the first through fourth sheets are respectively positioned in a manner overlapping with the ends of the first through fourth printed layers, some of the conductive paste is filled in the through holes when the first through fourth printed layers are printed, to form first through fourth filled areas corresponding to the relay segments IS1 to IS4.
Next, a suction transfer machine and press were used to stack on top of each other and thermally compress in the order shown in
Next, a sintering furnace was used to heat-treat multiple chips-before-heat-treatment in an atmospheric ambience at once. First, they were heated under the condition of approx. 300° C. for approx. 1 hour as the binder removal process. Second, they were heated under the condition of approx. 750° C. for approx. 2 hours as the oxide film forming process. Because of this heat treatment, the soft magnetic alloy grains packed together closely and formed a grain compact 1, while the silver grains were sintered and formed a coil 43, and a component body 41 was obtained as a result.
Next, external terminals 44, 45 were formed. A conductive paste containing 85 percent by weight of the aforementioned silver grains, 13 percent by weight of butyl carbitol (solvent), and 2 percent by weight of polyvinyl butyral (binder) was coated using a coating machine on both longitudinal ends of the component body 41, after which the coated component body was sintered in a sintering furnace under the condition of approx. 600° C. for approx. 1 hour. As a result, the solvent and binder disappeared and the silver grains were sintered to form external terminals 44, 45, and consequently a coil component was obtained.
A SEM (3000 magnifications) was used to confirm the presence of inter-bonding of oxide films in the grain compact of the obtained coil component, and a STEM bright-field image was obtained at 10000 magnifications to confirm the presence of continuous lattice bonds. A powder X-ray diffraction pattern of the grain compact of this coil component was obtained.
1: Grain compact, 11: Metal grain, 12: Oxide film, 22: Inter-bonding of oxide films, 30: Void, 40: Coil component, 41: Component body, 43: Coil, 44, 45: External terminal
| Number | Date | Country | Kind |
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| 2011-184223 | Aug 2011 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2012/050058 | 1/5/2012 | WO | 3/7/2014 |
| Publishing Document | Publishing Date | Country | Kind |
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| WO2013/031243 | 3/7/2013 | WO | A |
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