TW200932404A - Powder and facricating method thereof - Google Patents

Abstract

The powder of this invention includes a metal powder, an apatite layer covering the metal powder, and a silica particle adhered to the metal powder or the apatite layer. By means of the powder of the invention, it is capable of performing a high temperature annealing without damaging an insulating layer while fabricating a powder magnetic core. Therefore, a powder magnetic core which keeps an insulation property of the insulating layer and has full high permeability is obtained.

Description

200932404 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a powder which is suitable as a low powder magnetic core. [Prior Art] There are many uses of electromagnetics around us (ele gamma

, such as transformers, motors, generators, speakers (a heart), sense, heating H, various actuation H (aetuatOT) #. In order to achieve assimilation and miniaturization of these products, the performance improvement of the magnetic core of the powder molded body as a soft magnetic material is indispensable. Previously, the above-mentioned magnetic anger was produced by stamping the film of Shixia Steel and the insulating layer alternately, and then stamping it with a mold (electromagnetic steel, which corresponds to miniaturization and shape complication of the product). The X-ray defect 'has a problem in reducing the loss of thirst current. Chi Tai = such a problem, in recent years, as a moldability is excellent enough to record a low magnetic core, that is, soft magnetic metal powder is compression molded Acquired, 1, and went to the industry's research and development. It is to increase the magnetic flux density of such powder cores.

TZ, (magnetic permeability ) 〇 / C f magnetic core, mostly in alternating magnetic field (alternating magnetic use, if the iron loss is large, the energy conversion efficiency will be worse, so the iron is required to be smaller (low iron loss) Hysteresis loss and eddy current loss in C iron loss 3 200932404 ^The main problem is hysteresis loss and thirst current loss. The cause of the increase in hysteresis loss in the eight-pressure core is... In the soft magnetic gold f powder, the powder magnetic material is pressed to the core of the soft metal powder, so that the molded body obtained by reducing the hysteresis loss is annealed, thereby releasing the application to: The deformation is generally considered to be the better annealing temperature. On the other hand, in order to reduce the eddy current loss, it is effective = the material of the neomagnetic metal powder. Sincerely, the material usually has a pure surface with less hysteresis loss annealing. Then, the insulation material J is decomposed by the heat resistance, and the insulation (4) is lowered. Therefore, the reduction of the eddy current loss and the reduction of the hysteresis loss are very large. Therefore, in order to solve such a problem, the manufacturer is In the case of brittle insulation materials, in particular, the use of Lai powder as a soft magnetic metal is low in cost, and it is possible to manufacture a pressure with a high magnetic flux density. Various companies are conducting various studies. For example, Japanese (4) No. 0924 The bulletin towel, entangled with oxidized impurities ^ Excellent insulation is _ money. Shangyu 巾 towel Jielin Town ^ hot surface scaly treated iron powder and containing cerium oxide particles Drying, thereby obtaining the second oxidation, however, when the above-mentioned oxidized particles are coated as a powder magnetic tree, in order to fully obtain the connection of the metal powders to each other 4 200932404, the fire: the degree of the dish is set to 6 〇 0. The temperature of the usual step of the left and right is due to the iron's 'over-annealing temperature', then the magnetic property of the magnetic core is the tendency of emPemUre), so there is a powder ❹ 外 ^, Japanese Patent Special Opening _194273 In the bulletin, it is proposed that a layer, an A, a soft magnetic metal ▲ powder is formed on the surface of an oxide layer and an insulating environment of 33 m, and is subjected to a combination treatment under high temperature conditions, and the surface of the human magnetic metal powder is excellent in insulation. Single-layer. Uncovering - by the above-mentioned 专利本专利特开2007_194273号: Newspapers = Magnetic core: ? Yes,! When using this method, because of the same as step = =, ί! Cost is still not suitable for mass production, etc. The reason is that k is a soft magnetic metal powder that can be made thinner (four) green to obtain a film. Male T... (4) Wu is a high magnetic flux density of the genus, and an effective method is to form a thin and large-scale formation on the soft magnetic metal A simple and low-cost method is unknown. [Inventive content] The problem in the prior art described above is that the purpose of the invention is to provide a reduction in loss in the powder core and a reduction in eddy current loss. Moreover, it is a soft magnetic metal raw material powder having a high magnetic flux density. In order to solve the above problem, the present invention provides a layer of apatite layer having the above-mentioned metal powder, and a dioxide attached to the upper layer: gold f 5 200932404 powder or the apatite layer, according to the present invention, A powder formed by the benefit of a child. The oxidized stone particles are attached to the metal powder or the stone layer coated with the metal powder while allowing the two to form on the layer greater than or equal to the surface of the metal powder; the inventors: , the temperature = good heat resistance The dichroic membrane is tolerant to a compound larger than the equation layer containing the compound represented by the following Ca10(P〇4)6Xj b).

Ca , ( I ~ a) 1 〇 1 (mXn) /2) Mn (P 〇 4) 6X 2 ( I - b ) 4 = cation, atom or group; group, - represents an atom providing an valence anion; Two 〇) and less than or equal to 5, X is shown in Table P. St::Z' is better to use the organic group to carry out the 'best', it is better to use the surface-modified oxidized stone granules. In the formula, the compound represented by the formula (11) or (Π) is ^nSiX4.n ^ ) (wherein nAi q (melon) base, X represents a self-primary; the integer 'R', R2 represents a The organic powder of the valence is preferably a powder of a soft magnetic material. ❺ ❹ 200932404 Powder for powder core. Step: Step 1, the method, including the following apatite surface; and the third step C On the surface of the metal powder or the powder obtained in the second step, the powder of the powder and the apatite coated with the metal powder are obtained by the powder of the oxidized stone particles on the gold or the disc stone layer. Attached to the above-mentioned metal powder acid tn1 step break powder, (4) is to use phosphorus (the effect of the invention), the powder is coated with an insulating layer having an apatite layer and cerium oxide particles attached thereto This layer is excellent in heat resistance. Therefore, in the case of manufacturing a magnetic surface of a powder, insulation of a crucible, and destruction of an edge layer, it is possible to prevent insulation of the insulating layer and to have a sufficiently high magnetic permeability. The a powder core y is guaranteed to be excited; ^本Γ明ί The above features and advantages can be more clearly understood, the following specific areas only, and with the drawings as detailed below. Bu Wente [Embodiment] The powder of the present invention is a powder having a metal powder, a powdered limestone layer, and a powder formed by adhering to the above metal powder or the above-mentioned iridite fossil particles. Hereinafter, the oxygen constituent elements of the present invention are sequentially arranged. Each of the powders at the end of the Qin Dynasty (metal powder) 7 200932404 ▲ The metal powder used in the present invention can be used without any limitation if it has strong magnetic properties and exhibits metal powder read in the same saturation magnetic flux, specifically For example, iron powder, Shishi steel powder, sendust powder, amorphous powder (am()rphc) us p〇wder), permandur P〇wder ), soft ferrite magnet powder (1) the ferrite powder), amorphous magnetic alloy , Magnetic alloy powder, nanocrystal magnetic alloy powder and a high conductivity (pennau〇y) # soft magnetic material, the plurality of metal powder may be used alone or in admixture of two or more. Among them, iron powder is preferred in terms of magnetic strength and low price. Further, in the iron powder, pure iron powder is particularly preferable in terms of excellent magnetic properties such as saturation magnetic flux density or magnetic permeability and excellent compressibility. Specifically, examples of such a pure iron powder include a powder of pure iron powder and reduced iron powder, and the like, for example, a magnetic special 乍 粉 powder manufactured by Kobe Steel Co., Ltd., or a compression butterfly The use of the elements in the range of the fine ringing is carried out. Specifically, for example, an element such as a recording element, a snail, a smear, a chrome, a molybdenum or a copper may be added for the purpose of preventing the oxidation of the metal powder from being added to the element. g When the particles of == 2 ^ (Scanning Electron Microscope, SEM) are large, and the particles 3 in the range of 1 dance are equal to or greater than 1 in the range of 1 dance, it is easy to form 8 200932404 when making a powder core of &gt;1 The tendency is that if the particle # is less than or equal to 3, the eddy current of the magnetic core becomes large, and it is easy to coat, and the powder can suppress the pressure powder 1: the average of the two sieves is obtained. ::: Gold flat powder. Ding flat processing ❹ (Limeite layer) The apatite layer on the surface of the coated powder of the present invention, from this point of view, the surface of the two layers of the gray stone layer is coated in layers. Wei Wei 'refers to the material with apatite structure with Wei Shi == layer =: money X2 (Ia) ^a(10-(^n)/2)Mn(P〇4)6X2 ( I — b) supplied by (where M denotes an atom providing a cation, and m denotes an atom or a group of atoms of the valence anion of M.) For the 5 x table not providing one is (1 - b), provided The cation of the cation is preferably pinched to a well-behaved metal of 08. Specific examples of the metal include an ion half mirror: a metal of the lattice = 4 Å, for example: nano, m, erbium, chrome, manganese, iron, cobalt, nickel, zinc, lanthanum, cerium, zirconium, hafnium , 锗, 9 200932404 名巴,银,锡,锡,锡,录,蹄,钡,纲,钸,镨,叙,矩,钐'铕'This 'try'镝' Qin' oblique '钟'钂' Record 'give' in white 'gold' mercury, antimony, lead, antimony and so on. The oxime in the above formula (I-b) may be one type or two or more types. Further, in the above formula (I-b), the range of η is more than 0 and less than or equal to 5, preferably more than 0 and less than or equal to 2.5, and further preferably more than 0 and less than or equal to 1.0. In the above formula (I '-a) and formula (I-b), X is preferably a hydroxyl group and a halogen (F, α, B, I, etc.), more preferably a hydroxyl group and fluorine. In terms of excellent coating properties of the metal powder, X is preferably a hydroxyl group, and in terms of excellent strength, X is preferably a gas. In terms of insulation and heat resistance when the powder magnetic core is formed, and in terms of excellent mechanical properties, the apatite structure of the apatite layer is preferably of the above formula (I). a) The compound represented is particularly preferably a dietary limestone (Ca) 〇 (P〇4) 6 (〇H) 2 ) or a fluorotitalite (Ca 10 (PO 4 ) 6 F 2 ). In the powder of the present invention, "the use of the apatite layer to coat the metal powder" means that at least a part of the metal powder is covered with the apatite layer. Therefore, the "apatite-coated metal powder" to be described later may be in a state in which the metal powder is completely covered with the apatite or a state in which a part of the metal powder is exposed. On the other hand, in view of the fact that the cerium oxide to be described later is likely to adhere and the bending strength is improved, the degree of coating of the metal powder by the apatite layer is preferably high. Specifically, it is preferred to coat the surface of the metal powder with 90% or more of the surface of the metal powder, and more preferably 95% or more of the surface of the coated metal powder, and more preferably the entire surface (about 100%). ). 10 200932404 In the respective ends of the present specification, the thickness of the apatite layer is preferably nm 〜10 〇 0 nm, more preferably 2 〇 fine 〜5 〇〇 nm. If the thickness is more than the above, the insulating effect tends to be obtained, and if the thickness is the surface M, the effect of increasing the density tends to be obtained. (1) As a method of forming a phyllite layer on the above metal powder, a method may be employed in which an ion or a group of atoms containing a cation or a group of atoms m in the formula (Ib) is further contained in a specific ratio, and The aqueous solution containing the Wei ion is reacted, whereby the genomic substance is precipitated on the surface of the metal powder. In order to obtain a layer of apatite or structure, it is necessary to control the liquidity of the reaction solution to be neutral to the test mouth (ρΗ=6.0 or more). Further, in the acidic region, the calcium phosphate layer other than the material of the domain structure may be precipitated. When the phosphorus ash is precipitated as a discite layer by the base dish, the stoichiometric amount of the hydroxyapatite obtained by using the aqueous solution of calcium nitrate and the aqueous solution of ammonium dihydrogen phosphate is +. Ca]0(P〇4)6(OH)2 'but as long as most of it is a disc limestone and ^ is a structure that can be maintained, it can also be a non-stoichiometric composition called a part of graystone for CaiQ-z (HP 〇4) z(P〇4)6—z(0H)2_z can also be: SCa/P (atomic ratio) <LQ). The amount of the raw material of the apatite layer is preferably 0.1 part by weight to 0 part by weight, and the weight of the raw material of the apatite layer is preferably 0.4 parts by weight to 0.8 parts by weight. It is 〇5 weight and it is better to hurt. The amount of the raw material added to the right garnet layer is equal to or greater than i1. 7 Heavy Dong has a tendency to obtain a sufficient resistivity when the powder magnetic core is formed. Weight = part, then 11 200932404 The insulating layer obtained is uniform. If the amount of the raw material of the disc limestone layer is less than ==, the density of the molded body tends to decrease when the powder magnetic core is formed. The elemental analysis of the obtained powder was carried out and the amount of the metal M) was quantified. , and (- oxidized dream particles) ❹ = the dioxide used in the powder of the powder "wd silica". ΓοΐΓ·ί f ·Γ ^ Λ ^^ in terms of ease of comparison, compared to 1 aj SlllCa) and the like are not particularly limited in the shape of the actinic stone particles. In the case of dioxane, as the oxidized stone particles, in order to have film formability, it is preferable to use cerium oxide particles of various sizes. Specifically, _/, the oxygen having a particle diameter of less than or equal to a micron is preferably 50 nnJ or less. The average primary particle diameter of the particles is preferably less than or equal to ^m and (4) is less than equal money, and is dispersed. In the organic solvent, the dispersibility of the organic group-modified dioxygenation is not observed in the case where the second subunit is 31, and the cyclohexyl group, the stupid group, and the organic group are, for example, ~6. An alkyl group or the like. Soil, phenethyl, Ci~C6 (the carbon number is the use of such an organic base to repair m... 200932404 The bending strength of the powder magnetic core, as the case may be, the electrical resistivity can also be improved. As such a stone burning compound, Specifically, the alkoxydecane represented by (π) or the compound of the following formula (halogenosilane) can be used.

R]nSi(〇R2)4_n R^SiXtn

(wherein η is an integer of 1 to 3, R1 and R2 represent a group, and X represents a dentate.) Table (4) Organic, in the general formula (Π), and in the formula (dish) Specific examples of the modification of the oxygen-killing particles include dihexyl group, phenyl group, benzyl group, phenethyl group, and C1 to C6 (alkyl group having a carbon number, etc. Further, as R2, one may be mentioned. Specific examples of the organic group of the valence include a methyl group, an ethyl group, etc. Further, examples of x include chlorine, moth, moth, etc. The alkoxydecane represented by the above formula (π), specifically For example, y is exemplified by methyltrimethoxy hetero, ethyltrimethoxyhetero, n-propyltrimethoxy-11, isopropyltrioxazole, n-butyltrimethoxycarbazone, Second butyl trimethoxy carbaryl, n-pentyltrimethoxy sulphate, n-hexyl decyloxy Wei, cyclohexyltrimethoxywei, phenyltrimethoxydecane, benzyldimethoxydecane, benzene Trimethoxy decane such as ethyl trimethoxy decane; p methyl triethoxy sulphur, ethyl triethoxy sulphur, n-propyl triethoxy sulphur, isopropyl triethoxy Kewei, n-butyl triethoxy sulphur, second butyl triethoxy wei, n-pentyl triethoxy, n-hexyl triethoxy wei, cyclohexyl triethoxy wei, phenyl Triethoxy sulphur, 33 200932404 triethyl ethane such as benzyl diethoxy decane, stupid ethyl triethoxy decane; &amp; dimethyl dimethoxy decane, ethyl methyl methoxy Base decane, methyl n-propyl dimethoxy decane, methyl isopropyl dimethoxy decane, n-butyl. methyl dimethoxy decane, methyl tert-butyl dimethoxy decane,基正. Pentyldimethoxydecane, n-hexylmethyldimethoxydecane, cyclohexylmethyldimethoxydecane, methylphenyldimethoxydecane, benzyl fluorenyl dimethyl sulphate Dimethoate, phenethylmethyldimethoxy zeshi, etc. ❹ Dimethyldiethoxy Wei, ethylmethyldiethoxy residual propyl diethoxy decane , methyl isopropyl diethoxy decane, n-butyl methyl diethoxy decane, methyl tert-butyl diethoxy decane, methyl n-pentyl dioxononane, n-hexyl methyl di Oxydecane, cyclohexylmethyldiethoxymethane, methylphenyldiethoxyxanthate, fluorenyldiethoxyxanthine, phenethylmethyldiethoxyxanxi, etc. Further, as the dentate compound represented by the above formula (111), ❹ is specifically: for example, methyl chloroform, ethidium sulphate, and Propyl gas, isopropyl trichloromethane, n-butyl trichloromethane, tert-butyl, gas stone, n-pentyl trichloro-wei, n-hexyl tri-gas, Wei'-ring-[trichloro-wei , phenyl trichloro-Wei, benzyl trichloro-Wei, phenethyl tri-gas sulphate, etc.; trimethyl chlorodecane, ethyl methyl dioxane, methyl propyl Dihydromethane, mercapto isopropyl dichlorowei, n-butyl fluorenyl dichlorite, methyl tert-butyl dichlorite, methyl n-pentyl dichlorite, burning基曱基14 200932404 Dichloromethanol, cyclohexylcarbyl, its _chakimethyl chlorinated sulphur, sulphuric acid, methyl phenyl dichlorite, the above-mentioned stone smelting compound, earthy eight ^1石夕院, etc. Dichloro Xi Shi burning and so on. Used together. Knife should be used alone or in combination of two or more types: scatter = two: = often by dichlorinating: two. This;:=== Component 1 weighs 1 part, preferably right / T Ding force = followed, no or left unreacted and remains; if:: quantity =: = (four) from the machine base to the dioxins The modification effect of the emulsified stone ^ Γ Γ Γ ,, can also be divided into the threat of money spray. Under mild conditions; subsurface modification reaction ❿: acid contact ion exchange resin, etc. == j on 4 acids, formic acid, oxalic acid, etc. Since the acid usually degrades due to the reaction of the limestone, it is preferable that the volatile diacid is not in the upper part of the system, and further preferably the hydrochloric acid and: the addition amount of the heavy amount is formed with respect to the dioxate solid. It is preferred that one weight is 0.05 parts by weight to 1 part by weight. Biocontrol: Oxidation • Good hair is produced by MG~4(^ under the reaction). In addition, the above-mentioned dioxin I, 15 200932404 Shixi particles, better shouting the difference (4) organic solvents such as toluene, xylene, etc. - alcohol early methyl ether acetate, (manufacturing method) The method for producing a powder of the present invention is formed by coating a metal powder with a whey stone to form a step 1 (hereinafter, referred to as a county-coated metal powder layer) The coated metal powder ❹ 附着 powder is attached to the above-mentioned step 2 to obtain the above-mentioned temperature of the cerium oxide metal powder or the ash of the above-mentioned can stone layer The second step = step, at least 350, to obtain the above-mentioned metal powder, to coat the above-mentioned pre-hardened layer, to obtain the phoenix layer on the metal powder or the disc stone layer, and to adhere (metal powder) The powder obtained by the treatment of the cerium particles. In terms of the oxidation of the lean acid powder, it is preferable to make the metal: the phosphoric acid can be treated by the previously known =: treatment (formation of the ash layer) *: The method of forming an apatite layer on the gas is described in the following section: (4) The aqueous solution containing the lanthanum (and the yttrium or yttrium group) is reacted with an aqueous solution containing cerium ions to precipitate the ash stone on the metal powder table. In the following method, an aqueous solution and a metal powder as hydrazine are added to the flask, and while stirring, the water as a source of water is added dropwise = 16 or one of them may be added first.

200932404 liquid. In addition, the following method may be used: when the human water and the side of the flask are added to the flask simultaneously or successively, the aqueous solution as the calcium source and the second wire are successively added dropwise, and the dropping order is as follows. The contact 'as long as it is a water-soluble compound, there is no particular limitation on Lr', for example, one or two of the inorganic bases of the hydrogenolysis solution are not available! Acid dance salt, the wrong salt of organic acid in the acid salt, organic test ^ calcium alone. The phosphoric acid source may, for example, be phosphoric acid or a phosphate such as diammonium phosphate or diammonium phosphate. 、 In order to obtain a layer of apatite structure, the reaction solution is preferably in a neutral region, and the enthalpy value is preferably greater than or equal to 7, and further preferably equal to 8', more preferably greater than or equal to 9, especially Good is greater than or equal to 1〇. If it is in the acidic region, the acidity of the dish other than the disc stone may be analyzed. Therefore, it is preferable to preliminarily use the ammonia water (10) to treat the above-mentioned 7-bath of the liquid and the positive value of the aqueous solution as the source of the scaly acid. Adjusted to be greater than or equal to. The reaction temperature 'may be room temperature' but in order to promote the reaction, it is preferably greater than 5 ° C, more preferably 70 ° C or more, and particularly preferably greater than 90 ° C. When the solvent is water, the upper limit temperature is near the reaction, i.e., 1 Torr. When there is no reaction time, it is considered that the concentration of the aqueous solution as the calcium source and the aqueous solution as the phosphoric acid source is the same as that of the above, and if the concentration is low, the reaction is preferably extended. In the production method of the present invention, the concentration of the aqueous solution as the aqueous solution and the aqueous solution of the phosphorus arsenic is preferably in the range of 0.003 〇 to 〇·5 μ, and the reaction time at this time is better than that of 17 200932404. 1 hour ~ ίο hours. (Adhesion of cerium oxide powder) The ash-coated metal is oxidized to the dispersion of the diced particles obtained in the above manner. Fire the metal powder and temper the appropriate concentration. In addition: = organic dream sol, can also be diluted into the same organic base is commercially available, as described above, when the surface of the decane compound is used for surface repair; Further, the Wei stone layer used for the surface modification may be attached to the phosphor ash; and the surface may be adhered to the surface of the exposed metal powder. The solvent in which the θ k is sufficiently defective and is dispersed is not particularly limited and has a bismuth agent. In particular, the aromatic U-gel in the state of an aromatic solution solution represented by toluene makes it easy to maintain the rubber (pre-hardened) on the surface of the stone. Therefore, 4 ash, ## can be pre-hardened at the current (10) temperature.隹 3 3 hardens to form a strong heat-resistant film. If the material powder is not = pre-compressed, the production pressure = a tendency to transmit sufficient insulation. The temperature of the above pre-hardening is 18 200932404 100 C ~ 300. . . The amount of the dioxins added in the present invention is preferably (10) parts by weight to (2) Å 地 地 = 4 parts by weight of G.G., and the dioxo prior particles may be further to: J: gold = The upper view thus has the effect of improving the insulation and the effect of the woven surface. The right addition amount is less than that of the 7 slamming powder core to prevent the density of the molded body from decreasing, and the resistance of the powder core can be prevented. The tendency of f to decrease in strength. (Production of Powder Magnetic Core) For the magnetic powder of the present invention, the mixed powder is compression-molded to form a core-lubricating lubricant, and it can be used after stearic acid recording and fresh frying. It is a long-chain chimney that belongs to the soap. Into == mouth bell, etc. Gold 〜 ~ (10) paper. Further, in order to reduce the hysteresis loss, the core is annealed. The annealing temperature at this time is better than that of the secret magnet. This social gorge is carried out in ^5(9)c~_t:. Inert gas such as boring or helium

The residual A density and insulation produced by the above method. In addition, the inventors of the present invention presumed that the machine is the following machine, and the inventors presumed that the following is a machine that is characterized by a scale-specific layer of cerium oxide particles. The crack of the tarnish layer produced by the square in the form of the molding 19 ❹ ❹ 200932404 The seam position is effectively filled into the cerium oxide particles, thereby making it possible to use the ancient body density (for example, greater than or equal to 7) "/Thousands of 3 borrowing: the mouth is more than two heat-resistant and key (four) (10)h and can maintain a higher diameter. It is better than the above-mentioned 'can be considered' of the oxidized stone oxidized stone under the particle The reason is that the smaller second-effect filling of the crack portion of the cerium oxide layer can be more = greater than #7, Gg/em, and more preferably the larger material is equal to 7.4g/em3'. Then, the magnetic flux density of the powder magnetic core is increased. In addition, the surface of the powder magnetic core is: large: wide and further preferably greater than or equal to = then ^. If the resistance value is greater than or equal to 30 / ζ Ωιη, [实ΐΐιΓ The trend of the county of the 14-filament core is smooth. It is not limited (4) to say that the financial correction, but the invention and [Example 1] to the four-port of mL The Chinese and Canadians are adjusted to be greater than or equal to η __aqueous solution 75 K will be ^ value. In addition, to the second == made: pure iron powder 3_) adjust the pH to greater than or equal to 1 scalar dihydrogen: dissolve m α〇7_ι'_4Μ&gt; The funnel was then fixed on a four-burner ^ 20 200932404. - The contents of the four-necked flask were mixed at a temperature of (25 ° C), and the drops were added dropwise in 1 G minutes. Funnel__ aqueous solution of dihydrogen ammonium. ° Next, a four-necked flask was dispensed in a 9 (TC oil bath, and reacted for 2 hours. The obtained liquid was subjected to suction filtration at u =

Spectroscopy ^ XPS) 4® 进行 For analysis, the atomic presence rate is Fe: _ nr Ca/P ratio (mole ratio) is ι64. iX7/o, and, in turn, the obtained dish ash: indeed contains a fine solid component The concentration is 3. 〇, the capacity is 5 〇mL of polypropylene _10 = the grain is removed and transferred to a stainless steel dish, 2 〇. . , obtained, hardened by the powder pass = two = ^, __ dioxo coating SEM:; = = two or two coated iron powder profile of the stone coated iron powder profile = Na ^ particles On the surface of the job _ Kewei stone m coffee two will be obtained by attaching nano-dioxide ^ 匕 夕 夕 夕. 5.92 g is filled in a mold with an inner diameter of 14 coffee, and is formed into a cylindrical shape under the pressure of the iron-coated iron powder. At this time, the time is a little 5 coffee. The surface of the shaped tablet was ground by using a four-terminal resistor 91 Α Ώη at =60 200932404 at 60 CTC. Further, the volume resistivity (resistivity) was measured by a rate meter, and as a result, the density of 296 was 7.48 g/cm3. In a nitrogen atmosphere, at 6 Torr (: (1 hour annealing, after grinding the surface again, the volume resistivity (resistivity) was measured, and as a result, the density of 91 was 7.47 g/cm3. EXAMPLES: The same method was used to prepare the powdered powder of the base dish until it was halfway. That is, '25% of the four-necked flask was used.

氨 Ammonia water adjusts the value of ρΗ to 75 mL (1.79 mmol, 〇·024 M) of iron (11) acid dance aqueous solution and iron powder (300NH of pure iron powder manufactured by Kobe Steel Co., Ltd.) 30 g. In addition, 75 mL (1.07 mmol, 〇.〇14M) of an aqueous solution of linoleic acid dichlorohydrin with 25% ammonia water and a pH side of greater than or equal to u was added to the dropping funnel with a side tube, and the dropping was further carried out. The funnel was attached to a four-necked flask. While stirring the contents of the four-necked flask at room temperature (25 〇 under the ' - - - 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏The four-necked flask was mixed, and the mixture was subjected to a side-by-side. Then, the obtained liquid was subjected to suction filtration, and dried by filtration on a 110 towel to obtain a powder of ash S (yield 96: obtained). The powder passes through 250 _, and is obtained as _ ash stone 〇 ^ 。 powder. The stone 粦 粦 包覆 包覆 金属 金属 填充 填充 填充 填充 填充 填充 填充 填充 填充 填充 填充 填充 填充 填充 填充 填充 填充 填充 填充 填充 填充 填充 填充 填充 填充 填充 填充 内径 内径 内径&quot; 4 'The obtained lozenge of the thick Tang about i 5 mm 〇科占开J,,ϊ

200932404, the result is 144 / Ωιη. In addition, the density is 7.54 g/cm3. In a radon environment, the ground lozenge was annealed at 60 °C for 1 hour, and after re-polishing the surface, the volume resistivity (resistivity) was measured by a four-terminal resistivity meter. The result was 〇.54. In addition, the density was 7 53 twisted 3. [Comparative Example 2] ❹ Lu - No apatite layer was provided, and nano cerium oxide was attached to the nano cerium oxide by the method of attaching nano cerium oxide in Example 1. On the iron powder, that is, 20 g of iron powder (pure iron powder 300NH manufactured by Kobe Steel Co., Ltd.) and 2 g of a solution of nanometer fossil (solid content of 3.0 wt%) are mixed; After quenching for 10 minutes in a 50 mL polypropylene bottle, pre-hardening was performed for 3 minutes at 200 C. The pre-hardened powder was passed through a sieve of m/m to remove large aggregated particles. The metal powder to which the emulsified stone and the emulsified stone were attached was obtained. The 5 &amp; ribU in the obtained powder was a columnar rotary agent of 14 em and a thickness of 5.145 mm at a pressure of 1 MPa. 'Using a four-terminal resistance meter to measure the volume of the electric fruit to 79. In addition, the density is 7.57 ^ _ _ down to the ground spin For a measured volume resistivity; terminal resistivity 7.57gW density sheep) ,,,. The fruit is 20 Wm. In addition, ♦ The result of the density and resistivity of the (4) powder core is shown in this paper. 23 200932404 [Table l]

&amp; Referring to Table 1, in order to obtain a high electrical resistivity, both the base apatite coating and the two-part heterodip adhesion are indispensable. Further, in the molded article of Example, the density of the molded body was as shown in Example 1, and the apatite coating and the silica dioxide particles were adhered, but compared with the comparative example! There was almost no decrease in the density of the molded body of Comparative Example 2. It is presumed that the reason is that, in the case of (iv), it is destroyed during molding, and thus the cerium oxide particles are embedded in the pores of the crack of the apatite layer generated. Next, in order to estimate the strength of the adsorption force between the apatite layer and the cerium oxide particles, the cerium dioxide particles are attached to the iron powder and the stone-coated iron powder having different surface states, respectively. To compare what kind of 二% of the dioxins remain on the surface. Its green color will contain an organic cerium sol (media. toluene) of cerium oxide particles having an average particle diameter of 20 nm as measured by dynamic light scattering method using HPPS manufactured by Mlvern, Inc. (solid content concentration is 3.0). Gt%) 5.0 g was placed in a glass spiral tube having a maximum capacity of 10 mL, and various powders of 3 〇g were added thereto. The spiral tube was subjected to 3 small 4 stirring using a rotary mixer set to a rotational speed of 1 〇 5 rPm. Using a filter paper of N〇 5B (JIS p38〇1) for quantitative analysis, the stirred liquid was subjected to suction filtration, and the filtrate was washed with toluene and vacuum dried to obtain each powder. 24 200932404 Elemental analysis of the obtained powder by Inductively Coupled Plasma-Optical Emission Spectrometry (ICP-OES), quantifying the amount of cerium oxide particles attached to the powder by the amount of ruthenium atoms . The results are shown in Table 2. [Table 2]

No. Powder Si adsorption amount (wtppm) 1 Pure iron powder (300NH) Ϊ60 2 Asbestos-coated iron powder 360 From the results of Table 2, the amount of Shixia atom quantified from the apatite-coated iron powder is known. Compared with the amount of bismuth atoms of pure iron powder, it is about 2 times. Since the ruthenium atoms present are only derived from ruthenium dioxide particles, it is known that the ruthenium dioxide particles have a large amount of adhesion, and the apatite layer has a stronger adsorption force to the cerium oxide particles than the surface layer of the pure iron powder. . [Embodiment 2]

. In the first embodiment, iron powder was added to the aqueous calcium nitrate solution, and the mixture was stirred in a 30 C oil bath for 15 minutes. In other words, a 300 mL four-necked flask was charged with a calcium nitrate aqueous solution of 75 mL·(1.79 3H〇.024 M) adjusted to a value of U or higher with 25% ammonia water, and iron powder (purified by Kobe Steel Works Co., Ltd.). _ There is f M30 §, in the oil bath of 3 ° ° C (four) 15 minutes. After that, add 75 mL of dihydrogenated dihydrogen solution with 25% ammonia water to adjust the pH to 2 °. 1 〇7面〇1,〇〇14 The fixed funnel was fixed on a four-degree flask. The oil was mixed in a four-necked flask, and _ was added to the dropping funnel in minutes. 200932404

An aqueous solution of ammonium dihydrogen phosphate. Next, the temperature of the oil bath was raised from 305⁄4 to 9 ° C over 10 minutes, and the mixture was reacted at 90 ° C for 2 hours while stirring. The obtained slurry was subjected to suction filtration, and the filtrate was dried in an oven at ll ° C to obtain a gray powder. XPS (X-ray Photoelectron Spectroscopy, x-ray photoelectron spectroscopy) was used to analyze the atomic ratio near the surface of the obtained powder, and the atomic existence ratio was Fe: 3.31%, Ca: Π.1%, Ca/P Ο ratio. (Morby) was 1.63, and it was confirmed that the powder was coated with hydroxyapatite. Further, 2 g of the obtained disc stone-coated powder and 2 g of the organic stone solution # benzene solution (solid content concentration: 3 〇 wt%) were mixed, and the polypropylene bottle having a maximum content of 50 mL was mixed. After shaking for 1 minute, it is dried for 5 minutes at a pressure of 1 MPa or less, and the powder taken out at 2 〇〇〇c is subjected to 2 ^ minutes. The powder that passes the duty will pass through 250. 6g of iron powder is filled in the inner diameter

In the mold of Mmm, it is formed into a cylindrical gorge at a molding pressure of 1 〇〇〇Mpa/cm2. At this time, the thickness of the obtained blowing agent was about 5 faces. The surface of the shaped tablet was polished, and the volumetric electric power was determined by the four-terminal resistivity (the ratio (electricity) was 236. The density of the molded body was "5 〇g/c:" in a nitrogen atmosphere. After the surface of the grounded material was ground, the volume resistivity (resistivity) was measured by a four-terminal resistivity meter, and the density of the molded body was 7.5.实施g/cm2. [Example 3] In Example 2, the amount of ammonium dihydrogen phosphate water was added dropwise to the contents of the four-necked flask. 26 200932404 After the liquid was added, it was added to the oil of 3〇c for 15 hours. That is, 'to a 300 mL four-necked flask, the pH of the two-necked flask was adjusted to be greater than or equal to u, and the acid solution was 75 rainbow (179 mmo, 0.024 M) and iron powder (pure iron manufactured by Kobe Steel Works Co., Ltd.). Powder 300NH) 30g' was stirred in an oil bath of 3CTC for 15 minutes. Thereafter, 75 mL of an aqueous solution of bis(dihydrogen sulphate) adjusted to pH u or more with 25% ammonia water was added to a dropping funnel with a side tube. 1〇7〇1,〇〇14 (4), and then fix the dropping funnel on the four D. The oil ~= was mixed with a four-necked flask, and the mixture was added dropwise to the dropping funnel with _ acid dihydro junjun, and the surface temperature was stirred for 1.5 hours. Then 'oil bath with 1 〇 minute The temperature is from 30. (: The temperature is raised to 9 〇t, - the reaction is carried out for 2 hours under the thief. The obtained slurry is subjected to suction filtration, and dried in an oven at 110 C: xps is near the surface of the obtained powder. The original 4 is in the = Ο 皇 = = original: the existence rate of Fe: 5.56%, Ca: 14 85%, (10) ratio (Morby ratio) is 1.63, it can be confirmed that the powder is coated with _ gray stone. Further, it will be obtained Apatite coated powder toluene solution (solid concentration of 3 〇wt% g? 矽 sol large content of 50 mL of polypropylene oscillating vibration 2: the most content is removed and moved to a stainless steel dish ^, will The inside was dried for 5 minutes, and was dried at a pressure of 2 W: T_^ = HLMPa. The obtained iron powder obtained by pre-hardening was pre-hardened by two or two minutes to obtain the nanometer dioxate-attached vermiculite-coated iron powder. 6 27 200932404 g is filled in a mold with an inner diameter of 14 mm and formed into a cylindrical tablet under pressure. 'Milling 5 mni at 1000 MPa/cm2 this day. The surface of the tablet was subjected to &amp; the thickness of the obtained tablet was about the measured volume resistivity (resistivity), and the density of the body was 7.51 g/cm 2 using a four-terminal resistivity meter. The nitrogen was ^^11. , into the four! Ji ❹ Ο 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨 磨~= rate)' result is 55

Cljj 贯 Example 4] In Example 3, 9〇 will be used. (: The next g life is 10 minutes. The reaction time is changed from 2 hours to the same, that is, the 300 mL of the four-burning #yang value is adjusted to be greater than or equal to ^ ^ added to use (4) ammonia water will be brewed into the M) and Iron powder (God == solution 75 祉 (4) NH) 3Qg, the oil produced in Guan (4) pure iron powder has a side tube of the dropping funnel added _ 5" bell. Thereafter, the side of the aqueous mixed solution of heterodihydroammonium equal to u is set to be large M)' and the dropping funnel is fixed in four burners. P'0·014, wherein the dropping funnel is added dropwise for 1 minute. Within the ~acid-_aqueous solution, the money was mixed for 1.5 hours in the oil state. &amp; kept at 30 C. Next, the oil bath temperature was stirred for 10 minutes while stirring at 9 〇t, the dish was raised to 90 °C, and the liquid was fed into the rod ^ w 〇 knife buckle. Then, the obtained slurry was subjected to a disturbance. The drying was carried out in an oven of 11 (rc), and as a result, 28 200932404 gray iron powder was obtained. The ratio of fruit atom near the surface of the obtained powder by XPS was -%= ratio (Morby) is 1.44. ❹ ❹ Further, the obtained Wei Shi coated powder 2G g and benzene solution (solid content concentration of 3.0 wt%) 2 g in a maximum of 50 ml of polypropylene bottle After the vibration for 1 minute, the contents were taken in a stainless steel dish, and the taken powder was pre-cured at 200 ° C for 25 minutes under a pressure of not less than Mpa. The iron powder obtained by the second pass was passed through 25筛 。 。 。 。 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着The thickness of the obtained tablet was about 5 mm. The volume resistivity of the surface of the shaped tablet was measured to be 214 (four) m. In addition, the density of the molded body was 7 2 2. In the milk, in _. After using the polished tanning agent for 1 hour, the reflow rate is re-polished, and the four-terminal resistivity meter is used. The volume resistivity (resistivity) was found to be 53 Ωιη = 7.49 g/cm 2 . Further, the molded body density [Example 5] 5 hours in Example 3, the reaction time under the thief was changed from 2 hours to also That is, it is added to a 300 mL four-necked flask, which is equal to or greater than the aqueous solution; = 〇 〇 side (4) and iron powder (pure iron powder manufactured by Kobe Steel Works Co., Ltd. 29 ❹ ❹ 200932404 300NH) 30g, oil bath in Yu Stir for 15 minutes. After that, add 75 mL a〇7 mm〇i, 4 Μ), to the dropping funnel with the side tube, and adjust the pH value to 11 or more with 25% ammonia water. The wire funnel was fixed on a fine-necked flask, and the thief oil was mixed with a four-π flask, and the % acid dihydrogen in the dropping funnel was added dropwise thereto for ω minutes, and then stirred under a temperature of 1.5 hours. Then, the temperature of the oil bath was raised from 3 〇〇c to 9 10 in 10 minutes. 〇, the reaction was carried out for 5 hours while the obtained (four) liquid was dried in a tank of 110 c. The result was gray. Iron [.iffiXPS rides on the surface of the powder near the surface of the atomic rate

11 i Fe : 6.070/0 . ca : 13.980/0, Ca/P is . It is confirmed that the powder is coated with hydroxyapatite. Then, the obtained apatite-coated powdered toluene solution (solid content concentration: 3.0 wt%) 2J is most concentrated, and the bottle is shivered for 1 minute, and then the contents are taken out and moved into a stainless steel towel, at less than or equal to 1 The MPa's diligence depends on 5, and the powder is pre-hardened for 25 minutes. Pre-made: 3, the obtained nano-adhesive and 6 g of gray-coated iron powder were filled in a mold surface having an inner diameter of 14 mm, and the four-terminal electric rate was used: (4) m. In addition, the density of the molded body is 747 g / = 2 resistance 30 c 200932404 In the nitrogen atmosphere, the polished _ is annealed for 1 hour under _t', the surface is reground, and then measured by a four-terminal resistivity meter The volume resistivity (resistivity) was 93 m. In addition, the molded body was 7.47 g/cm 2 . The outer age (four degrees) [Example 6] The reaction temperature of 9 in Example 3: '(4) In a 4-mL, 0 mL flask, 75 mL (1.79:=G24 M) and iron powder (30 g of pure iron powder manufactured by Kobe Steel Co., Ltd.) were added to the four-necked flask with 25% ammonia water to adjust the P value to 11 or more. In the 30C oil bath, stir it for ls minutes. After that, add 75 ml of aqueous ammonium dihydrogen solution to the dropping funnel with the side tube to adjust the pH to a large f equal to 11 75 mL α〇7 mmo Bu 0.014 (4), and then fixed the rhyme (four) bucket on the four-necked flask. - Edge 30. (: Stirring: mouth flask '- side to 10 The clock dropping plus dropping funnel = % acid dihydrogen recording aqueous solution, and then stirring for 3.5 hours under the temperature of the oil bath. 7 ❹ The liquid in the box is filtered by suction, and the water is in U() °c~ Gray iron powder was obtained. It was confirmed by XPS that the atomic ratio of the vicinity of the surface of the obtained = was coated with hydroxyapatite. For example, 65', the obtained (iv) limestone coated toluene solution ( Solid into a public, general machine 矽 sol 5 〇 的 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ In the dish, the iron powder obtained is less than 笙^ 5 ^ , and the iron powder obtained is contacted by 25G ~ knife clock. In the pre-hardening, the mold of 1000MPa/cm20^,,, and 钇 is 14 mm. It is formed into a cylindrical spinner under the condition of strong productivity. Grinding is carried out by using: ^^5 faces. The surface resistivity (resistivity) of the surface of the shaped tablet is measured at 119 //〇,

= Γ&quot;. In addition, when the density of the molded body is 7.5 W, the polishing is performed for 1 small volume of electricity (the electronic resistivity meter measures 7.53 g/cm 2 , and the fruit is 31 #. In addition, the density is [Example 7] The reaction temperature of 9 〇t in Example 3 was changed to a machine. ❹ P was also added to a 30 〇mL four-necked flask by adding 25% ammonia water to adjust the pH to a side aqueous solution of 75 mL or more. M) and iron powder (Kobe Steel Institute Teli) 3Gg, stir in the oil bath of the machine for 15 minutes. After that, add = 25% ammonia water to the dropping funnel with the side officer to adjust the pH to 75 mL (1.07 mm. Bu 0 014 M) of the aqueous solution of ammonium dihydrogenate in the mixture of 11 or more, and then fix the dropping funnel. On a four-necked flask. While the flask was placed in an oil bath of 3 °, the aqueous solution of ammonium dihydrogen phosphate in the dropping funnel was added dropwise to the towel for 1 G minutes, and the mixture was stirred for 1.5 hours while maintaining the temperature of the oil bath at 3 Torr. 32 200932404 Next, the oil bath temperature is taken from 5 minutes. While mixing, the mixture was reacted at 5 (TC for 2 hours. = 5GC, - gas was passed through, and dried in a container of _ ten, c liquid was sampled, and the result of atomic presence = near: original, rate进而 In turn, Lai _ Wei Zheng;; Weiwei stone coating. f benzene solution (solid component indifference is 3 〇 2, the end, 夕 sol stainless steel dish === clock behind 'to remove the contents to The obtained ==== silk her. The pre-hardened and cut stone coated iron powder 6 ❹ The factory type is cylindrical: the molding 5 position. The thickness of the surface of the shaped tablet is about In order to measure the volume resistivity (resistivity), a four-ohmic terminal resistivity meter is used: sub-, : _ product two-two r body density is one in the third embodiment, c; 11 (TC calcination. C reaction temperature change) 30 °c, and not 33 200932404, that is, to a 300-neck four-necked flask, 75 mL (1 79 mmol, 0.024 Μ) of a terminal acid dance aqueous solution using 25% ammonia water to adjust the pH to 5 rm or more. And iron powder (pure hose made by Kobe Steel Works Co., Ltd.) 30g 'stirred in rc oil bath for 15 minutes. After that, add 25% ammonia water to the dropping funnel with side tube. The aqueous solution of ammonium dihydrogen phosphate adjusted to be greater than or equal to 11 is mL (1.07 mmol, 〇〇14 Μ). The funnel was fixed on a four-necked flask, and was placed in a four-necked flask. ,-to the (four) Η) minute drop into the dropping funnel _ acid two water test, and then stirring in the state of the bath while holding the machine for 3.5 hours. Then, the obtained slurry is pumped and filtered out The green steel system is isolated from the four (4) less than the wa (four) to obtain 4 gray iron powder. _ Which pairs of the surface near the surface of the child is analyzed, the presence of silk atoms is Fe · · 5.53%, Ca :, 13.63% ' Ca/P ratio (Morby ratio) is 152. · ❹

=, the apatite coated powder obtained by the household is 2〇g and the organic stone sol-gel, combined with the night (solid content concentration is 3. 〇wt%) 2g in the maximum content A polypropylene bottle After 10 minutes, remove the contents: in a stainless steel dish 'in less than _丨Mpa =. = The powder was pre-hardened for 25 minutes = and the iron powder received was passed through a 250 //m sieve. g Filled in a mold with a nano-dioxide-coated stone-coated iron powder 6 i t 4 mm, formed into a cylindrical gorge at 1000 chest (10) 2 . At this time, the thickness of the obtained (4) is about 34 200932404 5 coffee. The surface of the shaped tablet was ground. t The volume resistivity (resistivity) was measured, and the bulk density was 7. 2 using a &amp; sub-resistivity meter. In a nitrogen atmosphere, the 68-grinding lozenge is subjected to H, time annealing, and the county surface is in and out = the terminal resistivity is set to volume resistivity (t is four

〇m. In addition, the density of the molded body is 749 "2 drought", and the fruit is 56 A.

[Example 9] In Example 3, 9D°r is, "〇 + was burned and burned. The c reaction was changed to a thief, and it was changed to a pH of 75 mL (= _〇1 'face M) and iron powder (God (= 3〇_) 30 g) in a 300 mL four-necked flask. 'Stirring in an oil bath of 3 ° ° C ^ Pure ^ Add a side tube to the dropping funnel and add 2: : inch to 11 oil disc dihydrogen recording water, m / value 5 weeks is large (4), The dropping funnel was fixed again;: mL (1.07-01' caffeine was placed on a four-necked flask. On the other hand, at 30°, the anvil V:: mixed;: t bottle') was added dropwise thereto for 1 minute. The aqueous solution of the 从-ammonium solution in the liquid funnel was then dropped for 1.5 hours under the temperature of the oil bath. ^ L¥j , 軎, ^.5 4 The temperature of the oil bath was raised from 3 ° C to 50 ° C, one /曰/1 The contents of the four Γ Γ — 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 瑕 瑕 瑕 瑕 瑕 瑕 瑕 瑕 瑕The atomic presence rate near the surface of the gray iron powder 71 powder was 35 Ο ❹ 200932404 FV 4.89%, Ca: 15 ... :, , , .7, and it was confirmed that the powder was coated with hydroxyapatite. Stone coated powder 20 g and organic glue 50 mL tight knife / chen It is 3.0% by weight) 2 g in the maximum content of the stainless steel dish, = 2 surplus 1 〇 after the minute, the contents are taken out and transferred to the fine t: under the action of removing the ^ for 5 minutes, the obtained iron powder pass = 2 pre-hardening. Pre-hardened and oxidized so that 66 # t A m sieve. The obtained attached nano-tool, in ι_Λ = ί powder 6 § filled in the mold with inner diameter of 4 sides At this time, the (four) force is the cylindrical shape of the county, and the volume resistivity is measured by the 137 sub-resistance meter (resistance in a nitrogen atmosphere; in addition, the density of the molded body is 7.50-2. For the surface η, the polished tablet was subjected to a depressurization rate for 1 hour (the resistance was measured by a four-terminal resistivity meter to be 7.5 〇g/c! J was 44/ζΩιη. In addition, the molded body density [Example 10] In Example 3, no 110 〇C calcination was performed. That is, 'the positive value in the 300 mL four-necked vial was adjusted to be greater than or equal to u. ^= force: a dropping funnel with a side tube using 25% ammonia water Add 25^15: clock in the process. After that, adjust the PH value to 25/32/32 in the supplement with 25/〇虱 water for a water-soluble ammonium dihydrogen phosphate solution equal to 11 75 mL (丨〇7 Μ) 'The funnel was fixed on a four-necked flask. While stirring four times in oil cooling, the dihydrogen phosphate aqueous solution was added dropwise thereto in j minutes. Then, the oil bath temperature was stirred for 1.5 hours under the condition of the oil bath temperature. After 30C, the oil bath temperature was raised from 3 Torr to 10 Torr for 2 hours. The obtained slurry was vacuum dried at 0.2 MPa to obtain a gray color.愐XPS analyzes the obtained iron powder, and the result is atom =

Fe:^5〇/〇.Ca:l^ A1...^ The obtained disc lime-coated powder 2〇g and organic Shishisol 妓3.G Wt%) 2(9) The maximum amount of sacrificial is 1 and then moved to No 20 (ΤΓτΓ4α is dried at a pressure of 4 MPa for 5 minutes, and the obtained iron powder is pre-hardened and refined to obtain yttrium oxide coated with apatite. The force is formed into a row of grinding, using four ends. The surface of the forming agent is 137 θ -. The other two meters are measured, the resistivity (resistivity) is in the gas environment, at 600t, ^ Bulk density* 7.5〇g/Cm2. After re-grinding the surface of nitrogen, the lubricated agent is subjected to H, time annealing, rate (resistivity), =^ using a four-terminal resistivity meter to measure volume resistance, In addition, the density of the molded body was 7.50 37 200932404 g/cm 2 ° [Example 11] In Example 3, the nitrate was _1, and the acidity of the dish 4=:= was quantified 9-弋〇 36mmQl. Addition of thief (4) u7m_l changed to Η: Add 45% larger volume of ammonia to the 四 ❹ P 1 S〇_ M); Moon U U nitrate solution 75 mL (0.60 mmol, 0.008 M) ) and iron powder (God 3 喔) _, line. (10) ^Silver pure iron powder Add a 2 knives to the dropping funnel with a side tube. After that, 'the water is added to the aqueous solution of the mixed gas, which is equal to η, 75 ^ water and the positive value is adjusted to be large %), and the dropping funnel is fixed in four (.36_b〇 side Luo, stirring four mouths, - side to Use: - 3G ° C oil - acid dihydrogen solution aqueous solution, and then stir in the dropping funnel in the state of stirring for 1.5 hours., ', 'Sa X is maintained at 30. (: shape followed by 10 while stirring - at 90X; when the reaction is 2 / J, gas filtration, drying in the not in the box, the slurry is pumped powder. Using xps on the surface of the obtained powder: 2 gray iron analysis, As a result, the atomic existence rate of Fe: 7 , ', and the ratio of the existence of the sub-proportion (Mohr ratio) was 1.52. · ° ^ : 13.14%, Ca / p "further" the obtained asbestos-coated powder solution (solid content concentration: 3 • 〇 wt%) 2ji organic bismuth sol 50mL· in a polypropylene bottle, the large amount of content is the knives, and the contents are taken out and moved 2 38 200932404 'In the less than or equal to IMP ^ M force After drying for 5 minutes, the pre-hardening of the smear of the smear (10) is carried out for 25 minutes. The pre-hardened and == 25 〇 sieve is added. 6g iron powder coated with a nano-filled inner diameter surface of the mold 14

❹ = at this time, the thickness of the obtained tablet is === rate),: 11'12^: The terminal resistivity meter measures the volume resistivity (in the resistance environment, after grating under g Ϊ resistance C, after grinding, four terminals two Two Sr, the result was 3 〇-, and the formation of Si [Example 12] was changed from 178 mmol to U7 mmol to Example 3, and the acid addition amount was 2.98 mm 〇1, and ammonium dihydrogen phosphate was added. The amount of the nitric acid in the four-necked flask of 1.78 mmol.w was adjusted to be greater than or equal to n. The nitric acid used in the current ammonia water &gt;1, 〇·_ M) and iron powder (Kobe made 75 mL (2.98 300 bribe) 30 g In the oil bath of 3 (TC oil bath, the pure iron powder produced by the company has a side tube of the dropping funnel t plus 25. /- u minutes. After that, the solution is attached to a dihydrogen sulphate solution equal to 11 75 ° ^ adjust the positive value to a large M) 'and then fix the dropping funnel to four h78 mmol, 0.024 oil bath to ft mix four π flask, - side to the top. - edge 3 (TC's clock The dropping funnel 39 ❹ ❹ 200932404 dihydrogen ammonium chloride solution was added, and then the temperature of the oil bath was maintained at 30. The state of the oil bath was stirred for 1.5 hours. (4) The temperature of the oil bath was raised from 3 ° ° to 9 ° C for 1 G minutes. The reaction was carried out for 2 hours at 9 GG. The (four) solution was obtained and dried in an oven. The results obtained were gray iron=, ==:::r. (Mo Erbi = 67 Wh: 17.59. /. '^ Toluene, volume: obtained (four) apatite coated powder 2〇g and organic sputum sol A; "(solid content concentration of 3._%) under the boot: The obtained iron powder is hardened, and the pre-hardened and oxidized sieve is used. The obtained nano-device is coated with uTgo^p', and 6 g is filled with a molding agent having an inner diameter of 14 mm. The ingot surface formed into a cylindrical shape is polished, and the probability of using the f-money agent is as follows. The result is the volume resistivity of the crucible (resistance to nitrogen is additionally 'the density of the molded body is WgW. Fire, ==: Γ00. The milled spinner was purchased with a resistor of 4 = two mills: a 7-sheet resistivity meter was used to measure the product of 7.44 gW as 88 cores 111. In addition, the molded body density [Example 13] 200932404 and Example 11 m, The composition of the silk film is made up of a layer of powder. The private base vermiculite layer is a two-layer structure _ base apatite coated iron PH value adjustment flask 25% aqueous ammonia shaft Bu 〇._ M) '1 iron private, dance nitrate aqueous solution 75 mL (0.60

300NH) 3〇g, pure iron powder manufactured by Kobe Steel Co., Ltd. Add a minute to the dropping funnel with a side tube. Afterwards, 'attach to @_. equal to 11. Use 25/0 虱 water to adjust the pH to large (4), then 11 mL aqueous solution 75 mL (0.36 surface 1, 0.005 oil bucket fixed -. - side of the liquid funnel: Two watts were added to the contents of the mixture for 10 minutes, and the amount of 3 〇cC was added dropwise. The green color was stirred for 1.5 hours while keeping the secret temperature at L. The side spectrum was 0 minutes. The temperature of the oil bath is raised from 3 °C to 9 °C. C, the obtained pulp:: burned and reacted at 9 (rc for 2 hours). The selected fruit was filtered and filtered at 11 〇. Drying in an oven at °C, and obtaining a gray iron powder (yield of 96 wt%). Then, the obtained single-layer apatite layer 1 coating powder 28.8 g and pH value with 25% ammonia water Adjusted to a calcium nitrate aqueous solution equal to or greater than η, mL (〇*57mmobu 0.0081^[) was added to a four-necked flask of 30〇1]11^, and stirred in an oil bath of 3〇ΐ for 15 minutes. The dropping liquid with the side tube was added to 72 mL (0.34 mmol, 0.005 Μ) of the aqueous solution of ammonium dihydrogen phosphate adjusted to 大于 or more with 25% ammonia water, and the dropping solution of 200932404 was fixed in a four-necked flask. On the side of the 3 flask, - to the contents of the 10 minutes drop ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ (rc rise and react at 90 ° C for 2 hours while stirring. For dry e/JEt, one gas filtration, iio °c oven for dry welding, pumping

The ratio (Morby) is 1.59. * 13.84/0 &gt; Ca / P and then 'will be obtained two layers of apatite 2 layer machine Shixi sol toluene solution (solid 旻 旻 旻 旻 旻 旻 与 与 与 与 与 与 旻 . . . . . . . . . . . . . . . . . . . . . . . . . 2 g in the largest t-propene bottle shakes 1 〇c stainless steel, in the iMp force less than or equal;; you 5 knives 'under the view to take out the pre-hardened and get the 25-minute clock Pre-hardened.附着 Attached to the nano-sulphur dioxide white sputum ^ over 250 difficult sieve. The obtained 14-leg mold was filled with 6 g of gray stone coated iron powder in a columnar shape. Forming the surface of the suspected agent under the molding of the second and the second (2). The thickness of the reader is about 5 mm. For the molding ratio (resistivity), the junction 1 was measured by a four-terminal resistivity meter to have a volume resistance of 7.53 g/cm2. Yus] 31 #Ωιη. In addition, the density of the molded body was 1 hour, and the volume resistivity of the milled rotary agent was re-polished at 600 ° C in the cousin, and then measured by a four-terminal resistivity meter (resistance). Is 59. In addition, the molded body 42 200932404 has a bulk density of 7.53 g/em2. [Example 14] The structure of Sit:: stone was packaged, and the method of (4) was used to prepare a base apatite layer ~:: two: the same powder. Fishing layer, and the residue of the mouth structure of the apatite coated iron 7 value of 7 is _ water will mmo Bu 0 · _ JV 〇 and age w of the nitrate '^ dance aqueous solution 75 mL (0.60 300NH) 30g, ^^ (The pure iron powder manufactured by Kobe Steel Works Co., Ltd. has a side tube in the dropping funnel and added eight ali: two ==: r, 75 two == oil bath in the mixing four π flask bottle. One side at 30 ° C Within the _ dichlorinated water; liquid, = # use, minute drop plus dropping funnel state under the disturbance of 1.5 hours....' 4 in the temperature is maintained at 30 ° C φ 30 〇 c ^ ^ ^ 90 ° c &gt - powder. The L phase is dried and dried, and the result is gray iron. Then, the obtained asbestos 1 layer coated iron powder 2 is adjusted to a pH greater than or equal to u with 25% gas water. Add 0.5 ml of o.sub.10 (0.59 mm Gl, _8 M) to the oil of 30 C for 15 minutes. Thereafter, add phosphoric acid with 25% ammonia water to adjust the pH to n or more with the side #=liquid 43 200932404. 74 mL (0.35 mmol, 0.005 Torr) of aqueous ammonium hydroxide solution, the dropping funnel was fixed on a four-necked flask, and the mixture was stirred in a 3 Torr oil bath for four times, and the dropping funnel was added dropwise over 10 minutes. Ammonium dihydrogen phosphate water = liquid ' Then keep the oil bath temperature at 3 〇 (3 (: stir) 15 small

Next, the temperature of the oil bath was raised from 3 Torr to 9 ° C over 10 minutes, and the contents of the four-necked flask were stirred by a π while reacting at 9 Torr for 2 hours. The obtained liquid was evacuated and dried in an oven towel of n (rc) to obtain a gray iron powder. The obtained two layers of the disc stone were coated with iron powder of 29 5 g and using 25% ammonia. 7 The aqueous solution of the aqueous solution of yoghurt adjusted to a value of u or more was added to a 3 〇〇mL four-necked flask, and stirred at 3 :: wide for 15 minutes. Thereafter, the dropping funnel with the side tube is added: ammonium dihydrogen phosphate water =, 74 mL (0.35 mm 〇〇〇 〇〇〇 5 M) adjusted to a pH of 11 or more with 25% ammonia water, and then The dropping funnel is fixed = the upper side of the bottle is mixed with three oil in the oil cap of 3Gc&gt;c, and the side::: The aqueous solution of ammonium dihydrogen phosphate in the dropping funnel is added dropwise with 10 knives, and then the temperature is The mixture was kept at 3 G &lt; t for 1.5 hours. Next, the oil bath temperature was increased from 3 Torr over 10 minutes, and the temperature was raised to 9 Torr, and the reaction was carried out for 2 hours at 90 °. The obtained slurry was pumped for 11 Torr. Drying in the oven of C, the result is gray iron = end. _ Which pair of powders are analyzed, the atomic existence rate is Fe: 1, ~ 1G95% sheep ^ 44 200932404 ratio (mole ) is 1.69. Further, the obtained apatite 3-layer sol toluene solution (solid content concentration is 3 〇wt%) 2 bis = 50 mL of polypropylene squirting in the air for 1 minute and then ❹ Move to a stainless steel dish, and pre-harden the removed powder for 25 minutes at a pressure of less than or equal to __ to pre-5 obtain the side iron powder through the 25() _ sieve. The oxygen-cut apatite layer 3 is coated with 6 g of the inner layer with a crucible, and the crucible is formed into a cylindrical shape under the side force of 2". At this time, the obtained lozenge has a thickness of about 5 mm. Grinding the molded surface 'Measurement of volume resistivity (f resistivity) using a four-terminal resistivity meter results in 95 〃 Ωιη. In addition, the density of the molded body is 7 494 g / ii. In a nitrogen atmosphere at 6 〇 After the ruthenium was subjected to a small enthalpy annealing, the surface was reground, and the volume resistivity (resistivity) was measured by a four-terminal resistor, and the resulting bulk density was 7.5 Gg/cm2 at 31 Α Ωιη. [Example 15] In Example 3, the amount of iron powder added was changed to 33 times, and at the same time, the volume of the reaction container was also When the amount of the solvent or the like was changed to 3.3 times, the aqueous solution of ammonium dihydrogen phosphate was added dropwise to the contents of the flask, and the time for stirring in the oil bath of 3 (rc) was changed from 1.5 hours to 2 hours. To a 1000 mL four-necked flask, 25 mL of an aqueous solution of calcium nitrate adjusted to a value of 11 or more with 25% ammonia water (595 〇1, 0.024 M) and iron powder (pure iron manufactured by Kobe Steel Co., Ltd.) Powder 45 ❹ ❹ 200932404 300NH) l〇〇g, at 3〇. "In the dropping funnel with the side tube, the mixture is stirred for 15 minutes. After that, the value is adjusted to 0.014M by using 2% ammonia water to be equal to or greater than u_acid two islands, and the liquid is adjusted to 0.014M. 250 mL of liquid (3·57 〇 t t t: In the oil bath, mix four:: 匕 fixed on a four-necked flask. - Add 3 drops to the 3 hopper in the funnel. In the state of c, the lion is 2 hours' then keep the oil bath temperature at 30 side:: side = 3, the oil bath temperature is raised from 3 (rc to 9 (rc, - gas is too high, in the case of not) The obtained slurry was pumped too. ## Drying with t, the result is gray iron ===== analysis, the result of the atomic existence rate is covered by guacarite G/°'ca/p ratio丨.76, can be sure that the powder amber two pieces of apatite coated iron powder 60 g and organic bismuth sol 50 ί concentration is 3 * 〇 Wt%) 6 § in the maximum content is not two # 细After the bottle was shaken for 110 minutes, the contents were taken out and moved to 200. "^' was pre-hardened for 25 minutes under the force of less than 1 ΜΡ &amp; _ force for 25 minutes. Pre-hardened and 1 '4 Pass 250 (four) of cotton. Will get the attachment Nano j cut_grey stone coated iron powder 6 g is filled in a mold with an inner diameter of 14 faces: a key back of a cylindrical shape formed under the molding pressure of 1_MPa/em2. At this time, the thickness of the obtained key agent It is about 5 mm. For the molding of the bonding agent, the following is the measurement of the volume resistivity (resistance ^) by a four-terminal resistivity meter, and the result is 193 // Ω η. In addition, the density of the molded body is 7.51 g/cm 2 . 200932404 In the middle of the environment, the pair is ground _, the result of the electric call is 7.51 g/cm2. The force outside the molded body is the same as that obtained in the first to the fifteenth embodiments. The word "1", which is related to the rice oxidized fine gray stone coated iron powder, is shown in Table 3 to Table 5.

[Table 3] Example Apatite raw material addition amount (relative to iron powder) (mass%) Synthetic condition Apatite coated iron powder synthesis step Attached with a dioxide dream apatite coated iron powder synthetic step stone powder (r) Synthesis time @30°C (min) Synthesis time @丁匚(min) Drying @no°c Drying @200°C Example 1 0.6 30 0 120 (T=90) 11 &gt;&gt;. Example 2 —-____________ 0.6 30 25 120 (Τ=90) Yes — ~~ There are Examples 3 0.6 30 115 120 (Τ=90) There is a poor example 4 0.6 30 115 10 (Τ=90) There are examples 5 ----__ 0.6 30 115 300 (Τ=90) ----- There is a treasure example 6 0.6 30 235 0 There are examples 7 0.6 30 115 120 (Τ = 50) There are implementations Example 8 A 0.6 30 25 0 ------ No Example 9 0.6 30 115 120 (Τ=50) None _Example] 〇0.6 30 115 120 (Τ=90) No Example 11 -- ---------· 0.2 30 115 120 (Τ=90) There are examples 12 1.0 30 115 120 (Τ=90) There are two cases 13 0.6 (x2) 3 factory 115 (x2) 120 (Τ=90)(χ2) There are examples 14 0.6 (x3) 30 115 (x3) 120 (Τ=90) (χ3) There is no [Ϊ^ΓΤ5 0.6 100 165 120 (Τ=90 ) Yes Yes _ Ο 47 200932404 [Table 4]

Example xps data (atomic ratio, %) Coverage ratio 01s + Ca2p + P2p / (01s + Ca2p + Fe2p + P2p) xlOO Ca / P Cls Nls Ols Ca2p Fe2p P2p Example 1 16.7 0 53.5 15.7 4.6 9.6 94.5 1.67 Example 2 13.9 0 55.2 17.1 3.3 10.5 96.2 1.63 Example 3 34.1 0 56.4 14.9 5.6 9.1 93.5 1.63 Example 4 14.5 0 57.0 12.8 6.9 8.9 92.1 1.43 Example 5 14.0 0 57.6 14.0 6.1 8.4 92.9 1.67 Example 6 16.3 0 57.1 11.7 7.8 7.1 90.6 1.65 Example 7 15.1 0 57.2 13.2 7.1 7.5 91.7 1.77 Example 8 16.8 0 55.1 13.6 5.5 8.9 93.4 1.52 Example 9 12.3 0 58.5 15.5 4.9 8.8 94.4 1.77 Example 10 11.0 0 57.9 16.6 3.9 10.6 95.7 1.56 Example 11 15.7 0 55.2 13.1 7.3 8.7 91.4 1.52 Example 12 1L1 0 58.0 17.6 2.8 10.5 96.9 1.67 Example 13 13.6 0 56.8 13.8 7.1 8.7 91.8 1.59 Example 14 14.6 0 57.7 11.0 10.3 6.5 87.9 1.69 Example 15 16.3 0 55.9 15.3 3.9 8.7 95.4 1.76

[Table 5] Example Powder Core Characteristics Molded Body Density (g/cm3) Resistivity (β Ω γπ) Example] 7.47 91 Example 2 7.50 75 Example 3 7.51 55 Example 4 7.49 53 Example 5 7.47 93 Implementation Example 6 7.53 31 Example 7 7.47 53 Example 8 7.48 56 Example 9 7, 50 44 Example 10 7.50 30 Example 11 7.56 30 Example 12 7.44 88 Example 13 7.53 59 Example 14 7.50 31 Example 15 7.51 41 48 200932404 Referring to Table 4, it is understood that even if the synthesis method is different, the base wall gray stone layer can be formed on the metal powder with the same degree of coverage. Further, as can be seen from Tables 3 and 5, in the production step, the powder magnetic core of the hydroxyapatite-coated iron powder to which the nano cerium oxide is attached, which is subjected to the pre-hardening step, is subjected to a pre-hardening step, and the display thereof is shown. Has a higher electrical resistivity and molded body density. Although the present invention has been disclosed in the above embodiments, it is not intended to limit the invention, and any one of ordinary skill in the art can make some modifications and refinements without departing from the spirit and scope of the invention. The scope of protection is defined by the scope of the patent application attached to the following [simplified description of the schema] - year. 1 is a photograph showing a scanning electron microscope (SEM) image of a hydroxyapatite package obtained in Example 1 (magnification lb (8) FIG. 2 is a photograph showing an SEM image of a hydroxyapatite package profile obtained in Example 1. FIG. (magnification·· 50000 times). Fig. 3 is a view showing that the brain 1 of the cross section of the iron-coated iron powder coated with the nano-dibasic disc-coated iron powder obtained in Example 1 was 1000 times). Y, and sheet (magnification: ^, SEM image, 100,000 times of the cross section of the hydroxy sapphire-coated iron powder to which nano-oxidation was obtained in Example 1). Outline ~ Sheet (magnification: [Major component symbol description] 49

Claims (1)

200932404 VII. Patent Application Range: 1. A powder comprising a metal powder, an apatite layer covering the metal powder, and a silica particle attached to the metal powder or the apatite layer. 2. The powder according to claim 1, wherein the apatite layer contains a compound represented by the following formula (Ϊ -a) or formula (1 - b), ❹ Ca10 (P〇4) 6X2 Ga (1〇—(njxn) /2) Μη(Ρ〇4)6χ I — a (I —b) Lu (wherein M represents an atom providing a cation, and m represents a valence t of a cation provided by M, n is greater than 〇 and less than or equal to 5, and χ represents an atom or a group of atoms providing a monovalent anion). = the powder described in the scope of the patent or the second item, the cerium oxide oxidized heteropoly is a surface-modified dioxide which is described in the third paragraph of the patent scope of claim 3 The powder is organically modified, and the surface compound is RlnSi(〇R2) 驮SiXh n ( Π ) r -X' rb ( Βί 其中 X 其中 利用 利用 利用 X X X X X X X X X X X X X X X X X X X X X X X X X X X X ), ^ _ :n is an integer of Bu 3, Ri and Rule 2 represent a monovalent organic group, and X represents Nansu) 5 If you apply for a special _ fresh! The powder according to the item, wherein the above metal 50 200932404 powder is a powder of a soft magnetic material. 6. The powder used in the application for patents. A method for producing a powder of the same type of powder, comprising: a first step of coating a metal powder-metal powder with apatite; and apatite coating with a step of apatite = step two The oxidized impurities are attached to the surface of the metal powder or the surface of the county stone layer coated with the metal powder of the above-mentioned shale, and the second (four) powder is pre-hardened at a temperature of 35 Gt or less. A powder having the above metal powder, the metal powder_grey stone layer, and the bismuth oxide particles attached to the metal powder or the apatite layer is obtained. 8. The method for producing a powder according to claim 7, wherein the metal powder treated with the squaric acid is used as the metal powder supplied to the first step. 51 200932404 IV. Designated representative map: (1) The designated representative figure of the case: Figure (1). (2) A brief description of the symbol of the representative figure: None 0. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: ❹ No.