201202439 六、發明說明： 【發明所屬之技術領域】 本發明係關於具有優異之磁特性的Fe-系非晶 帶，及由該Fe-系非晶質合金帶所構成之磁心；特別 Fe-系非晶質合金帶與其可用於各種變壓器、反應器 零件（如用於主動濾波器之抗流線圈、平流抗流線圈 抗流線圈等）、雷射電源供應器、加速器之磁脈衝電j 馬達、發電機等的磁心。 【先前技術】 矽鋼與Fe-系非晶質合金帶係已知爲具有用於 壓器；反應器、減噪零件（如用於主動濾波器之抗流 平流抗流線圈、共模抗流線圈與電磁遮板）、雷射電 器、加速器之磁脈衝能源零件、馬達、發電機等之 磁通量密度及低磁心損失的磁性合金。雖然矽鋼具 通量密度且成本低，但缺點是在高頻率應用中會承 損失。Fe-系非晶質合金具有較矽鋼低之飽和磁通量 而導致有較大之磁心尺寸。該等亦具有大的磁致伸 其特性易因應力而劣化。 作爲用於變壓器之磁心材料，J P 9 - 3 1 6 1 0 A揭 用來製造非晶質Fe-Si-B-M合金帶之方法，其中Μ 種選自包括Al、Ti、S、Μη與Zr之群組中至少一種 避免的不純物。該非晶質合金在80A/m磁場中具有 上之磁通量密度。 質合金 係關於 、減噪 、共模 ]零件、 各種變 線圏、 源供應 高飽和 有高磁 受磁心 密度， 縮，且 示一種 表示一 之不可 1 ·4Τ 以 201202439 作爲用於改善Fe-系非晶質合金之磁心損失的3 10_324961 A揭示一種用於製造pe-Si-B-M非晶質合 方法，其中Μ爲選自包括Mn'Co、Ni與Cr之群組 一種。於該方法中’在磁場中、於中等或高溫下進 熱處理之前’於相對低溫下進行熱處理至少6小時 然而’上述傳統之Fe-系非晶質合金帶因磁通量 而不適合作爲用於變壓器之磁心材料。由於磁通量 則最大操作磁通量密度必然爲低，故具有低磁通量 磁心必然具有大的體積或重量。 雖然已有人在得自上述傳統Fe-系非晶質合金 板上硏究過磁心損失，但並未對於作用於磁心時所 力進行過硏究。再者，由於在由JP 10-324961所提 造方法中的熱處理需要長時間，其極爲不利於量產 由於非晶質Fe-Si-B或Fe-Si-B-C合金在適合於 磁通量密度的組成物中具有低結晶溫度，故該等應 下進行熱處理。在此情況下，由於在作用於用於變 磁心的Fe-系非晶質合金中所產生之應力未充分鬆 Fe-系非晶質合金之磁特性極爲不佳。 【發明內容】 發明之目的 因此，本發明之一目的係在於提供一種具有改 和磁通量密度及軟磁特性的Fe-系非晶質合金帶，其 相對短時間之熱處理來充分地鬆弛其應力。 ί 法，JP 金帶的 中至少 行傳統 以上。 密度低 密度低 密度之 帶的平 產生應 出之製 〇 筒飽和 在低溫 壓器之 弛，故 善之飽 中藉由 -4- 201202439 本發明之另一目的係在於提供一種由該F e-系非晶質 合金帶所構成之磁心。 發明之槪述 如本發明之具有優異磁特性之第一種Fe-系非晶質合 金帶係藉由下列通式來表示：FeaSibBcMx，其中 Μ爲 Cr 及/或Ni，a爲78〜86原子％，b爲0.001〜5原子％，c爲 7〜20原子％，X爲〇.〇1〜5原子％，而（a+b+c+x)爲 100。當Μ爲Cr時，X以0.01〜1原子％爲佳；而Μ爲Ni 時，則X以0. 1〜5原子％爲佳。在預定之條件下之熱處理 可提供該具有經改善之磁通量密度與已充分鬆弛之應力的 Fe-系非晶質合金帶。該Fe-系非晶質合金帶係以具有25〜 4 0μιη之厚度、1 .6T以上之飽和磁通量密度、及在80A/m 磁場中爲1 . 5 T以上之磁通量密度爲佳。 | 以a爲78〜85原子％、1»爲0.001〜3原子％、c爲10〜 20原子％、及X爲0.02〜4原子％來提供具有更加改善之磁 通量密度與充分鬆弛之應力的Fe-系非晶質合金帶爲較佳= 該Fe-系非晶質合金帶具有1.65T以上之飽和磁通量密度、 及於80A/m磁場中爲1.6T以上之磁通量密度。 根據本發明之具有優異磁特性之第二種Fe-系非晶質 合金帶係以下列通式來表示：FeaSibBcCdMx，其中Μ爲Cr 及/或Ni，a爲78〜86原子％，b爲0.001〜5原子％，c爲 7〜20原子％，d爲0.001〜4原子％，及X爲0.01〜5原子 %，而（a+b+c+d+x)爲 100。當 Μ 爲 Cr 時，X 以 0.01 〜 201202439 1原子％爲佳，而Μ爲N i時，則x以〇 . 1〜5原子％爲佳。 在預定之條件下之熱處理可提供該具有經改善之磁通量密 度與已充分鬆弛之應力的Fe-系非晶質合金帶。該Fe-系非 晶質合金帶係以具有25〜40μιη之厚度、1.6T以上之飽和 磁通量密度、及在80A/m磁場中爲1.5Τ以上之磁通量密度 爲佳。 以a爲78〜85原子％、1)爲0.001〜3原子％、c爲10〜 20原子％、d爲0.01〜3原子％、及X爲〇.〇2〜4原子％來 提供具有更加改善之磁通量密度與充分鬆弛之應力的Fe-系非晶質合金帶爲較佳。該Fe-系非晶質合金帶具有1.6 5T 以上之飽和磁通量密度、及於80A/m磁場中爲1.6T以上之 磁通量密度。 本發明之磁心係由上述Fe-系非晶質合金帶之任一種 藉由截斷搭接（cut lap)或階式搭接（step lap)方法所構成而 具有用於變壓器之形狀。 較佳樣態之詳細說明 [1 ]組成 本發明之第一 Fe -系非晶質合金係以下列通式： FeaSibBcMx所表示，其中]^爲Cr及/或Ni、a爲78〜86原 子％、b爲0.001〜5原子％、c爲7〜20原子％、及\爲 0.01 〜5 原子 ％，其中（a+b+c+x)爲 1〇〇。 本發明之第二Fe-系非晶質合金係以下列通式： FeaSibBcCdMx所表示，其中Μ爲Cr及/或Ni、a爲78〜86 201202439 原子％、b爲0.001〜5原子％、c爲7〜20原子％、d爲 0.001〜4原子％、及X爲0.01〜5原子％，其中（a+b+c + d + X )爲 100。 當使用包含Cr及/或Ni之本發明的Fe-系非晶質合金 時，藉由熱處理來充分鬆弛在製造磁心時所產生之應力》 Cr係作用來提供具有減低之熔融黏度、及隨輥與表面條件 改善之濕潤度的合金。Cr與Ni亦具有加速在熱處理時Fe-系非晶質合金中之應力鬆弛的效果，從而改善其軟磁特性。 然而，當所包含之Cr及/或Ni的量太小時則不能得到充分 的效果；而當其含量過多時則居禮溫度與飽和磁通量密度 會明顯劣化。因此，基於100原子％之合金主成份（a + b + c + x 或a + b + c + d + x)計，Cr及/或Ni的含量爲0.01〜5原子％， 而以0.02〜4原子％爲佳，以0.1〜4原子％爲較佳。 當Μ爲C r時，X範圍則以0. 〇 1〜1原子％爲佳，以 0.02〜0.5原子％爲較佳。當Μ爲Ni時，X範圍則以0.1〜 5原子％爲佳，以0.3〜4原子％爲較佳。因此在必需量方 面，Cr與Ni有所不同。Cr係小量即能有效鬆弛在形成磁 心時所產生之應力，而Ni係較Cr大量始能有效鬆弛在形 成磁心時所產生之應力。可隨所要求之磁特性與應力鬆弛 速度來適當地選擇Cr和Ni。201202439 6. TECHNOLOGICAL FIELD OF THE INVENTION [Technical Field] The present invention relates to an Fe-based amorphous ribbon having excellent magnetic properties, and a magnetic core composed of the Fe-based amorphous alloy ribbon; Amorphous alloy ribbons and their use in various transformers, reactor parts (such as anti-flow coils for active filters, anti-flow coils for anti-current coils, etc.), laser power supplies, accelerators, magnetic pulse motors, The core of a generator or the like. [Prior Art] Tantalum and Fe-based amorphous alloy ribbons are known to have pressure regulators; reactors, noise-reducing parts (such as anti-flow anti-flow coils for active filters, common mode choke coils) Magnetic alloys with magnetic flux density and low core loss for magnetic pulse energy components, magnetic devices, generators, etc. with electromagnetic shutters, lasers, accelerators, etc. Although Nd steel has flux density and low cost, it has the disadvantage of bearing losses in high frequency applications. Fe-based amorphous alloys have a lower saturation magnetic flux than tantalum and result in a larger core size. These also have large magnetic elongation and their characteristics are easily deteriorated by stress. As a core material for a transformer, JP 9 - 3 1 6 1 0 A discloses a method for producing an amorphous Fe-Si-BM alloy ribbon, wherein the species is selected from the group consisting of Al, Ti, S, Μη and Zr. At least one impurity that is avoided in the group. The amorphous alloy has a magnetic flux density in a magnetic field of 80 A/m. The quality of the alloy is related to, noise reduction, common mode] parts, various variable line 圏, source supply, high saturation, high magnetic core density, shrinkage, and a kind of indication that one can not be 1 · 4 Τ with 201202439 as used to improve Fe-line A core loss of amorphous alloys is disclosed in a method for producing a pe-Si-BM amorphous conjugate, wherein ruthenium is selected from the group consisting of Mn'Co, Ni and Cr. In the method, 'heat treatment at a relatively low temperature in a magnetic field, before being subjected to heat treatment at medium or high temperature, at least 6 hours. However, the above-mentioned conventional Fe-based amorphous alloy ribbon is not suitable as a magnetic core for a transformer due to magnetic flux. material. Since the maximum operating magnetic flux density is inevitably low due to the magnetic flux, the magnetic flux having a low magnetic flux must have a large volume or weight. Although the core loss has been studied on the conventional Fe-based amorphous alloy plate, it has not been studied for the action on the core. Furthermore, since the heat treatment in the method proposed by JP 10-324961 takes a long time, it is extremely disadvantageous for mass production due to the composition of the amorphous Fe-Si-B or Fe-Si-BC alloy suitable for the magnetic flux density. The material has a low crystallization temperature, so these should be heat treated. In this case, the magnetic properties generated in the Fe-based amorphous alloy which acts on the Fe-based amorphous alloy for the magnetic core are not sufficiently loose, and the magnetic properties of the Fe-based amorphous alloy are extremely poor. DISCLOSURE OF THE INVENTION Accordingly, it is an object of the present invention to provide an Fe-based amorphous alloy ribbon having a modified magnetic flux density and soft magnetic properties which is heat-treated for a short period of time to sufficiently relax the stress. The ί method, the JP gold belt, at least the traditional above. The density of the low-density, low-density belt is flat and the cylinder is saturated in the low-temperature press. Therefore, it is further to -4-201202439. Another object of the present invention is to provide a system for the F e-system. A magnetic core composed of an amorphous alloy ribbon. SUMMARY OF THE INVENTION A first Fe-based amorphous alloy ribbon having excellent magnetic properties according to the present invention is represented by the following formula: FeaSibBcMx, wherein yttrium is Cr and/or Ni, and a is 78 to 86 atoms. %, b is 0.001 to 5 atom%, c is 7 to 20 atom%, X is 〇.〇1 to 5 atom%, and (a+b+c+x) is 100. When the Μ is Cr, X is preferably 0.01 to 1 atom%; and when Μ is Ni, X is preferably 0.1 to 5 atom%. The heat treatment under the predetermined conditions can provide the Fe-based amorphous alloy ribbon having an improved magnetic flux density and a sufficiently relaxed stress. The Fe-based amorphous alloy ribbon preferably has a thickness of 25 to 40 μm, a saturation magnetic flux density of 1.6 T or more, and a magnetic flux density of 1.5 T or more in a magnetic field of 80 A/m. | Fe having a more improved magnetic flux density and sufficient relaxation stress with a of 78 to 85 atom%, 1» of 0.001 to 3 atom%, c of 10 to 20 atom%, and X of 0.02 to 4 atom%. A-type amorphous alloy ribbon is preferable. The Fe-based amorphous alloy ribbon has a saturation magnetic flux density of 1.65 T or more and a magnetic flux density of 1.6 T or more in a magnetic field of 80 A/m. The second Fe-based amorphous alloy ribbon having excellent magnetic properties according to the present invention is represented by the following formula: FeaSibBcCdMx, wherein yttrium is Cr and/or Ni, a is 78 to 86 atom%, and b is 0.001. 〜5 atom%, c is 7 to 20 atom%, d is 0.001 to 4 atom%, and X is 0.01 to 5 atom%, and (a+b+c+d+x) is 100. When Μ is Cr, X is preferably 0.01 to 201202439 1 atom%, and when Μ is N i , then x is 〇 1 to 5 atom%. The heat treatment under the predetermined conditions provides the Fe-based amorphous alloy ribbon having an improved magnetic flux density and a sufficiently relaxed stress. The Fe-based non-crystalline alloy ribbon preferably has a thickness of 25 to 40 μm, a saturation magnetic flux density of 1.6 T or more, and a magnetic flux density of 1.5 Å or more in a magnetic field of 80 A/m. Providing a further improvement in which a is 78 to 85 atom%, 1) is 0.001 to 3 atom%, c is 10 to 20 atom%, d is 0.01 to 3 atom%, and X is 〇.〇2 to 4 atom%. The Fe-based amorphous alloy ribbon having a magnetic flux density and a sufficiently relaxed stress is preferable. The Fe-based amorphous alloy ribbon has a saturation magnetic flux density of 1.6 5T or more and a magnetic flux density of 1.6T or more in a magnetic field of 80 A/m. The magnetic core of the present invention has a shape for a transformer by any one of the above Fe-based amorphous alloy ribbons by a cut lap or a step lap method. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT [1] The first Fe-based amorphous alloy constituting the present invention is represented by the following formula: FeaSibBcMx, wherein ^^ is Cr and/or Ni, and a is 78 to 86% by atom. b is 0.001 to 5 at%, c is 7 to 20 at%, and \ is 0.01 to 5 at%, wherein (a+b+c+x) is 1 Å. The second Fe-based amorphous alloy of the present invention is represented by the following formula: FeaSibBcCdMx, wherein Μ is Cr and/or Ni, a is 78 to 86 201202439 atom%, b is 0.001 to 5 atom%, c is 7 to 20 at%, d is 0.001 to 4 at%, and X is 0.01 to 5 at%, wherein (a+b+c + d + X ) is 100. When the Fe-based amorphous alloy of the present invention containing Cr and/or Ni is used, the stress generated during the manufacture of the core is sufficiently relaxed by heat treatment to provide a reduced melt viscosity and a roll. An alloy with improved wetness of surface conditions. Cr and Ni also have an effect of accelerating the stress relaxation in the Fe-based amorphous alloy at the time of heat treatment, thereby improving the soft magnetic properties thereof. However, when the amount of Cr and/or Ni contained is too small, a sufficient effect cannot be obtained; and when the content is too large, the Curie temperature and the saturation magnetic flux density are remarkably deteriorated. Therefore, based on 100 atom% of the alloy main component (a + b + c + x or a + b + c + d + x), the content of Cr and/or Ni is 0.01 to 5 atom%, and 0.02 to 4 The atomic % is preferably from 0.1 to 4 atom%. When Μ is C r , the X range is preferably 0. 〇 1 to 1 atom%, preferably 0.02 to 0.5 atom%. When niobium is Ni, the X range is preferably 0.1 to 5 atom%, more preferably 0.3 to 4 atom%. Therefore, Cr is different from Ni in terms of necessary amount. A small amount of Cr can effectively relax the stress generated when the core is formed, and the Ni system can effectively relax the stress generated when the core is formed. Cr and Ni can be appropriately selected depending on the required magnetic characteristics and stress relaxation rate.
Si係爲了使該合金成爲非晶質、且將該合金之居禮溫 度維持在高至某個程度的必需元素。當Si含量過小時，該 合金之居禮溫度對實際應用來說過低。另一方面，當其含 201202439 量過多時，該合金之磁心損失增加，且在該合金中之Fe及 /或B的百分比減少，而造成磁通量密度與熱穩定度降低。 因此’基於1 00原子％之合金主成份計，Si含量爲0.001〜 5原子％ ’以0.001〜3原子％爲佳。 B係用來使合金變成非晶質之重要元素。當B含量過 小時，該合金不易變成非晶質，導致軟磁特性降低且磁心 損失増加。另一方面，當B含量過多時，合金中之Fe及/ 或Si的百分比減少，而造成磁通量密度與熱穩定度降低。 因此，基於100原子％之合金主成份計，B含量爲7〜20 原子％，以1 0〜2 0原子％爲佳。 C能有效於降低合金之熔融黏度和改善與輥之濕潤性。 然而，過多的C會導致因老化而造成之磁特性劣化。因此’ 基於100原子％之合金主成份計，C含量爲0.001〜4原子 %，以0.01〜3原子％爲佳，以0.1〜3原子％爲較佳。In order to maintain the alloy amorphous, the Si system maintains the temperature of the alloy to a certain level. When the Si content is too small, the alloy temperature of the alloy is too low for practical use. On the other hand, when it contains too much 201202439, the core loss of the alloy increases, and the percentage of Fe and/or B in the alloy decreases, resulting in a decrease in magnetic flux density and thermal stability. Therefore, the Si content is 0.001 to 5 at% based on 100 parts by atom of the alloy main component, preferably 0.001 to 3 atom%. B is an important element used to make an alloy amorphous. When the B content is too small, the alloy does not easily become amorphous, resulting in a decrease in soft magnetic properties and a loss of core loss. On the other hand, when the B content is excessive, the percentage of Fe and/or Si in the alloy is decreased, resulting in a decrease in magnetic flux density and thermal stability. Therefore, the B content is 7 to 20 atom% based on 100 atom% of the alloy main component, preferably 10 to 20 atom%. C can effectively reduce the melt viscosity of the alloy and improve the wettability with the roll. However, excessive C causes deterioration in magnetic properties due to aging. Therefore, the C content is 0.001 to 4 atom% based on 100 atom% of the alloy main component, preferably 0.01 to 3 atom%, more preferably 0.1 to 3 atom%.
Fe爲平衡物質，其對於得到高磁通量密度爲重要元素。 然而，過多Fe導致磁心損失提高與熱穩定性不佳。因此’ 基於100原子％之合金主成份計，Fe含量爲78〜86原子 %，以78〜85原子％爲佳。 本發明的Fe-系非晶質合金可包含基於1〇〇原子％之 上述合金主成份計爲約0.0002〜0.2原子％含量之Μη、P、 S、Cu、Al、Sn、Pb、Ca、Ti與Zr中至少一種作爲不可避 免的不純物。 201202439 [2]製造方法 藉由單輕法等來驟冷上述組成物之溶融體、並在預定 溫度下熱處理所得之.Fe -系非晶質合金來鬆驰合金中之應 力’而得到本發明的Fe-系非晶質合金。雖然藉由單輥法等 來驟冷通常是在空氣中、在Ar或He之大氣中、或減壓之 大氣中進行’其亦可在含有氮氣、一氧化碳或二氧化碳之 大氣中進行。雖然通常在Ar、He、N2等鈍氣之大氣中或在 真空中進行熱處理，其亦可在空氣中進行。 該熱處理係希望在通常具有-30 °C以下之露點的鈍氣 大氣中進行。由於在熱處理後合金帶具有小的不均勻度， 故該熱處理係希望在具有-60 °C以下之露點的鈍氣大氣中 進行爲較佳。從量產的觀點來看，在恆溫下之熱處理的情 況下，該溫度保持時間通常爲2 4小時以下，以4小時以下 爲佳。在熱處理當中，平均溫度提升速度係以0.1-200。(：/ 分爲佳，以〇.i-i〇〇°C /分爲較佳，而平均冷卻速度係以 〇·卜3000 °C/分爲佳，以0.1-100 °C/分爲較佳。在該範圍內 之熱處理可提供具有低磁心損失之合金。該熱處理係可藉 由單步驟或多步驟來進行，或者可重複多次。再者，可供 給DC、AC或脈衝電流於該合金中，來產生用於熱處理的 熱。 必要時，本發明的Fe-系非晶質合金帶可以用下列 (1)〜（3 )進行被覆，來作爲夾層絕緣·· （ 1 ) S i Ο 2、M g 〇、 A1203等之粉末或薄膜、（2 )由化學轉化處理所形成之絕 201202439 緣層、或（3 )由陽極氧化處理所形成之絕緣氧化層。該等 處理會減輕在高頻率中特別通過層間之渦電流的影響，從 而減少在高頻率之磁心損失。該等處理對由寬如50mm之 具有良好表面條件的合金帶所構成之磁心特別有效。再者， 可在磁心之製造中進行含浸、被覆等。 如第1、2圖所示，本發明的Fe-系非晶質合金帶可作 成用於變壓器、馬達與發電機等之磁心1之環。藉由截斷 搭接或階式搭接法將本發明的Fe-系非晶質合金帶1 〇適當 地形成變壓器之形狀來提供磁心。 參照以下實施例來說明本發明，但本發明係不受其限 制。 【實施方式】 實施例1 具有以如示於表1之FeaSibBeMx(a+b+c+x=l〇〇) 所表示之組成物的合金熔融體藉由單輥法來驟冷，來製造 5mm寬與25 μηι厚的非晶質合金帶。 將每種Fe-系非晶質合金帶捲繞形成外徑19mm與內徑 15mm之環狀磁心’其中在/^氣大氣中熱處理。於熱處理 中’在隨該磁心之磁線所排列的方向上施加i kA/m之磁場， 並提高溫度至3 2 0 °C〜3 7 0 °C間之最適熱處理溫度，於此得 到最高飽和磁通量密度及其他軟磁性質，在該溫度下超過 2小時、保持在每種熱處理溫度1小時、然後冷卻至2〇〇〇c 超過1小時。該熱處理後之合金帶主要爲非晶質。測量所 -10- 201202439 得之環狀磁心的飽和磁通量密度B s、在8 0 A/m磁場中之磁 通量密度B8Q、在50Hz頻率之1.3T磁通量密度中之磁心損 失W^/5。、與在50Hz頻率之1 ·4Τ磁通量密度中之磁心損 失 W 1 4/ 5 0。 如第4圖所示，將每種裁切成10·5 ( π · rg) cin之Fe-系非晶質合金帶10捲繞在具有R〇 crn直徑之石英管11上 而形成單片試樣，並在形成環時於如上之同樣條件下進行 熱處理來鬆弛應力。測量相當於從石英管n取下之c _形 試樣1〇’之圓形的直徑R,，來測定以通式：Rs= ( Rq/Ri) xl〇〇[%]表示之應力鬆弛速度Rs ’來作爲表示以退火（熱 處理）所鬆驰之延伸應力的參數。100%之應力鬆弛速度Rs 表示應力完全被鬆驰。 該結果示於表1。 -11 - 201202439 表1 試樣 編號 組成 Bs [T1 Βδ〇 fTl w13/50 [W/kg] W14/50 『W/kgl Rs [%.l 1-1 Feg2Sl2B i5.95Cr〇.〇5 1.64 1.62 0.27 0.35 92.5 1-2 Fe82Si2B 15.9Cr〇. 1 1.64 1.63 0.20 0.26 95.7 1-3 Fe82Sl2Bi5.5Cr〇.5 1.62 1.51 0.20 0.24 98.8 1-4 Fe82Si2Bi5Cri 1.60 1.50 0.24 0.30 99.0 1-5 Feg2si2B15.98Nio.02 1.64 1.60 0.28 0.36 92.3 1-6 Fe82Sl2Bi5.9Ni〇.i 1.64 1.57 0.21 0.28 95.1 1-7 Fe82Sl2Bi5.5Ni〇.5 1.63 1.57 0.21 0.29 97.0 1-8 Fe82Si2B15Ni1 1.60 1.54 0.25 0.33 97.2 1-9 Fe82si2B15.8cro.lNio.! 1.62 1.58 0.27 0.37 93.1 1-10 Feg2Si2Bi5.5Cr〇.3Ni〇.2 1.61 1.56 0.23 0.31 95.2 1-11 Feg2Si2Bi5Cr〇.5Ni〇.5 1.60 1.52 0.25 0.33 97.3 1-12 Fe83.9Sio.1B15.9Cro.! 1.63 1.61 0.31 0.44 94.4 1-13 Fe83SiiBi5.9Cr〇.i 1.64 1.62 0.22 0.29 94.7 1-14 Fe§ 1 S13B15.9Cr〇. i 1.62 1.60 0.22 0.27 95.1 1-15 Fes3.9Si2B i4Cr〇. i 1.64 1.63 0.21 0.26 96.0 1-16 Feg〇.9Si2Bi7Cr〇.i 1.61 1.56 0.22 0.29 95.6 1-17 Fe8I>5Si〇.〇iBi7.99Ni〇.5 1.68 1.65 0.28 0.37 92.1 1-18 Fe8〇Si〇.〇iBi7.99Ni2 1.68 1.66 0.30 0.35 92.5 4-19 Fe77Si〇.〇iBi7.99Ni5 1.65 1.63 0.32 0.35 93.3 1-20 Fesi.5SiiBi7Ni〇.5 1.67 1.65 0.29 0.35 93.4 1-21 FesoSi 1B17N12 1.67. 1.65 0.29 0.36 93.3 1-22 FC77SiiBi7Nl5 1.65 1.63 0.31 0.38 95.6 1-23 Fe8i.5Si2Bi6Ni〇.5 1.68 1.65 0.25 0.31 93.0 1-24 F e8〇Si2B 16N12 1.67 1.65 0.24 0.29 93.2 1-25 Fe77Si2B 16N15 1.65 1.62 0.28 0.37 93.1 1-26* Fes2Si0.01B17.99 1.64 1.63 0.38 0.49 90.2 1-27* Feg2SiiBi7 1.64 1.63 0.35 0.48 91.3 1-28* Fe82Sl2Bi6 1.64 1.62 0.30 0.41 92.2 1-29* Fe72Si〇.〇iBi7.99Nii〇 1.58 1.57 - - - 1-30* Fe72Si]Bi7Nii〇 1.58 1.55 - - - 1-31* Fe72Si2Bi6Nii〇 1.64 1.61 0.35 0.51 89.9 1-32* Fe82Si2Bi〇Cr6 1.55 1.49 - - - 1-33* Fe82Si2B i〇Ni6 1.58 1.48 - - - 1-34* Fe82Si2B6Cr5Ni5 1.51 1.45 - - - 1-35* Fe79Si6B15.95Cr0.05 1.58 1.55 - - - 1-36* Fe76SigB15.95Cr0.05 1.52 1.45 - - - 1-37* Fe84.9Sii〇B5Cr〇.i 1.61 1.57 0.39 0.59 92.4 1-38* Fe75.9Si2B22Cr〇. 1 1.50 1.45 - - - 註：*本發明之試樣外部 -12- 201202439 從表1當可明瞭試樣1-1〜1-25具有較試樣 1- 28、1-3 1與1-37大的應力鬆弛速度rs，以致於 其形成環時所產生之應力會充分鬆弛。在磁心損失 與W14/5〇方面，試樣1_1〜1_25比試樣卜26〜1-38 多改善。 當在1 .3 T以上之操作磁通量密度下使用具有低 密度之合金時，其承受極大之例如W14/5〇的磁心損 不適用作爲磁心材料。然而，由於本發明之Fe-系非 金帶具有高如1.6T以上之飽和磁通量密度，故可提 作磁通量密度至1·4Τ，以致於其磁心損失W14/50小 得該磁心能承受實際應用。因此，本發明之Fe-系非 金帶可提供比傳統者小及性能較高之磁心。 實施例2 · . 以與實施例1同樣方法製造及熱處理各種組成 2- 1〜2-1 1與2-12〜2 - 16。每種所得之Fe-系非晶質 之磁心損失增加率W r與組成、熱處理溫度、飽和磁 度Bs、應力鬆弛速度RS、平均表面粗糙度Ra、與 數同時示於表2。以與實施例1同樣之方法測量該 通量密度Bs與應力鬆弛速度RS〇 該磁心損失增加率Wr係表示當操作磁通量 1.3T提高至1.4T時之磁心損失增加率的參數，其係 表不： 1 -26 〜 該等當 W 13/50 得到較 磁通量 失，而 晶質合 高其操 到可使 晶質合 之試樣 合金帶 通量密 空間參 飽和磁 密度從 以下式 -13- 201202439Fe is a balanced substance which is an important element for obtaining high magnetic flux density. However, too much Fe leads to an increase in core loss and poor thermal stability. Therefore, the Fe content is 78 to 86 atom% based on 100 atom% of the alloy main component, preferably 78 to 85 atom%. The Fe-based amorphous alloy of the present invention may comprise Μη, P, S, Cu, Al, Sn, Pb, Ca, Ti in an amount of about 0.0002 to 0.2 at% based on 1 〇〇 atom% of the above-mentioned alloy main component. At least one of Zr and Zr is inevitable as an impurity. 201202439 [2] Manufacturing method The present invention is obtained by quenching a melt of the above composition by a single light method or the like, and heat-treating the obtained Fe-based amorphous alloy at a predetermined temperature to relax the stress in the alloy Fe-based amorphous alloy. Although quenching by a single roll method or the like is usually carried out in the air, in the atmosphere of Ar or He, or in a reduced pressure atmosphere, it can also be carried out in an atmosphere containing nitrogen, carbon monoxide or carbon dioxide. Although heat treatment is usually carried out in an atmosphere of an inert gas such as Ar, He or N2 or in a vacuum, it can also be carried out in the air. This heat treatment is desirably carried out in an atmosphere of blunt gas which usually has a dew point of -30 ° C or less. Since the alloy ribbon has a small unevenness after the heat treatment, it is preferred that the heat treatment be carried out in an atmosphere of an air having a dew point of -60 ° C or less. From the viewpoint of mass production, in the case of heat treatment under a constant temperature, the temperature holding time is usually 24 hours or less, preferably 4 hours or less. In the heat treatment, the average temperature increase rate is 0.1-200. (: / is divided into good, 〇.ii 〇〇 ° C / is better, and the average cooling rate is preferably 〇 卜 3,000 ° C / divided into 0.1-100 ° C / divided into better. The heat treatment within this range can provide an alloy having a low core loss. The heat treatment can be performed in a single step or in multiple steps, or can be repeated multiple times. Further, DC, AC or pulsed current can be supplied to the alloy. To generate heat for heat treatment. If necessary, the Fe-based amorphous alloy ribbon of the present invention can be coated with the following (1) to (3) as interlayer insulation (1) S i Ο 2. Powder or film of M g 〇, A1203, etc., (2) a layer of 201202439 formed by chemical conversion treatment, or (3) an insulating oxide layer formed by anodizing. These treatments are alleviated at high frequencies. The core loss at high frequencies is particularly reduced by the influence of eddy currents between the layers. These processes are particularly effective for cores composed of alloy strips having a good surface condition as wide as 50 mm. Furthermore, in the manufacture of cores Perform impregnation, coating, etc. As shown in Figures 1 and 2, this issue The Fe-based amorphous alloy ribbon can be used as a ring for the core 1 of a transformer, a motor, a generator, etc. The Fe-based amorphous alloy ribbon of the present invention is 1 by a bridging lap or a step lap joint method. The shape of the transformer is appropriately formed to provide a magnetic core. The present invention will be described with reference to the following examples, but the present invention is not limited thereto. [Embodiment] Embodiment 1 has FeaSibBeMx (a+b+ as shown in Table 1). c+x=l〇〇) The alloy melt of the composition shown is quenched by a single roll method to produce an amorphous alloy ribbon of 5 mm wide and 25 μη thick. Each Fe-based amorphous material The alloy ribbon is wound to form an annular core having an outer diameter of 19 mm and an inner diameter of 15 mm, wherein the heat treatment is performed in a gas atmosphere. In the heat treatment, a magnetic field of i kA/m is applied in a direction in which the magnetic wires of the core are arranged. And increasing the temperature to an optimum heat treatment temperature between 3 2 0 ° C and 370 ° C, thereby obtaining the highest saturation magnetic flux density and other soft magnetic properties, at this temperature for more than 2 hours, maintaining at each heat treatment temperature for 1 hour, Then cooled to 2 〇〇〇c for more than 1 hour. The heat treated alloy strip To be amorphous. The saturation magnetic flux density B s of the toroidal core obtained by the measurement institute -10- 201202439, the magnetic flux density B8Q in the magnetic field of 80 A/m, and the core loss W in the 1.3 T magnetic flux density at the frequency of 50 Hz ^/5., and core loss W 1 4/ 5 0 in a magnetic flux density of 1 Τ 4 at a frequency of 50 Hz. As shown in Fig. 4, each of the cuts of 10·5 (π · rg) cin Fe The amorphous alloy ribbon 10 is wound around a quartz tube 11 having a R 〇 crn diameter to form a single-piece sample, and heat-treated under the same conditions as above to form a ring to relax stress. The diameter R corresponding to the circular shape of the c _shaped sample taken from the quartz tube n is measured to determine the stress relaxation rate expressed by the general formula: Rs = ( Rq / Ri) xl 〇〇 [%] Rs ' is taken as a parameter indicating the elongation stress relaxed by annealing (heat treatment). The 100% stress relaxation rate Rs indicates that the stress is completely relaxed. The results are shown in Table 1. -11 - 201202439 Table 1 Sample No. Composition Bs [T1 Βδ〇fTl w13/50 [W/kg] W14/50 『W/kgl Rs [%.l 1-1 Feg2Sl2B i5.95Cr〇.〇5 1.64 1.62 0.27 0.35 92.5 1-2 Fe82Si2B 15.9Cr〇. 1 1.64 1.63 0.20 0.26 95.7 1-3 Fe82Sl2Bi5.5Cr〇.5 1.62 1.51 0.20 0.24 98.8 1-4 Fe82Si2Bi5Cri 1.60 1.50 0.24 0.30 99.0 1-5 Feg2si2B15.98Nio.02 1.64 1.60 0.28 0.36 92.3 1-6 Fe82Sl2Bi5.9Ni〇.i 1.64 1.57 0.21 0.28 95.1 1-7 Fe82Sl2Bi5.5Ni〇.5 1.63 1.57 0.21 0.29 97.0 1-8 Fe82Si2B15Ni1 1.60 1.54 0.25 0.33 97.2 1-9 Fe82si2B15.8cro.lNio.! 1.62 1.58 0.27 0.37 93.1 1-10 Feg2Si2Bi5.5Cr〇.3Ni〇.2 1.61 1.56 0.23 0.31 95.2 1-11 Feg2Si2Bi5Cr〇.5Ni〇.5 1.60 1.52 0.25 0.33 97.3 1-12 Fe83.9Sio.1B15.9Cro.! 1.63 1.61 0.31 0.44 94.4 1-13 Fe83SiiBi5.9Cr〇.i 1.64 1.62 0.22 0.29 94.7 1-14 Fe§ 1 S13B15.9Cr〇. i 1.62 1.60 0.22 0.27 95.1 1-15 Fes3.9Si2B i4Cr〇. i 1.64 1.63 0.21 0.26 96.0 1 -16 Feg〇.9Si2Bi7Cr〇.i 1.61 1.56 0.22 0.29 95.6 1-17 Fe8I>5Si〇.〇iBi7.99Ni〇.5 1.68 1.65 0.28 0.37 92.1 1-18 Fe8 Si〇.〇iBi7.99Ni2 1.68 1.66 0.30 0.35 92.5 4-19 Fe77Si〇.〇iBi7.99Ni5 1.65 1.63 0.32 0.35 93.3 1-20 Fesi.5SiiBi7Ni〇.5 1.67 1.65 0.29 0.35 93.4 1-21 FesoSi 1B17N12 1.67. 1.65 0.29 0.36 93.3 1-22 FC77SiiBi7Nl5 1.65 1.63 0.31 0.38 95.6 1-23 Fe8i.5Si2Bi6Ni〇.5 1.68 1.65 0.25 0.31 93.0 1-24 F e8〇Si2B 16N12 1.67 1.65 0.24 0.29 93.2 1-25 Fe77Si2B 16N15 1.65 1.62 0.28 0.37 93.1 1- 26* Fes2Si0.01B17.99 1.64 1.63 0.38 0.49 90.2 1-27* Feg2SiiBi7 1.64 1.63 0.35 0.48 91.3 1-28* Fe82Sl2Bi6 1.64 1.62 0.30 0.41 92.2 1-29* Fe72Si〇.〇iBi7.99Nii〇1.58 1.57 - - - 1 -30* Fe72Si]Bi7Nii〇1.58 1.55 - - - 1-31* Fe72Si2Bi6Nii〇1.64 1.61 0.35 0.51 89.9 1-32* Fe82Si2Bi〇Cr6 1.55 1.49 - - - 1-33* Fe82Si2B i〇Ni6 1.58 1.48 - - - 1- 34* Fe82Si2B6Cr5Ni5 1.51 1.45 - - - 1-35* Fe79Si6B15.95Cr0.05 1.58 1.55 - - - 1-36* Fe76SigB15.95Cr0.05 1.52 1.45 - - - 1-37* Fe84.9Sii〇B5Cr〇.i 1.61 1.57 0.39 0.59 92.4 1-38* Fe75.9Si2B22Cr〇. 1 1.50 1.45 - - - Note: *External sample of the present invention - 12-201202439 From Table 1, it can be seen that the samples 1-1 to 1-25 have a stress relaxation rate rs larger than that of the samples 1-28, 1-3 1 and 1-37, so that they are formed when the ring is formed. The stress will be fully relaxed. In terms of core loss and W14/5〇, the samples 1_1 to 1_25 were more improved than the sample cloths 26 to 1-38. When an alloy having a low density is used at an operating magnetic flux density of 1.3 T or more, a core loss which is extremely subjected to, for example, W14/5 不 is not suitable as a core material. However, since the Fe-based non-gold belt of the present invention has a saturation magnetic flux density as high as 1.6 T or more, it can be made to have a magnetic flux density of 1.4 μm, so that the core loss W14/50 is small and the magnetic core can withstand practical application. . Therefore, the Fe-based non-gold belt of the present invention can provide a core which is smaller and more powerful than the conventional one. Example 2: Various compositions 2 - 1 to 2 - 1 and 2 - 12 to 2 - 16 were produced and heat-treated in the same manner as in Example 1. The Fe-based amorphous core loss increase rate W r and the composition, the heat treatment temperature, the saturation magnetic force Bs, the stress relaxation rate RS, the average surface roughness Ra, and the number of each obtained are shown in Table 2. The flux density Bs and the stress relaxation rate RS are measured in the same manner as in the first embodiment. The core loss increase rate Wr is a parameter indicating the rate of increase in core loss when the operating magnetic flux 1.3T is increased to 1.4T. : 1 -26 ~ When W 13/50 is obtained, the magnetic flux is lost, and the crystal is high, which can be used to make the crystalline alloy sample with a flux-tight spatial density of saturated magnetic density from the following formula -13-201202439
Wr=( Wi4/5〇 — Wi3/5〇)/Wi3/5〇xl〇〇[%] . · .(2)， 其中Wu/so表示在1.3T磁通量密度與50Hz頻率下之 磁心損失’及w μ / 5 ο表示在1 · 4 T磁通量密度與5 Ο Η z頻率 下之磁心損失。於試樣2-1 2中，當形成環狀磁心時所產生 之應力未充分地鬆弛，且其飽和磁通量密度小。因此，其 在1 · 4 T之操作磁通量密度中具有大Wr的磁心損失有相當 幅度地增加。雖然試樣2 - 1 3具有高飽和磁通量密度，但其 因爲在形成環狀磁心時所產生之應力鬆弛速度低而具有大 的Wr。由於藉由熱處理而使包含適量Cr或Ni之試樣2-1〜 2-1 1的應力充分地鬆弛，以及高飽和磁通量密度之故，該 等磁心損失增加率Wr較試樣2 -1 2〜2 -1 3小。 爲了測量表面粗糙度，將每種Fe_系非晶質合金帶裁成 5mm寬、25 μηι厚、與1 2cm長之長方形，並以與上述同樣 方法來進行熱處理。表面粗糙度的側量是在該合金帶之寬 度方向來進行算數平均。進一步測量由每種Fe-系非晶質合 金帶所構成之磁心的空間參數。通常，表面粗糙度Ra愈小， 該磁心之空間參數愈大。適量添加C r及/或N i係作用來減 少該合金之熔融體黏度，從而該合金熔融體能使輥有良好 之濕潤性。因此，所得之非晶質合金帶具有比不包含Cr或 Ni之傳統非晶質合金帶較平滑之表面。.具有較平滑表面之 Fe-系非晶質合金帶提供具有較大空間參數之磁心，從而使 該磁心變得較小並且重量較輕。 -14- 201202439 表2 試樣 編號 組成 Bs [T] Wr [%] Rs [%] Ra⑴ [μιη] 空間參數[%] 2-1 Fe82Si2Bj5.95CrO.O5 1.64 29.6 92.5 0.28 87 2-2 Fe82Si2Bi5.9Cr〇.i 1.64 30.0 95.7 0.28 88 2-3 Fe82Si2Bi5.5Cr〇.5 1.62 20.0 98.8 0.26 87 2-4 Fe83.9Si2B i4Cr〇.i 1.64 28.3 96.0 0.31 88 2-5 Fe8〇.9Si2Bi7Cr〇.i 1.61 31.8 95.6 0.33 87 2-6 Fe8i.5SiiBi7Ni〇.5 1.67 20.7 93.4 0.25 91 2-7 Fe8〇SiiBi7Ni2 1.67 24.1 93.3 0.26 90 2-8 Fe77 Si 1B17N15 1.65 22.6 95.6 0.41 86 2-9 Fe8I.5Sl2Bi6Ni〇.5 1.68 24.0 93.0 0.29 93 2-10 Fe8〇Si2Bi6Ni2 1.67 20.8 93.2 0.23 92 2-11 Fe77Si2Bi6Ni5 1.65 32.1 93.1 0.36 89 2-12* Fe79Si9Bj2 1.58 32.5 90.1 0.44 86 2-13* Fe82Si2B 16 1.64 36.7 92.2 0.45 85 2-14* Fe8K5Si2Bi6Co〇.5 1.68 25.1 94.2 0.25 86 2-15* Fe8〇Sl2Bi6C〇2 1.69 23.3 94.3 0.25 87 2-16* Fe77Si2B 16C05 1.71 31.2 93.1 0.28 90 註：*本發明之試樣外部 (1)算數平均後之表面粗糙度 因在形成磁心時所產生之應力之故，由試樣2-12與2-13 之合金帶所製作之環狀磁心比由相同組成之單板試樣所製 作之環狀磁心，具有較小飽和磁通量密度Bs。另—方面， 由於在由本發明範圍中之試樣2·1〜2·11的合金帶所製作之 環狀磁心中，應力會藉由熱處理而充分地鬆弛’故在飽和磁 通量密度方面僅有少許降低’且該等降低率比試樣2 -1 2與 2-13之降低率小很多。 當添加用於改善磁心損失與抗腐蝕之元素於該F e-系非 晶質合金中時，通常該合金之磁特性會同時劣化。然而’包 -15- 201202439 含適量能有效於鬆驰應力之Cr及/或Ni之本發明的Fe-系非 晶質合金帶對未包含Cr或Ni之合金來說，具有相似之飽和 磁通量密度。因此，本發明之Fe-系非晶質合金帶具有優異 之磁特性，由於在製造磁心中所產生之應力充分地鬆弛，故 適用於用於變壓器之磁心。 如所熟知，Co之添加會提高該Fe-系非晶質合金之飽和 磁通量密度。包含Co之試樣2-14〜2-16具有大的飽和磁通 量密度與空間參數。然而，由於Co爲稀有金屬，故Co之 添加會提高該Fe-系非晶質合金的成本。另一方面，Ni與 Cr較Co廉價，如果以適量添加Ni或Cr，會使該Fe·系非 晶質合金帶具有如Co之添加之改善的磁通量密度與空間參 數。因此，適量之Ni及/或Cr之添加係有效於提供具有充 分鬆弛後之應力與優異磁性質的Fe-系非晶質合金帶，其使 小、重量輕之磁心的製造變成可行。 實施例3 藉由單輥法驟冷具有以如表3所示之FeaSibBeCdMx (a + b + c + d + x = 100 )所表示之組成的合金熔融體，來形成 5mm寬與25 μηι厚的Fe-系非晶質合金帶。將每種所得之Fe-系非晶質合金帶捲繞形成外徑19mm與內徑15mm之環狀磁 心，並以與實施例1同樣方法來進行熱處理。該熱處理後之 合金主要爲非晶質。 以與實施例1同樣之方法來測量各試樣之飽和磁通量密 度B S、在8 0 A/m磁場中之磁通量密度B 8〇、在1 · 3 T磁通量密 度與50Hz頻率之磁心損失W13/5Q、在1 ·4Τ磁通量密度與50Hz 頻率之磁心損失W14/5〇、及應力鬆驰速度Rs。結果示於表3。 -16 · 201202439 表3 試樣 編號 組成 Bs [T] B 80 [T] W13/50 [W/kg] W13/50 [W/kg] Rs [%] 3-1 Feg2Si2Bi3.95C2Cr0.05 1.64 1.61 0.28 0.38 95.2 3-2 Fe82Si2Bi3.9C2Cr〇.i 1.64 1.61 0.20 0.23 97.2 3-3 Fe82Si2Bi3.5C2Cr〇,5 1.63 1.60 0.21 0.25 99.5 3-4 Fe§2 SI2 B13 C2Cr 1 1.62 1.54 0.25 0.30 99.2 3-5 Fe82Si2Bu.9gC2Ni0.02 1.64 1.61 0.28 0.38 95.0 3-6 Fe82Si2B13.9C2Ni〇.i 1.63 1.59 0.23 0.29 95.1 3-7 Fe82Si2Bi3.5C2Ni0.5 1.63 1.57 0.26 0.30 98.3 3-8 Feg2Si2Bi3C2Nii 1.62 1.55 0.27 0.33 99.0 3-9 Fe8i.5Si2Bi4C2Ni〇.5 1.67 1.63 0.28 0.31 94.9 3-10 Feg〇Si2Bi4C2Ni2 1.67 1.64 0.25 0.31 95.1 3-11 Ρ6778ΐ2Βΐ4〇2ΝΪ5 1.66 1.63 0.27 0.35 95.0 3-12 Fe82Si2Bn.8C2Cro.1Nio.! 1.63 1.61 0.23 0.28 93.0 3-13 Fe82Si2Bi3.5C2Cr〇.3Ni〇.2 1.63 1.60 0.25 0.30 96.3 3-14 Fe82Si2B13C2Cr〇.5Ni〇.5 1.60 1.57 0.28 0.35 97.3 3-15 Fe83.9Sio.1B] 3.9C2Cr〇,i 1.64 1.60 0.35 0.47 94.5 3-16 Fe83Si]Bi3.9C2Cr〇.i 1.63 1.61 0.23 0.28 96.8 3-17 Fe81Si3Bi3.9C2Cr〇.i 1.62 1.61 0.24 0.27 97.1 3-18 Feg〇9Si2Bi5C2Cr〇.i 1.61 1.53 0.25 0.31 96.8 3-19 ¥\-jC2CrQ_\ 1.60 1.52 0.26 0.32 95.4 3-20* Fe82Sl2Bi4C2 1.65 1.63 0.29 0.39 94.9 3-21* Fe79Si2BiiC2Cl*6 1.54 1.48 - - • 3-22* Fe79 S12B11C2N16 1.51 1.45 - - - 3-23* Fe76Si2Bi〇C2Cr5Ni5 1.50 1.39 - - - 3-24* Fe77Si5B17.s7Co.ogCro.05 1.57 1.45 - - - 3-25* Fe77Si5B14.95C3Cro.05 1.58 1.46 - - - 3-26* Fe77Si5B".95C6Cr〇.〇5 1.52 1.45 - - - 3-27* Fe76Si8Bi3.9C2Cr〇.i 1.52 1.44 - - - 3-28* Fe82.9Si]〇B5C2Cr〇>i 1.62 1.60 0.29 0.42 94.6 3-29* Fe739Si2B22C2Cr〇.i 1.51 1.44 - - - 註：*本發明之試樣外部 -17- 201202439 從表3當可明瞭試樣3-1〜3-19具有比試樣3_21〜3_29 較改善之磁心損失W13/5Q與w14/5〇。 實施例4 藉由單輥法驟冷與實施例1〜3同樣之合金熔融體，得 到25 μηι厚與50mm寬的Fe-系非晶質合金帶。藉由截斷搭 接或階式搭接法將每種合金帶捲繞成爲外徑丨9mm與內徑 1 5mm之用於變壓器的環狀磁心，並以與實施例1同樣方法 來進行熱處理。由於在該非晶質合金中包含適量之Cr及/ 或Ni，故在形成環時所產生之應力會藉由熱處理而分地鬆 弛’導致用於變壓器之磁心具有窄的間隙與優異之磁特性。 具有高飽和磁通量密度與低磁心損失之本發明Fe_系 非晶質合金帶係可使用於電源變壓器與反應器、減噪零件 (如用於主動濾波器之抗流線圈、平流抗流線圏、共模抗流 線圈、電磁遮板等）、雷射電源供應器、用於加速器之脈衝 電力線路的零件、馬達、發電機等等。在本發明之包含適 量之Cr及/或Ni的Fe -系非晶質合金帶中，由於應力可在 相當短時間內藉由熱處理來充分鬆弛，故其適於量產。特 別是在藉由如第3圖所示之截斷搭接或階式搭接法所製成 之用於電源變壓器的磁心中，可使該磁特性劣化與磁心損 失變得極小。 以適量Cr及/或Ni之添加來降低該合金熔融體之黏 度，從而藉由該合金熔融體來使輥具有良好濕潤性’因此 改善所得之F e -系非晶質合金帶的表面條件。該具有平滑表 -18 - 201202439 面之合金帶使得生產具有高空間參數之小的、重量輕的磁 心變成可行。 【圖式簡單說明】 第1(a)圖係顯示由本發明之Fe-系非晶質合金帶所構 成之環狀磁心範例的平面圖示。 第1(b)圖係延著第1(a)圖之A-A直線的截面圖。 第2 (a)圖係顯示由本發明之F e-系非晶質合金帶所構 成之環狀磁心之另一範例的平面圖示。 第2(b)圖係延著第2(a)圖之B-B直線的截面圖。 第3(a)圖係顯示藉由截斷搭接或階式搭接方法所製造 之環狀磁心的局部放大平面圖。 第3(b)圖係延著第3(a)圖之C-C直線的截面圖。 第4圖係顯示測量應力鬆弛速度之方法的槪略圖。 【主要元件符號說明】 1 磁心 10 Fe-系非晶質合金帶 1 05 形試樣 11 石英管 R〇 直徑 Ri C-形試樣10’之直徑 -19-Wr=( Wi4/5〇— Wi3/5〇)/Wi3/5〇xl〇〇[%] . (2), where Wu/so represents the core loss at 1.3T magnetic flux density and 50Hz frequency and w μ / 5 ο represents the core loss at a magnetic flux density of 1 · 4 T and a frequency of 5 Ο Η z. In Sample 2-12, the stress generated when the annular core was formed was not sufficiently relaxed, and its saturation magnetic flux density was small. Therefore, the core loss having a large Wr in the operating magnetic flux density of 1 · 4 T is considerably increased. Although the sample 2 - 13 has a high saturation magnetic flux density, it has a large Wr because the stress relaxation rate generated when the annular core is formed is low. Since the stress of the samples 2-1 to 2-1 1 containing an appropriate amount of Cr or Ni is sufficiently relaxed by heat treatment, and the high saturation magnetic flux density, the core loss increase rate Wr is higher than that of the sample 2 -1 2 ~2 -1 3 small. In order to measure the surface roughness, each of the Fe-based amorphous alloy ribbons was cut into a rectangular shape of 5 mm wide, 25 μη thick, and 12 cm long, and heat-treated in the same manner as above. The side amount of the surface roughness is arithmetically averaged in the width direction of the alloy ribbon. The spatial parameters of the core composed of each of the Fe-based amorphous alloy ribbons were further measured. Generally, the smaller the surface roughness Ra, the larger the spatial parameter of the core. An appropriate amount of Cr and/or N i is added to reduce the viscosity of the melt of the alloy, so that the alloy melt can impart good wettability to the roll. Therefore, the obtained amorphous alloy ribbon has a smoother surface than a conventional amorphous alloy ribbon not containing Cr or Ni. A Fe-based amorphous alloy ribbon having a relatively smooth surface provides a core having a large spatial parameter, thereby making the core smaller and lighter in weight. -14- 201202439 Table 2 Sample No. Composition Bs [T] Wr [%] Rs [%] Ra(1) [μιη] Spatial Parameter [%] 2-1 Fe82Si2Bj5.95CrO.O5 1.64 29.6 92.5 0.28 87 2-2 Fe82Si2Bi5.9Cr 〇.i 1.64 30.0 95.7 0.28 88 2-3 Fe82Si2Bi5.5Cr〇.5 1.62 20.0 98.8 0.26 87 2-4 Fe83.9Si2B i4Cr〇.i 1.64 28.3 96.0 0.31 88 2-5 Fe8〇.9Si2Bi7Cr〇.i 1.61 31.8 95.6 0.33 87 2-6 Fe8i.5SiiBi7Ni〇.5 1.67 20.7 93.4 0.25 91 2-7 Fe8〇SiiBi7Ni2 1.67 24.1 93.3 0.26 90 2-8 Fe77 Si 1B17N15 1.65 22.6 95.6 0.41 86 2-9 Fe8I.5Sl2Bi6Ni〇.5 1.68 24.0 93.0 0.29 93 2-10 Fe8〇Si2Bi6Ni2 1.67 20.8 93.2 0.23 92 2-11 Fe77Si2Bi6Ni5 1.65 32.1 93.1 0.36 89 2-12* Fe79Si9Bj2 1.58 32.5 90.1 0.44 86 2-13* Fe82Si2B 16 1.64 36.7 92.2 0.45 85 2-14* Fe8K5Si2Bi6Co〇. 5 1.68 25.1 94.2 0.25 86 2-15* Fe8〇Sl2Bi6C〇2 1.69 23.3 94.3 0.25 87 2-16* Fe77Si2B 16C05 1.71 31.2 93.1 0.28 90 Note: *The surface roughness of the sample outside the (1) arithmetic average of the present invention Ring made of alloy strips of samples 2-12 and 2-13 due to the stress generated during the formation of the core The core has a smaller saturation magnetic flux density Bs than a toroidal core made of a single-plate sample of the same composition. On the other hand, in the annular core made of the alloy ribbon of the sample 2·1 to 2·11 in the range of the present invention, the stress is sufficiently relaxed by the heat treatment, so there is only a small amount in the saturation magnetic flux density. Lowering 'and these reduction rates are much smaller than the reduction rates of samples 2 -1 2 and 2-13. When an element for improving core loss and corrosion resistance is added to the Fe-based amorphous alloy, the magnetic properties of the alloy are usually deteriorated at the same time. However, the package of the Fe-based amorphous alloy of the present invention containing an appropriate amount of Cr and/or Ni which is effective for relaxation stress has a similar saturation magnetic flux density for an alloy not containing Cr or Ni. . Therefore, the Fe-based amorphous alloy ribbon of the present invention has excellent magnetic properties, and is suitable for use in a magnetic core for a transformer because the stress generated in the manufacturing of the core is sufficiently relaxed. As is well known, the addition of Co increases the saturation magnetic flux density of the Fe-based amorphous alloy. Samples 2-14 to 2-16 containing Co have large saturation magnetic flux density and spatial parameters. However, since Co is a rare metal, the addition of Co increases the cost of the Fe-based amorphous alloy. On the other hand, Ni and Cr are less expensive than Co, and if Ni or Cr is added in an appropriate amount, the Fe-based non-crystalline alloy ribbon has an improved magnetic flux density and spatial parameter such as addition of Co. Therefore, an appropriate amount of addition of Ni and/or Cr is effective for providing an Fe-based amorphous alloy ribbon having a stress after sufficient relaxation and excellent magnetic properties, which makes it possible to manufacture a small and lightweight core. Example 3 An alloy melt having a composition represented by FeaSibBeCdMx (a + b + c + d + x = 100 ) as shown in Table 3 was quenched by a single roll method to form a 5 mm wide and 25 μη thick Fe-based amorphous alloy ribbon. Each of the obtained Fe-based amorphous alloy ribbons was wound to form an annular core having an outer diameter of 19 mm and an inner diameter of 15 mm, and heat treatment was carried out in the same manner as in the first embodiment. The alloy after the heat treatment is mainly amorphous. The saturation magnetic flux density BS of each sample, the magnetic flux density B 8 在 in a magnetic field of 80 A/m, the magnetic flux loss at a magnetic flux density of 1 · 3 T and the frequency of 50 Hz W13/5Q were measured in the same manner as in the first embodiment. The magnetic core loss W14/5〇 at a magnetic flux density of 1·4Τ and a frequency of 50Hz, and the stress relaxation rate Rs. The results are shown in Table 3. -16 · 201202439 Table 3 Sample No. Composition Bs [T] B 80 [T] W13/50 [W/kg] W13/50 [W/kg] Rs [%] 3-1 Feg2Si2Bi3.95C2Cr0.05 1.64 1.61 0.28 0.38 95.2 3-2 Fe82Si2Bi3.9C2Cr〇.i 1.64 1.61 0.20 0.23 97.2 3-3 Fe82Si2Bi3.5C2Cr〇,5 1.63 1.60 0.21 0.25 99.5 3-4 Fe§2 SI2 B13 C2Cr 1 1.62 1.54 0.25 0.30 99.2 3-5 Fe82Si2Bu. 9gC2Ni0.02 1.64 1.61 0.28 0.38 95.0 3-6 Fe82Si2B13.9C2Ni〇.i 1.63 1.59 0.23 0.29 95.1 3-7 Fe82Si2Bi3.5C2Ni0.5 1.63 1.57 0.26 0.30 98.3 3-8 Feg2Si2Bi3C2Nii 1.62 1.55 0.27 0.33 99.0 3-9 Fe8i.5Si2Bi4C2Ni 〇.5 1.67 1.63 0.28 0.31 94.9 3-10 Feg〇Si2Bi4C2Ni2 1.67 1.64 0.25 0.31 95.1 3-11 Ρ6778ΐ2Βΐ4〇2ΝΪ5 1.66 1.63 0.27 0.35 95.0 3-12 Fe82Si2Bn.8C2Cro.1Nio.! 1.63 1.61 0.23 0.28 93.0 3-13 Fe82Si2Bi3. 5C2Cr〇.3Ni〇.2 1.63 1.60 0.25 0.30 96.3 3-14 Fe82Si2B13C2Cr〇.5Ni〇.5 1.60 1.57 0.28 0.35 97.3 3-15 Fe83.9Sio.1B] 3.9C2Cr〇,i 1.64 1.60 0.35 0.47 94.5 3-16 Fe83Si ]Bi3.9C2Cr〇.i 1.63 1.61 0.23 0.28 96.8 3-17 Fe81Si3Bi3.9C2Cr〇.i 1.62 1.61 0.24 0.27 97.1 3-18 F eg〇9Si2Bi5C2Cr〇.i 1.61 1.53 0.25 0.31 96.8 3-19 ¥\-jC2CrQ_\ 1.60 1.52 0.26 0.32 95.4 3-20* Fe82Sl2Bi4C2 1.65 1.63 0.29 0.39 94.9 3-21* Fe79Si2BiiC2Cl*6 1.54 1.48 - - • 3-22* Fe79 S12B11C2N16 1.51 1.45 - - - 3-23* Fe76Si2Bi〇C2Cr5Ni5 1.50 1.39 - - - 3-24* Fe77Si5B17.s7Co.ogCro.05 1.57 1.45 - - - 3-25* Fe77Si5B14.95C3Cro.05 1.58 1.46 - - - 3 -26* Fe77Si5B".95C6Cr〇.〇5 1.52 1.45 - - - 3-27* Fe76Si8Bi3.9C2Cr〇.i 1.52 1.44 - - - 3-28* Fe82.9Si]〇B5C2Cr〇>i 1.62 1.60 0.29 0.42 94.6 3-29* Fe739Si2B22C2Cr〇.i 1.51 1.44 - - - Note: *External sample of the present invention-17- 201202439 From Table 3, it can be seen that the samples 3-1 to 3-19 have better than the samples 3_21 to 3_29. The core loss is W13/5Q and w14/5〇. Example 4 The same alloy melts as in Examples 1 to 3 were quenched by a single roll method to obtain a Fe-based amorphous alloy ribbon having a thickness of 25 μm and a width of 50 mm. Each of the alloy ribbons was wound into a toroidal core for a transformer having an outer diameter of mm9 mm and an inner diameter of 15 mm by a cut-off lap or a step lap method, and heat-treated in the same manner as in the first embodiment. Since an appropriate amount of Cr and/or Ni is contained in the amorphous alloy, the stress generated when the ring is formed is loosened by heat treatment, resulting in a magnetic core having a narrow gap and excellent magnetic properties. The Fe_based amorphous alloy ribbon of the present invention having high saturation magnetic flux density and low core loss can be used for power transformers and reactors, noise reduction parts (such as anti-flow coils for active filters, advection anti-flow lines 圏, common mode choke coil, electromagnetic shutter, etc.), laser power supply, parts for the pulse power line of the accelerator, motor, generator, etc. In the Fe-based amorphous alloy ribbon containing an appropriate amount of Cr and/or Ni of the present invention, since the stress can be sufficiently relaxed by heat treatment in a relatively short time, it is suitable for mass production. In particular, in the core for a power transformer which is formed by the cut-off lap or the step lap method as shown in Fig. 3, the deterioration of the magnetic characteristics and the core loss can be made extremely small. The addition of an appropriate amount of Cr and/or Ni reduces the viscosity of the alloy melt, so that the roll has good wettability by the alloy melt, thereby improving the surface condition of the obtained Fe-based amorphous alloy ribbon. The alloy belt with smooth surface -18 - 201202439 makes it possible to produce small, lightweight cores with high spatial parameters. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1(a) is a plan view showing an example of a toroidal core formed of the Fe-based amorphous alloy ribbon of the present invention. Fig. 1(b) is a cross-sectional view taken along the line A-A of Fig. 1(a). Fig. 2(a) is a plan view showing another example of the annular core formed of the F e-based amorphous alloy ribbon of the present invention. Fig. 2(b) is a cross-sectional view taken along the line B-B of Fig. 2(a). Fig. 3(a) is a partially enlarged plan view showing a toroidal core manufactured by a cut-and-lap or step-and-lap method. Fig. 3(b) is a cross-sectional view taken along the line C-C of Fig. 3(a). Figure 4 is a schematic diagram showing a method of measuring the rate of stress relaxation. [Main component symbol description] 1 Core 10 Fe-based amorphous alloy ribbon 1 05 specimen 11 Quartz tube R〇 Diameter Ri C-shaped specimen 10' diameter -19-