JP5891578B2 - 方向性電磁鋼板 - Google Patents
方向性電磁鋼板 Download PDFInfo
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- JP5891578B2 JP5891578B2 JP2010217370A JP2010217370A JP5891578B2 JP 5891578 B2 JP5891578 B2 JP 5891578B2 JP 2010217370 A JP2010217370 A JP 2010217370A JP 2010217370 A JP2010217370 A JP 2010217370A JP 5891578 B2 JP5891578 B2 JP 5891578B2
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- 229910000976 Electrical steel Inorganic materials 0.000 title claims description 4
- 238000000576 coating method Methods 0.000 claims description 62
- 239000011248 coating agent Substances 0.000 claims description 60
- 229910000831 Steel Inorganic materials 0.000 claims description 38
- 239000010959 steel Substances 0.000 claims description 38
- 229910001224 Grain-oriented electrical steel Inorganic materials 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 230000014509 gene expression Effects 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 51
- 238000000137 annealing Methods 0.000 description 32
- 229910052742 iron Inorganic materials 0.000 description 22
- 238000000034 method Methods 0.000 description 18
- 238000001953 recrystallisation Methods 0.000 description 14
- 230000005381 magnetic domain Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000035882 stress Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000005097 cold rolling Methods 0.000 description 5
- 239000011162 core material Substances 0.000 description 5
- 229910052839 forsterite Inorganic materials 0.000 description 5
- 238000005098 hot rolling Methods 0.000 description 5
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- 229910052711 selenium Inorganic materials 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000005261 decarburization Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000000866 electrolytic etching Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000004148 curcumin Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- JOPDZQBPOWAEHC-UHFFFAOYSA-H tristrontium;diphosphate Chemical compound [Sr+2].[Sr+2].[Sr+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JOPDZQBPOWAEHC-UHFFFAOYSA-H 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
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- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
- H01F1/16—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of sheets
- H01F1/18—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of sheets with insulating coating
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- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
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- C21D8/1288—Application of a tension-inducing coating
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
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- C23C22/08—Orthophosphates
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- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
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- C23C22/24—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds
- C23C22/33—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds containing also phosphates
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- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
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- C23F17/00—Multi-step processes for surface treatment of metallic material involving at least one process provided for in class C23 and at least one process covered by subclass C21D or C22F or class C25
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- C21D2201/00—Treatment for obtaining particular effects
- C21D2201/05—Grain orientation
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
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Description
そのためには、鋼板中の二次再結晶粒を、(110)[001]方位(いわゆる、ゴス方位)に高度に揃えることや、製品鋼板中の不純物を低減することが重要である。しかしながら、結晶方位の制御や、不純物を低減することは、製造コストとの兼ね合い等で限界がある。そこで、鋼板の表面に対して物理的な手法で不均一歪を導入し、磁区の幅を細分化して鉄損を低減する技術、すなわち磁区細分化技術が開発されている。
また、特許文献2には、仕上げ焼鈍済みの鋼板に対して、882〜2156 MPa(90〜220 kgf/mm2)の荷重で地鉄部分に深さ:5μm 超の溝を形成したのち、750℃以上の温度で加熱処理することにより、磁区を細分化する技術が提案されている。
さらに、特許文献3には、鋼板の圧延方向とほぼ直角な方向に、幅が30μm以上300μm以下、深さが10μm以上70μm以下であって、圧延方向の間隔が1mm以上である線状刻み目(溝)を導入する技術が提案されている。
上記したような種々の磁区細分化技術の開発により、鉄損特性が良好な方向性電磁鋼板が得られるようになってきている。
さらには、作業性の問題だけではなく、溝部が引っかかることによって、鋼板に局所的な応力が掛かり、鋼板がひずむことで磁気特性が劣化するという問題が生じる場合もあった。
1.深さ:10〜50μmの線状溝を設けた鋼板の表面に、絶縁コーティングを施した方向性電磁鋼板において、該線状溝の底面部における該絶縁コーティングの膜厚a1(μm)と、該線状溝部以外の鋼板表面の該絶縁コーティング膜厚a2(μm)と、該線状溝の深さa3(μm)とが、下記式(1)および(2)を満足することを、特徴とする方向性電磁鋼板。
記
0.3μm≦a2≦3.5μm ・・・(1)
a2+a3−a1≦15μm ・・・(2)
(ただし、上記式(2)において、a 2 +a 3 −a 1 =0μmである場合は除く)
通常、鋼板の表面に線状溝(以下、単に溝ともいう)を形成する際には、鋼板の絶縁性を確保するために、溝を形成したのち、鋼板表面にフォルステライト被膜を形成させ、さらにその上に、絶縁のための被膜(以下、絶縁コーティング、または、単にコーティングという)を付与する。
上記フォルステライト被膜は、方向性電磁鋼板を製造する際の脱炭焼鈍において、鋼板表面にSiO2主体の内部酸化層を形成し、その上にMgOを含有する焼鈍分離剤を塗布して、高温・長時間で仕上焼鈍を行うことによって、内部酸化層とMgOの両者を反応させて形成するものである。
これらの被膜は、鋼板との間に熱膨張率の差を有するために、高温で形成し、付与された後に常温に冷却されると、収縮率の小さい被膜が鋼板に引っ張り応力を与える働きがある。
発明者らは、前記した課題を検討したところ、図1に示したコーティング膜厚a1と、コーティング膜厚a2と、線状溝深さa3とを適正に制御することで、前記課題が解決できることを見出した。
0.3μm≦a2≦3.5μm ・・・(1)
a2+a3−a1≦15 (μm)・・・(2)
というのは、式(2)左辺の値を低下させると、鋼板全体に凹凸が小さくなって、フラットな形状となるため、鋼板のハンドリング中の引っかかりがなくなって作業性が改善されると同時に、局所的な応力が加わわることで、鋼板がひずみ磁気特性が劣化するという問題も生じなくなるからである。なお、線状溝深さa3は、鋼板表面からの深さであるが、フォルステライト被膜の厚みも、線状溝深さa3に含むものとする。また、上記式(2)の好ましい下限値は、3(μm)である。
というのは、本発明では、溝部においてコーティングの膜厚を増大させるため、張力が局所的に高くなる。その結果、鋼板表面における応力分布が不均一になり、絶縁コーティングの被膜が剥離しやすくなる。これを防止するためにコーティング張力を低下させることが好ましい。
なお、コーティング被膜により発生する張力の下限値は、特に制限はないが、張力効果による鉄損改善の観点から、4MPa程度とするのが好ましい。
このような低張力のコーティングを付与することにより、線状溝部と線状溝部以外との膜厚差による張力の変化の程度が小さくなるため、コーティングが剥離しにくくなる。
なお、線状溝部以外1とは、図1に示したように、線状溝部2を除外した部分である。
まず、測定面にテープを貼ってアルカリ水溶液に浸漬させることで非測定面の絶縁被膜を剥離し、次に図2に示すように、鋼板の反り具合としてL部とX部を測定し、LMとXMを求めておく。
ついで、次式(3)および(4)
L=2Rsin(θ/2) ・・・(3)
X=R{1−cos(θ/2)} ・・・(4)
を用いて、曲率半径Rは、次式(5)
R=(L2+4X2)/8X ・・・(5)
と求められることから、
この式(5)に、L=LMおよびX=XMを代入して、曲率半径Rを求める。さらに、この曲率半径Rを、次式(6)に代入すれば、地鉄表面の引張応力σを算出することができる。
σ=E・ε=E・(d/2R) ・・・(6)
ただし、E:ヤング率(E100=1.4×105MPa)
ε:地鉄界面歪み(板厚中央でε=0)
d:板厚
また、インヒビターを利用する場合、例えばAlN系インヒビターを利用する場合であればAlおよびNを、またMnS・MnSe系インヒビターを利用する場合であればMnとSeおよび/またはSを適量含有させればよい。勿論、両インヒビターを併用してもよい。この場合におけるAl、N、SおよびSeの好適含有量はそれぞれ、Al:0.01〜0.065質量%、N:0.005〜0.012質量%、S:0.005〜0.03質量%、Se:0.005〜0.03質量%である。
この場合には、Al、N、SおよびSe量はそれぞれ、Al:100 質量ppm以下、N:50 質量ppm以下、S:50 質量ppm以下、Se:50 質量ppm以下に抑制することが好ましい。
C:0.15質量%以下
Cは、熱延板組織の改善のために添加をするが、0.15質量%を超えると製造工程中に磁気時効の起こらない50質量ppm以下までCを低減することが困難になるため、0.15質量%以下とすることが好ましい。なお、下限に関しては、Cを含まない素材でも二次再結晶が可能であるので特に設ける必要はない。
Siは、鋼の電気抵抗を高め、鉄損を改善するのに有効な元素であるが、含有量が2.0質量%に満たないと十分な鉄損低減効果が達成できず、一方、8.0質量%を超えると加工性が著しく低下し、また磁束密度も低下するため、Si量は2.0〜8.0質量%の範囲とすることが好ましい。
Mnは、熱間加工性を良好にする上で必要な元素であるが、含有量が0.005質量%未満ではその添加効果に乏しく、一方1.0質量%を超えると製品板の磁束密度が低下するため、Mn量は0.005〜1.0質量%の範囲とすることが好ましい。
Ni:0.03〜1.50質量%、Sn:0.01〜1.50質量%、Sb:0.005〜1.50質量%、Cu:0.03〜3.0質量%、P:0.03〜0.50質量%、Mo:0.005〜0.10質量%およびCr:0.03〜1.50質量%のうちから選んだ少なくとも1種
Niは、熱延板組織を改善して磁気特性を向上させるために有用な元素である。しかしながら、含有量が0.03質量%未満では磁気特性の向上効果が小さく、一方1.5質量%を超えると二次再結晶が不安定になり磁気特性が劣化する。そのため、Ni量は0.03〜1.5質量%の範囲とするのが好ましい。
なお、上記成分以外の残部は、製造工程において混入する不可避的不純物およびFeである。
なお、本発明おいては、鋼板に張力コーティングを付与する際、前述したように、線状溝底面部のコーティング膜厚a1(μm)と線状溝部以外のコーティング膜厚a2(μm)、さらに溝深さa3(μm)をそれぞれ適正に制御することが肝要である。
ついで、825℃で脱炭焼鈍を施したのち、MgOを主成分とする焼鈍分離剤を塗布し、二次再結晶と純化を目的とした最終仕上げ焼鈍を1200℃、10hの条件で実施した。
そして、張力コーティング処理液を塗布し、830℃で、張力コーティング焼付けを兼ねた平坦化焼鈍を行って製品とした。その際、表1に示すようにコータロールの硬度、コート液粘度、コーティング液組成を変化させることにより、各種の膜厚条件でコーティングを塗布、乾燥して焼き付けた。これを用いて、1000kVAの油入り変圧器を製造し、鉄損を測定した。また、得られた製品について、磁気特性、コーティング張力、占積率、錆発生率および層間抵抗をそれぞれ評価した。
なお、磁気特性、占積率および層間抵抗はJIS C2550に記載の方法に準拠し、錆発生率は温度:50℃、露点:50℃で、大気中に50時間保持後、錆発生率を目視判定することで測定した。またコーティング張力は、前述の方法に従って測定を行い求めた。
上記した測定結果をそれぞれ表2に併記する。
しかしながら、前掲式(1)を満足しない試験No.1,7や、前掲式(2)を満足しない試験No.8,9の方向性電磁鋼板は、変圧器に組んだ際の鉄損特性に劣っていた。
2 線状溝部
Claims (3)
- 深さ:10〜50μmの線状溝を設けた鋼板の表面に、絶縁コーティングを施した方向性電磁鋼板において、該線状溝の底面部における該絶縁コーティングの膜厚a1(μm)と、該線状溝部以外の鋼板表面の該絶縁コーティング膜厚a2(μm)と、該線状溝の深さa3(μm)とが、下記式(1)および(2)を満足することを、特徴とする方向性電磁鋼板。
記
0.3μm≦a2≦3.5μm ・・・(1)
a2+a3−a1≦15μm ・・・(2)
(ただし、上記式(2)において、a 2 +a 3 −a 1 =0μmである場合は除く) - 前記絶縁コーティングによる鋼板への付与張力が8MPa以下であることを特徴とする、請求項1に記載の方向性電磁鋼板。
- 前記絶縁コーティングが、リン酸塩-シリカ系のコーティング処理液により形成したものであることを、特徴とする請求項1または2に記載の方向性電磁鋼板。
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