KR20120091655A - Multilayer ceramic electronic part and a manufacturing method thereof - Google Patents

Multilayer ceramic electronic part and a manufacturing method thereof Download PDF

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KR20120091655A
KR20120091655A KR1020110011551A KR20110011551A KR20120091655A KR 20120091655 A KR20120091655 A KR 20120091655A KR 1020110011551 A KR1020110011551 A KR 1020110011551A KR 20110011551 A KR20110011551 A KR 20110011551A KR 20120091655 A KR20120091655 A KR 20120091655A
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layer
active layer
oxide
multilayer ceramic
dielectric
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KR1020110011551A
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Korean (ko)
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권상훈
김휘영
손성범
허강헌
홍민희
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삼성전기주식회사
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Abstract

PURPOSE: A multi-layered ceramic electronic part and a manufacturing method thereof are provided to obtain an electronic part with superior reliability, moisture-proof insulating resistance, and high-temperature insulating resistance by minimizing voids or cracks after plasticization. CONSTITUTION: A multi-layered ceramic capacitor(100) comprises an active layer, a cover layer, and outer electrodes(120a,120b). The active layer comprises a dielectric layer formed of a dielectric composition including ceramic powder with an average grain size of 100-300nm and an inner electrode layer. The cover layer is formed on the top and/or bottom surface of the active layer out of a dielectric composition including the same kind of ceramic powder as the active layer, having an average grain size of 50-250nm. The outer electrodes are electrically connected to the inner electrode layer.

Description

Multilayer ceramic electronic part and a manufacturing method thereof

The present invention relates to a multilayer ceramic electronic component and a method for manufacturing the same, which improve reliability by minimizing the occurrence of structural defects such as pores and cracks after firing.

Recently, as miniaturization, light weight, and multifunctionalization of electric and electronic products are rapidly progressing, multilayer ceramic electronic components, especially multilayer ceramic capacitors (MLCC), which are used, have also been miniaturized and high in capacity.

Accordingly, the dielectric layers used for the multilayer ceramic capacitors are also increasingly thin and highly stacked.

Important considerations in developing ultra-high capacity multilayer ceramic capacitors include the implementation of capacitance and the high reliability of voltage application.

In general, the reliability of a multilayer ceramic capacitor is determined from evaluation results of hot insulation resistance and humidity insulation resistance.

The high temperature insulation resistance characteristic mainly depends on the material aspect (for example, the deterioration characteristic of the dielectric or internal electrode constituting the capacitor, and poor microstructure).

On the other hand, moisture resistance insulation resistance characteristics of the structural aspects (for example, pores or delamination occurring during the compression / cutting, structural defects such as uncoated areas or cracks between the internal electrode after firing, etc. within the external electrode Pores, etc.).

Among them, moisture resistance insulation resistance is known as a direct cause of the IR resistance of multilayer ceramic capacitors due to direct current application. Especially, in a small ultra high capacity multilayer ceramic capacitor manufactured by stacking hundreds of layers of ultra-thin dielectrics This phenomenon appeared frequently and became a problem.

The present invention provides a multilayer ceramic electronic component and a method for manufacturing the same, which improve reliability by minimizing the occurrence of structural defects such as pores and cracks after firing.

One embodiment of the present invention is an active layer of alternating dielectric layers and internal electrode layers formed of a dielectric composition comprising a ceramic powder having an average particle diameter of 100 to 300 nm; A cover layer formed on at least one surface of an upper surface and a lower surface of the active layer, the cover layer formed of a dielectric composition having an average particle diameter of 50 to 250 nm and comprising ceramic powder of the same kind as the active layer; And an external electrode electrically connected to the internal electrode layer.

The average particle diameter of the ceramic powder forming the cover layer may be 50 to 100 nm smaller than the ceramic powder forming the active layer.

The ceramic powder may be at least one selected from barium titanate (BaTiO 3) based, lead complex perovskite teugye and strontium titanate (SrTiO 3) the group consisting of step.

The thickness of the cover layer may be 3 to 10 times thicker than one dielectric layer of the active layer.

The thickness of the one dielectric layer may be 0.5 to 1.5 μm.

The dielectric composition may further include magnesium oxide (MgO), rare earth oxide, manganese oxide (MnO), and borosilicate-based glass.

The rare earth oxide may be at least one selected from the group consisting of yttrium oxide (Y 2 O 3 ), holmium oxide (Ho 2 O 3 ), dysprosium oxide (Dy 2 O 3 ), and ytterbium oxide (Yb 2 O 3 ).

Another embodiment of the present invention comprises the steps of: providing an active layer in which a dielectric layer formed of a dielectric composition comprising a ceramic powder having an average particle diameter of 100 to 300 nm and an internal electrode layer are alternately stacked; Providing a cover layer formed of a dielectric composition having an average particle diameter of 50 to 250 nm and comprising ceramic powder of the same kind as the active layer; Stacking the cover layer on at least one surface of an upper surface and a lower surface of the active layer to form a laminate; Cutting the laminate to manufacture a green chip; And firing the green chip to manufacture a ceramic element.

The multilayer ceramic electronic component according to the present invention has an effect of minimizing the generation of structural defects such as pores and cracks after firing.

For this reason, the multilayer ceramic electronic component according to the present invention has excellent reliability, moisture resistance insulation resistance, and high temperature insulation resistance.

1 is a schematic perspective view showing a multilayer ceramic capacitor according to an embodiment of the present invention.
FIG. 2 is a cross-sectional view taken along line AA ′ of FIG. 1.
3 is a manufacturing process chart for manufacturing a multilayer ceramic capacitor according to another embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings.

However, embodiments of the present invention may be modified in various other forms, and the scope of the present invention is not limited to the embodiments described below. Further, the embodiments of the present invention are provided to more fully explain the present invention to those skilled in the art. Accordingly, the shape and size of elements in the drawings may be exaggerated for clarity, and the elements denoted by the same reference numerals in the drawings are the same elements.

1 is a schematic perspective view illustrating a multilayer ceramic capacitor according to an exemplary embodiment of the present invention, and FIG. 2 is a cross-sectional view taken along line AA ′ of FIG. 1.

1 and 2, a multilayer ceramic electronic component, in particular, a multilayer ceramic capacitor 100 according to an exemplary embodiment of the present invention, may include a dielectric layer 111 formed of a dielectric composition including ceramic powder having an average particle diameter of 100 to 300 nm. ) And an active layer 101 in which the internal electrode layers 112 are alternately stacked; A cover layer 102 formed on at least one of the upper and lower surfaces of the active layer 101 and having an average particle diameter of 50 to 250 nm and formed of a dielectric composition containing the same kind of ceramic powder as the active layer 101. ; And external electrodes 120a and 120b electrically connected to the internal electrode layers.

Hereinafter, among the multilayer ceramic electronic components, a multilayer ceramic capacitor will be specifically described as an embodiment of the present invention.

In general, a multilayer ceramic capacitor is formed by alternately stacking a ceramic dielectric layer and a metal internal electrode layer, and the top and bottom layers are manufactured by stacking a dielectric layer thicker than the internal dielectric layer.

In this case, the inner dielectric layer region adjacent to the metal inner electrode layer is defined as an active layer, and the outermost dielectric layer region not adjacent to the inner electrode layer is defined as a cover layer.

In general, the active layer has better sinterability than the cover layer, which is largely caused by two causes.

First, during the sintering process of the multilayer ceramic capacitor, dielectric powder, ceramic additive powder, or the like flows into the dielectric layer from the metal internal electrode layer to promote sintering of the active layer.

Second, in the case of the cover layer, the amount of residual coal at the sintering temperature is relatively higher than that of the active layer, and the residual coal delays the sintering of the dielectric powder.

The sintering shrinkage mismatch occurs due to the difference in sintering properties between the cover layer and the active layer, which in turn causes fine cracks between the cover layer and the active layer.

In the multilayer ceramic capacitor according to the exemplary embodiment of the present invention, the dielectric compositions of the active layer 101 and the cover layer 102 are made of two kinds of ceramic powders having different particle sizes, respectively, and the sheet molding and lamination are performed to reduce the sinterability. Made to minimize

The ceramic powder may be made of a ceramic material having a high dielectric constant, but is not limited thereto. For example, a barium titanate (BaTiO 3 ) -based material, a lead composite perovskite-based material, or a strontium titanate (SrTiO 3 ) -based material Etc. can be used.

Specifically, a ceramic powder having an average particle diameter of 100 to 300 nm, particularly barium titanate (BaTiO 3 ), may be used for the dielectric composition for forming the active layer 101.

In addition, a ceramic powder having an average particle diameter of 50 to 250 nm, particularly barium titanate (BaTiO 3 ), may be used for the dielectric composition for forming the cover layer 102.

In addition, the dielectric composition for forming the cover layer 102 may use the same kind of ceramic powder as the active layer 101 in order to simultaneously and uniformly bake to minimize plastic shrinkage mismatch.

As described above, according to an embodiment of the present invention, by applying different particle sizes of the ceramic powder used for forming the active layer and the cover layer, there is an effect of minimizing the occurrence of structural defects such as pores and cracks after firing.

Therefore, there is no occurrence of structural defects such as pores and cracks, and according to an embodiment of the present invention, there is an effect of improving the reliability of the multilayer ceramic capacitor.

The average particle diameter of the ceramic powder forming the cover layer may be 50 to 100 nm smaller than the ceramic powder forming the active layer.

When the difference in particle size is less than 50 nm, there is little difference in sinterability, and thus there is no effect of improving reliability compared to the case of applying the same size ceramic powder.

In addition, when the difference in particle size exceeds 100 nm, there is a problem in that the sinterability is so severe that reliability deteriorates in comparison with a conventional multilayer ceramic capacitor to which ceramic powders of the same size are applied.

On the other hand, the multilayer ceramic capacitor according to one embodiment of the present invention has excellent reliability, moisture resistance insulation resistance, and high temperature insulation resistance.

When applying the same size ceramic powder, when firing is carried out at a temperature range for densely sintering the active layer, the cover layer having a low sinterability is relatively unbaked so that a large number of pores exist.

For this reason, the conventional multilayer ceramic capacitors to which ceramic powders of the same size are applied have a problem of deteriorating moisture resistance insulation resistance.

On the contrary, when firing is performed in a temperature range for densely sintering the cover layer, the active layer having high sinterability is relatively under-fired, resulting in uneven microstructure.

In addition, there is a problem that the metal internal electrode layer is agglomerate heavily, deteriorating the high temperature insulation resistance characteristics.

According to the present embodiment, uniform application of the active layer and the cover layer is possible by simultaneously applying different particle sizes of the ceramic powder used for the active layer 101 and the cover layer 102.

By minimizing the sintering shrinkage mismatch due to the uniform firing, it is possible to prevent the generation of pores and cracks to produce a multilayer ceramic capacitor having excellent reliability, moisture resistance insulation resistance, and high temperature insulation resistance.

The cover layer 102 may be formed on at least one of the upper and lower surfaces of the active layer 101, and when the cover layer 102 is formed on both the upper and lower surfaces, the effect of lowering the crack generation rate is excellent.

The thickness of the cover layer may be 3 to 10 times thicker than one dielectric layer of the active layer, and the thickness of the one dielectric layer is not particularly limited, but may be 1.5 μm per layer to implement an ultra-thin high capacity capacitor, and 0.5 to It is preferred that it is 1.5 μm.

According to one embodiment of the present invention, each of the dielectric compositions for forming the active layer 101 and the cover layer 102 includes barium titanate (BaTiO 3 ) as a ceramic dielectric, and the remaining ceramic additive powders are added to the two compositions. All can be applied equally.

The composition and size of the ceramic additive powders may be the same in both compositions.

The dielectric composition may further include magnesium oxide (MgO), rare earth oxide, manganese oxide (MnO), and borosilicate glass as ceramic additives.

The rare earth oxide is not particularly limited, and for example, yttrium oxide (Y 2 O 3 ), holmium oxide (Ho 2 O 3 ), dysprosium oxide (Dy 2 O 3 ) and ytterbium oxide (Yb 2 O 3 ) It may be one or more selected from the group consisting of.

The content of the dielectric composition may vary according to the purpose of the present invention, for example, magnesium oxide (MgO) 0.5 to 2.0, rare earth oxide 0.1 to 1.0, manganese oxide ( MnO) may be 0.05 to 1.0 and borosilicate-based glass may be 1.0 to 3.0 molar parts.

As described above, the multilayer ceramic capacitor according to the exemplary embodiment of the present invention is formed outside the ceramic body 110 and the ceramic body 110 including the active layer 101 and the cover layer 102, and the internal electrode layer and External electrodes 120a and 120b are electrically connected to each other.

The active layer 101 has a structure in which the dielectric layer 111 and the internal electrode layer 112 are alternately stacked, and the cover layer 102 is a ceramic powder having a different particle size from that of the ceramic powder used in the active layer 101. Is formed using.

Therefore, according to the exemplary embodiment of the present invention, the ceramic powders used in the active layer and the cover layer have different particle sizes, which enables uniform firing, thereby minimizing structural defects such as pores and cracks, thereby providing excellent reliability. It provides a multilayer ceramic capacitor having.

3 is a manufacturing process chart for manufacturing a multilayer ceramic capacitor according to another embodiment of the present invention.

Referring to FIG. 3, according to another embodiment of the present invention, a method of manufacturing a multilayer ceramic electronic component, in particular, a multilayer ceramic capacitor, alternates between a dielectric layer and an internal electrode layer formed of a dielectric composition including ceramic powder having an average particle diameter of 100 to 300 nm. Providing a stacked active layer; Providing a cover layer formed of a dielectric composition having an average particle diameter of 50 to 250 nm and comprising ceramic powder of the same kind as the active layer; Stacking the cover layer on at least one of an upper surface and a lower surface of the active layer to form a laminate; Cutting the laminate to manufacture a green chip; And firing the green chip to produce a ceramic body.

First, an active layer 101 in which a dielectric layer formed of a dielectric composition containing ceramic powder having an average particle diameter of 100 to 300 nm and an internal electrode layer are alternately stacked may be provided.

Specifically, in the preparation of the active layer 101, first, a plurality of green sheets may be prepared (a).

The ceramic green sheet may be prepared by mixing a ceramic powder, a binder, and a solvent to prepare a slurry, and the slurry may be manufactured in a sheet shape having a thickness of several μm by a doctor blade method.

In addition, internal electrode layers 130a and 130b may be formed on the green sheet using the conductive paste for internal electrodes (b).

After the internal electrode layers 130a and 130b are formed as described above, the green sheet may be separated from the carrier film, and then the active layers 101 may be prepared by overlapping each of the green sheets (c).

Next, a cover layer 102 formed of a dielectric composition containing the same kind of ceramic powder as the active layer 101 may be provided (d).

Subsequently, the cover layer 102 is laminated on at least one of the upper and lower surfaces of the active layer 101 to form a laminate, and the laminate is compressed at high temperature and high pressure (e). The green chip may be manufactured by cutting to a predetermined size through a cutting process (f) (g).

Thereafter, the ceramic element 110 may be manufactured by sintering, firing, and polishing, and the multilayer ceramic electronic component, in particular, the multilayer ceramic capacitor 100 may be completed through external electrodes 120a and 120b and a plating process.

Therefore, according to one embodiment of the present invention, by uniformly applying different particle sizes of the ceramic powder used for the active layer 101 and the cover layer 102, the active layer and the cover layer can be uniformly baked at the same time.

By minimizing the sintering shrinkage mismatch due to the uniform firing, it is possible to prevent the generation of pores and cracks to produce a multilayer ceramic capacitor having excellent reliability, moisture resistance insulation resistance, and high temperature insulation resistance.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the scope of the present invention is not limited thereto.

Example  1 to 20

According to one embodiment of the present invention, Examples 1 to 20 first mixed and dispersed two organic compositions containing barium titanate (BaTiO 3 ) having different particle sizes, respectively, with an organic solvent.

Next, a slurry was prepared by adding an organic binder, and applied to the film at about 2 μm to prepare molding sheets for the active layer and the cover layer, respectively.

Subsequently, nickel (Ni) internal electrode paste was printed on the active layer dielectric sheet, and 100 dielectric layers on which the internal electrodes were printed were laminated.

Thereafter, a cover dielectric sheet was further laminated on the top and bottom of the laminate.

Thereafter, the laminate was cut by cooling equilibrium press (Cold Isotatic Press) to prepare a specimen.

The specimens were heat-treated at 300 ° C. for at least 4 hours to remove organic binders, dispersants, and the like, and were sintered in a range of 1050 to 1150 ° C. using a firing furnace capable of temperature and atmosphere control.

At this time, the oxygen partial pressure in the firing atmosphere was controlled to 10 −9 to 10 −13 atmospheres.

After the sintered specimens were coated with an external electrode with copper (Cu), electrode firing was performed at 700 to 900 ° C., and after the electrode firing was completed, a plating process was performed to complete the specimen preparation.

Table 1 shows the types of dielectric compositions of the present invention, and the electrical properties and reliability evaluation results of the multilayer ceramic capacitor specimens of Examples 1 to 20 fabricated using the same are shown in [Table 2].

Comparative example  1 to 13

Comparative Examples 1 to 13 are the same as in Examples 1 to 20 except that the difference between the particle size of the barium titanate (BaTiO 3 ) and the two particle sizes of the active layer and the cover layer is outside the claims of the present invention. It was produced by the method.

In Table 2, the electrical properties and the reliability evaluation results of the specimens of the multilayer ceramic capacitors according to Comparative Examples 1 to 13 were compared with Examples 1 to 20.

Composition name chief ingredient Subsidiary ingredient additive (mole parts by weight based on 100 mole parts by weight of main ingredient) Barium titanate
(BaTiO 3 )
Magnesium Oxide (MgO) Yttrium Oxide (Y 2 O 3 ) Manganese Oxide (MnO) Borosilicate
Glass (Li 2 OB 2 O 3 -SiO 2 )
A 100 1.5 1.0 0.3 1.5 B 100 1.5 1.0 0.3 1.0 C 100 1.0 0.5 0.1 2.0 D 100 1.0 0.5 0.1 1.5 E 100 1.0 0.5 0.1 1.0

BaTiO 3 Size (nm) dielectric
Composition
Firing temperature
(℃)
permittivity High Temperature Insulation Resistance (1Vr = 6.3 V / ㎛) Moisture resistance
Active layer Cover layer Example One 100 50 E 1050 3000 2 120 50 E 1050 2900 3 150 100 E 1100 4000 4 150 80 D 1080 3800 5 150 80 E 1100 4100 6 150 50 E 1100 3900 7 200 150 B 1100 4300 8 200 150 D 1080 4000 9 200 100 B 1100 4500 10 200 100 B 1100 4300 11 200 100 E 1120 4500 12 300 200 A 1150 4000 13 300 250 A 1150 4200 14 300 250 B 1150 4500 15 300 230 A 1150 4200 16 300 230 B 1150 4400 17 300 200 A 1150 4300 18 300 200 B 1150 4500 19 300 200 C 1120 4000 20 300 200 D 1150 4100 Comparative example One 100 100 E 1050 3000 × 2 100 70 E 1050 2900 × 3 100 30 E 1050 2800 × 4 150 150 D 1100 3300 × 5 150 150 E 1080 3800 × 6 150 120 E 1080 4000 × 7 150 30 E 1080 3500 8 200 200 B 1100 4300 × 9 200 180 B 1100 4500 10 200 80 B 1100 4300 × × 11 300 300 A 1150 4500 × 12 300 270 A 1150 4300 13 300 180 A 1150 4000 × ×

Note 1) High temperature insulation resistance evaluation level

X: defective (critical insulation resistance is 3 Vr or less)

△: Normal (3 ~ 7Vr)

○: Excellent (7Vr or more)

Note 2) Moisture resistance rating level

×: defective (number of samples with insulation breakdown)

△: Normal (1-5 pieces)

○: Excellent (0)

As can be seen in Table 2, the samples of the embodiment according to the present invention were superior in terms of reliability than the samples of the comparative example, and in particular, the moisture resistance and the insulation resistance were greatly improved.

In particular, in the case of Examples 10, 12, 17, it can be seen that not only high reliability but also dielectric constant showed good results.

The present invention is not limited by the above-described embodiments and the accompanying drawings, but is defined by the appended claims. Therefore, it will be apparent to those skilled in the art that various forms of substitution, modification, and alteration are possible without departing from the technical spirit of the present invention described in the claims, and the appended claims. Will belong to the technical spirit described in.

100: multilayer ceramic capacitor 101: active layer
102: cover layer 110: ceramic body
111: dielectric layer 112: internal electrode layer
120a, 120b: external electrode

Claims (14)

  1. An active layer in which a dielectric layer formed of a dielectric composition containing ceramic powder having an average particle diameter of 100 to 300 nm and an internal electrode layer are alternately stacked;
    A cover layer formed on at least one surface of an upper surface and a lower surface of the active layer, the cover layer formed of a dielectric composition having an average particle diameter of 50 to 250 nm and comprising ceramic powder of the same kind as the active layer; And
    An external electrode electrically connected to the internal electrode layer;
    Laminated ceramic electronic component comprising a.
  2. The method of claim 1,
    The multilayer ceramic electronic component having an average particle diameter of the ceramic powder forming the cover layer is 50 to 100 nm smaller than the ceramic powder forming the active layer.
  3. The method of claim 1,
    The ceramic powder is barium titanate (BaTiO 3) based, lead complex perovskite teugye and strontium titanate (SrTiO 3) one or more multilayer ceramic electronic device selected from the group consisting of step.
  4. The method of claim 1,
    The cover layer has a thickness of 3 to 10 times thicker than one dielectric layer of the active layer.
  5. The method of claim 1,
    The multilayer ceramic electronic component having a thickness of the one dielectric layer is 0.5 to 1.5 μm.
  6. The method of claim 1,
    The dielectric composition may further include magnesium oxide (MgO), rare earth oxide, manganese oxide (MnO), and borosilicate glass.
  7. The method of claim 6,
    The rare earth oxide is at least one multilayer ceramic electron selected from the group consisting of yttrium oxide (Y 2 O 3 ), holmium oxide (Ho 2 O 3 ), dysprosium oxide (Dy 2 O 3 ) and ytterbium oxide (Yb 2 O 3 ) part.
  8. Providing an active layer in which a dielectric layer formed of a dielectric composition containing ceramic powder having an average particle diameter of 100 to 300 nm and an internal electrode layer are alternately stacked;
    Providing a cover layer formed of a dielectric composition having an average particle diameter of 50 to 250 nm and comprising ceramic powder of the same kind as the active layer;
    Stacking the cover layer on at least one of an upper surface and a lower surface of the active layer to form a laminate;
    Cutting the laminate to manufacture a green chip; And
    Firing the green chip to manufacture a ceramic body;
    Method of manufacturing a multilayer ceramic electronic component comprising a.
  9. The method of claim 8,
    The method of manufacturing a multilayer ceramic electronic component having an average particle diameter of the ceramic powder forming the cover layer is 50 to 100 nm smaller than the ceramic powder forming the active layer.
  10. The method of claim 8,
    The ceramic powder is barium titanate (BaTiO 3) based, lead complex perovskite teugye and strontium titanate (SrTiO 3) method of manufacturing a multilayer ceramic electronic device is at least one selected from the group consisting of step.
  11. The method of claim 8,
    The cover layer has a thickness of 3 to 10 times thicker than one dielectric layer of the active layer.
  12. The method of claim 8,
    The thickness of the one dielectric layer is a method of manufacturing a multilayer ceramic electronic component is 0.5 to 1.5 μm.
  13. The method of claim 8,
    The dielectric composition further comprises a magnesium oxide (MgO), rare earth oxide, manganese oxide (MnO) and borosilicate-based glass manufacturing method of a multilayer ceramic electronic component.
  14. The method of claim 13,
    The rare earth oxide is at least one multilayer ceramic electron selected from the group consisting of yttrium oxide (Y 2 O 3 ), holmium oxide (Ho 2 O 3 ), dysprosium oxide (Dy 2 O 3 ) and ytterbium oxide (Yb 2 O 3 ) Method of manufacturing the part.
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