WO2011122742A1 - Insulation material composition for dc power cable and the dc power cable using the same - Google Patents

Insulation material composition for dc power cable and the dc power cable using the same Download PDF

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Publication number
WO2011122742A1
WO2011122742A1 PCT/KR2010/005650 KR2010005650W WO2011122742A1 WO 2011122742 A1 WO2011122742 A1 WO 2011122742A1 KR 2010005650 W KR2010005650 W KR 2010005650W WO 2011122742 A1 WO2011122742 A1 WO 2011122742A1
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Prior art keywords
power cable
magnesium oxide
insulation material
material composition
weight
Prior art date
Application number
PCT/KR2010/005650
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French (fr)
Inventor
Yoon-Jin Kim
Chang-Mo Ko
Jin-Ho Nam
Ho-Souk Cho
Young-Ho Park
Original Assignee
Ls Cable Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ls Cable Ltd. filed Critical Ls Cable Ltd.
Priority to CN201080011002.0A priority Critical patent/CN102812521B/en
Priority to EP10849064.0A priority patent/EP2436014B1/en
Priority to US13/228,566 priority patent/US8648257B2/en
Publication of WO2011122742A1 publication Critical patent/WO2011122742A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/222—Magnesia, i.e. magnesium oxide

Definitions

  • the present invention relates to an insulation material composition for direct current (DC) power cables.
  • An insulation formed from the insulation material composition of the present invention may be used to DC power cables which are suitable as high voltage DC transmission lines of submarine cables, etc.
  • a power cable being currently used in the country comprises a conductor 1, an inner semiconducting layer 2, an insulation 3, an outer semiconducting layer 4, a lead sheath 5 and a polyethylene (PE) sheath 6, as shown in FIGs. 1a and 1b.
  • PE polyethylene
  • Magnesium oxide basically has a face centered cubic (FCC) crystal structure, but it may have various shapes, purity, crystallinity and properties according to synthesis methods. Magnesium oxide has cubic, terrace, rod-like, porous and spherical shapes, as shown in FIGs. 2a through 2e, and each shape may be used depending on specific properties.
  • spherical magnesium oxide is used to suppress a space charge of a power cable, as suggested in Japanese Patent Nos. 2541034 and 3430875. As mentioned above, studies have been made to suppress a space charge in a power cable with an insulation made from polyethylene or crosslinked polyethylene.
  • an insulation material composition for a DC power cable comprises 0.5 to 5 parts by weight of surface-modified nano-sized cubic magnesium oxide, per 100 parts by weight of a crosslinked low-density polyethylene base resin.
  • a DC power cable with an insulation formed using an insulation material composition of the present invention has an increased volume resistivity and an excellent space charge suppression effect.
  • FIG. 1a is a cross-sectional view of a DC power cable.
  • FIG. 1b is a view illustrating the structure of the DC power cable.
  • FIG. 2a is a scanning electron microscopy (SEM) image of cubic magnesium oxide.
  • FIG. 2b is an SEM image of terrace magnesium oxide.
  • FIG. 2c is an SEM image of rod-like magnesium oxide.
  • FIG. 2d is a TEM (TEM) image of porous magnesium oxide.
  • FIG. 2e is an SEM image of spherical magnesium oxide.
  • FIG. 3a is a focused ion beam (FIB)-SEM image of an insulation of the present invention.
  • FIG. 3b is an enlarged view of FIG. 3a, illustrating the particle size of cubic magnesium oxide particles included in the insulation.
  • FIG. 3c is a TEM image of the insulation of the present invention.
  • An insulation material composition of the present invention comprises 0.5 to 5 parts by weight of surface-modified nano-sized cubic magnesium oxide, per 100 parts by weight of a crosslinked low-density polyethylene base resin.
  • the present invention may further comprise 0.1 to 3 parts by weight of a dicumyl peroxide crosslinking agent, and 0.1 to 2 parts by weight of at least one additive selected from the group consisting of an antioxidant and an ion scavenger.
  • the magnesium oxide is surface-modified with vinyl silane, stearic acid, oleic acid, amonopolysiloxane and so on.
  • the magnesium oxide is hydrophilic, i.e., having high surface energy
  • the polyethylene base resin is hydrophobic, i.e., having low surface energy, and thus, dispersion of the magnesium oxide in the polyethylene base resin is low and electrical properties are deteriorated.
  • it is preferred to modify the surface of the magnesium oxide.
  • surface modification of magnesium oxide with vinyl silane allows an excellent dispersion in the polyethylene base resin and improved electrical properties.
  • Hydrolysable groups of vinyl silane are chemically bonded to the surface of magnesium oxide by a condensation reaction, so that magnesium oxide is surface-modified.
  • a silane group of the surface-modified magnesium oxide reacts with the polyethylene base resin, ensuring excellent dispersion.
  • the magnesium oxide has a purity between 99.9 and 100% and an average particle size of 500 nm or less, and the magnesium oxide may have both monocrystalline and polycrystalline structures.
  • the surface-modified nano-sized cubic magnesium oxide at an amount of 0.5 to 5 parts by weight.
  • the content of the surface-modified nano-sized cubic magnesium oxide is less than 0.5 parts by weight, it has a space charge suppression effect, but exhibits a relatively low DC breakdown strength.
  • the content of the surface-modified nano-sized cubic magnesium oxide exceeds 5 parts by weight, it reduces the mechanical performance and continuous extrudability.
  • the antioxidant of the present invention may use at least one selected from the group consisting of amine-based, dialkylester-based, thioester-based and phenol-based antioxidants.
  • the ion scavenger of the present invention may use aryl-based silane, and may allow a space charge suppression effect.
  • An insulation formed using an insulation material composition for a power cable according to the present invention may be used in manufacturing a DC power cable.
  • Insulation material compositions of examples and comparative examples were prepared according to composition of the following table 1, to find out changes in performance depending on the shape and particle size of magnesium oxide of an insulation material composition for a DC power cable.
  • the unit of content in Table 1 is parts by weight.
  • FIG. 3a a FIB-SEM image
  • FIG. 3b is an enlarged view of FIG. 3a, illustrating cubic magnesium oxide contained in the insulation.
  • FIG. 3c a TEM image.
  • the insulations according to examples 1 to 3 and comparative examples 1 to 3 were thermocompressed to manufacture a 0.1mm-thick section for measuring volume resistivity and DC breakdown strength, and a 1mm-thick sheet-type section for measuring impulse strength, and the sections were tested for volume resistivity, DC breakdown strength (ASTM D149) and impulse strength, and the test results are shown in the following Table 2.
  • the test conditions are briefly described as follows.
  • volume resistivity (x 10 14 ⁇ cm) is measured.
  • DC breakdown strength (kV) is measured at 90°C.
  • a 1mm-thick sheet-type section is connected to electrodes, with increasing voltage from 50kV by 5kV until the section is broken, and impulse strength is measured.
  • the sections of examples 1 to 3 exhibited relatively higher volume resistivity and DC breakdown strength than comparative example 1 (without magnesium oxide), comparative example 2 (with terrace magnesium oxide), and comparative example 3 (with spherical magnesium oxide). That is, the sections of examples 1 to 3 using cubic magnesium oxide according to the present invention have excellent electrical insulating properties.
  • the sections of examples 1 to 3 hardly have a reduction in impulse strength when compared with comparative example 1 (without magnesium oxide). That is, although the sections of the present invention used the surface-modified magnesium oxide which is an inorganic additive, to exhibit excellent electrical insulating properties, they showed a similar level of impulse strength to that of comparative example 1 without any inorganic additive such as magnesium oxide.
  • an insulation made from an insulation material composition for a DC power cable and a power cable provided therewith had excellent effects in volume resistivity, DC breakdown strength and impulse strength for the following reasons:
  • cubic magnesium oxide was used to suppress a space charge.
  • magnesium oxide was surface-modified, such that the surface energy of the surface-modified magnesium oxide is similar to that of polyethylene base resin, inducing a chemical bond between the surface-modified magnesium oxide and the polyethylene base resin to ensure an optimum dispersion.
  • the components of the insulation material composition were mixed at a proper content.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Organic Insulating Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Inorganic Insulating Materials (AREA)

Abstract

Provided is an insulation material composition for a DC power cable, comprising 0.5 to 5 parts by weight of surface-modified nano-sized cubic magnesium oxide, per 100 parts by weight of a crosslinked low-density polyethylene base resin. A DC power cable with an insulation made from the insulation material composition of the present invention has an increased volume resistivity and an excellent space charge suppression effect.

Description

INSULATION MATERIAL COMPOSITION FOR DC POWER CABLE AND THE DC POWER CABLE USING THE SAME
The present invention relates to an insulation material composition for direct current (DC) power cables. An insulation formed from the insulation material composition of the present invention may be used to DC power cables which are suitable as high voltage DC transmission lines of submarine cables, etc.
<Cross-Reference to Related Application>
This application claims priority to Korean Patent Application No. 10-2010-0030232 filed in Republic of Korea on April 2, 2010, the entire contents of which are incorporated herein by reference.
A power cable being currently used in the country comprises a conductor 1, an inner semiconducting layer 2, an insulation 3, an outer semiconducting layer 4, a lead sheath 5 and a polyethylene (PE) sheath 6, as shown in FIGs. 1a and 1b.
Polyethylene and crosslinked polyethylene have been widely used as the insulation 3 of the power cable. However, in case where a power cable with an insulation made from polyethylene or crosslinked polyethylene is used as a high voltage transmission line, several problems may occur. The worst problem is that when a high voltage DC is applied to a cable, a space charge is liable to generate due to movement of electric charges from an electrode into an insulation and the influence of crosslinking by-products. And, if such a space charge is accumulated in a polyethylene insulation by a high voltage DC applied to a power cable, the electric field strength of the power cable near a conductor increases, resulting in reduced breakdown voltage of the cable.
To solve the problem, solutions have been suggested to form an insulation using magnesium oxide. Magnesium oxide basically has a face centered cubic (FCC) crystal structure, but it may have various shapes, purity, crystallinity and properties according to synthesis methods. Magnesium oxide has cubic, terrace, rod-like, porous and spherical shapes, as shown in FIGs. 2a through 2e, and each shape may be used depending on specific properties. In particular, spherical magnesium oxide is used to suppress a space charge of a power cable, as suggested in Japanese Patent Nos. 2541034 and 3430875. As mentioned above, studies have been made to suppress a space charge in a power cable with an insulation made from polyethylene or crosslinked polyethylene.
Therefore, it is an object of the present invention to provide an insulation material composition for a DC power cable, with an excellent space charge suppression effect.
To achieve this object, an insulation material composition for a DC power cable according to the present invention comprises 0.5 to 5 parts by weight of surface-modified nano-sized cubic magnesium oxide, per 100 parts by weight of a crosslinked low-density polyethylene base resin.
A DC power cable with an insulation formed using an insulation material composition of the present invention has an increased volume resistivity and an excellent space charge suppression effect.
The accompanying drawings illustrate the preferred embodiments of the present invention and are included to provide a further understanding of the spirit of the present invention together with the detailed description of the invention, and accordingly, the present invention should not be limitedly interpreted to the matters shown in the drawings.
FIG. 1a is a cross-sectional view of a DC power cable.
FIG. 1b is a view illustrating the structure of the DC power cable.
FIG. 2a is a scanning electron microscopy (SEM) image of cubic magnesium oxide.
FIG. 2b is an SEM image of terrace magnesium oxide.
FIG. 2c is an SEM image of rod-like magnesium oxide.
FIG. 2d is a TEM (TEM) image of porous magnesium oxide.
FIG. 2e is an SEM image of spherical magnesium oxide.
FIG. 3a is a focused ion beam (FIB)-SEM image of an insulation of the present invention.
FIG. 3b is an enlarged view of FIG. 3a, illustrating the particle size of cubic magnesium oxide particles included in the insulation.
FIG. 3c is a TEM image of the insulation of the present invention.
Hereinafter, the present invention will be described in detail.
An insulation material composition of the present invention comprises 0.5 to 5 parts by weight of surface-modified nano-sized cubic magnesium oxide, per 100 parts by weight of a crosslinked low-density polyethylene base resin.
And, according to another object, the present invention may further comprise 0.1 to 3 parts by weight of a dicumyl peroxide crosslinking agent, and 0.1 to 2 parts by weight of at least one additive selected from the group consisting of an antioxidant and an ion scavenger.
Preferably, the magnesium oxide is surface-modified with vinyl silane, stearic acid, oleic acid, amonopolysiloxane and so on. Typically, the magnesium oxide is hydrophilic, i.e., having high surface energy, while the polyethylene base resin is hydrophobic, i.e., having low surface energy, and thus, dispersion of the magnesium oxide in the polyethylene base resin is low and electrical properties are deteriorated. To solve the problem, it is preferred to modify the surface of the magnesium oxide.
Without surface modification of the magnesium oxide, a gap is generated between the magnesium oxide and the polyethylene base resin, which causes a reduction in mechanical properties, and electrical properties such as breakdown strength.
On the other hand, surface modification of magnesium oxide with vinyl silane allows an excellent dispersion in the polyethylene base resin and improved electrical properties. Hydrolysable groups of vinyl silane are chemically bonded to the surface of magnesium oxide by a condensation reaction, so that magnesium oxide is surface-modified. Next, a silane group of the surface-modified magnesium oxide reacts with the polyethylene base resin, ensuring excellent dispersion.
Preferably, the magnesium oxide has a purity between 99.9 and 100% and an average particle size of 500 nm or less, and the magnesium oxide may have both monocrystalline and polycrystalline structures.
And, it is preferred to include the surface-modified nano-sized cubic magnesium oxide at an amount of 0.5 to 5 parts by weight. In case where the content of the surface-modified nano-sized cubic magnesium oxide is less than 0.5 parts by weight, it has a space charge suppression effect, but exhibits a relatively low DC breakdown strength. In case that the content of the surface-modified nano-sized cubic magnesium oxide exceeds 5 parts by weight, it reduces the mechanical performance and continuous extrudability.
The antioxidant of the present invention may use at least one selected from the group consisting of amine-based, dialkylester-based, thioester-based and phenol-based antioxidants.
The ion scavenger of the present invention may use aryl-based silane, and may allow a space charge suppression effect.
An insulation formed using an insulation material composition for a power cable according to the present invention may be used in manufacturing a DC power cable.
Hereinafter, the present invention will be described in detail through examples. However, the description proposed herein is just a preferable example for the purpose of illustrations only, not intended to limit the scope of the invention, so it should be understood that the examples are provided for a more definite explanation to an ordinary person skilled in the art.
Insulation material compositions of examples and comparative examples were prepared according to composition of the following table 1, to find out changes in performance depending on the shape and particle size of magnesium oxide of an insulation material composition for a DC power cable. The unit of content in Table 1 is parts by weight.
Table 1
Components Example 1 Example 2 Example 3 Comparative example 1 Comparative example 2 Comparative example 3
Content of base resin 100 100 100 100 100 100
Magnesium oxide Content 2.0 2.0 2.0 None 2.0 2.0
Shape Cubic Cubic Cubic Terrace Spherical
D50(nm) 70 100 240 100 100
D99(nm) 110 150 270 150 150
Purity(%) 99.95 99.95 99.95 99.95 99.95
Content of crosslinking agent 2 2 2 2 2 2
Content of antioxidant 0.4 0.4 0.4 0.4 0.4 0.4
[Components of Table 1]
- Base resin: Crosslinked low-density polyethylene resin (LG chem., LE2030; Density: 0.85~0.95 kg/m3, Melt index (MI): 1~2)
- Magnesium oxide: Powdery magnesium oxide surface-modified with vinyl silane. For improved dispersion, roll mixing milling is made such that D99 (maximum particle size) is not three times more than D50 (average particle size)
- Crosslinking agent: Dicumyl peroxide
- Antioxidant: tetrakis-(methylene-(3,5-di-(tert)-butyl-4-hydrocinnamate))methane
Property measurement and evaluation
Master batch compounds were prepared using insulation material compositions of examples 1 to 3 and comparative examples 1 to 3, and extruded using a twin screw extruder whose screw diameter is 25 mm(L/D=60). The resulting insulation of the present invention is shown in FIG. 3a as a FIB-SEM image, and FIG. 3b is an enlarged view of FIG. 3a, illustrating cubic magnesium oxide contained in the insulation. And, the insulation of the present invention is shown in FIG. 3c as a TEM image.
The insulations according to examples 1 to 3 and comparative examples 1 to 3 were thermocompressed to manufacture a 0.1mm-thick section for measuring volume resistivity and DC breakdown strength, and a 1mm-thick sheet-type section for measuring impulse strength, and the sections were tested for volume resistivity, DC breakdown strength (ASTM D149) and impulse strength, and the test results are shown in the following Table 2. The test conditions are briefly described as follows.
1) Volume resistivity
When a DC electric field of 80 kV/mm is applied, volume resistivity (x 1014 Ω·cm) is measured.
2) DC breakdown strength
DC breakdown strength (kV) is measured at 90℃.
3) Impulse strength
A 1mm-thick sheet-type section is connected to electrodes, with increasing voltage from 50kV by 5kV until the section is broken, and impulse strength is measured.
Table 2
Items Example 1 Example 2 Example 3 Comparative example 1 Comparative example 2 Comparative example 3
Volume resistivity(x10 14Ω·cm) 10 8 8 4 5 6
DC breakdown strength(kV/mm) 125 115 110 55 80 95
Impulse strength(kV/mm) 110 105 100 120 60 80
As shown in Table 2, the sections of examples 1 to 3 exhibited relatively higher volume resistivity and DC breakdown strength than comparative example 1 (without magnesium oxide), comparative example 2 (with terrace magnesium oxide), and comparative example 3 (with spherical magnesium oxide). That is, the sections of examples 1 to 3 using cubic magnesium oxide according to the present invention have excellent electrical insulating properties.
And, the sections of examples 1 to 3 hardly have a reduction in impulse strength when compared with comparative example 1 (without magnesium oxide). That is, although the sections of the present invention used the surface-modified magnesium oxide which is an inorganic additive, to exhibit excellent electrical insulating properties, they showed a similar level of impulse strength to that of comparative example 1 without any inorganic additive such as magnesium oxide.
Among the sections of examples 1 to 3, particularly the section of example 1 with the smallest average particle size had excellent effects in volume resistivity, DC breakdown strength and impulse strength.
As seen in the above results, an insulation made from an insulation material composition for a DC power cable and a power cable provided therewith had excellent effects in volume resistivity, DC breakdown strength and impulse strength for the following reasons: First, cubic magnesium oxide was used to suppress a space charge. Secondly, magnesium oxide was surface-modified, such that the surface energy of the surface-modified magnesium oxide is similar to that of polyethylene base resin, inducing a chemical bond between the surface-modified magnesium oxide and the polyethylene base resin to ensure an optimum dispersion. Thirdly, the components of the insulation material composition were mixed at a proper content.
Hereinabove, the preferred embodiments of the present invention are described in detail. It should be understood that the terms used in the specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation.

Claims (5)

  1. An insulation material composition for a direct current (DC) power cable, the composition comprising:
    0.5 to 5 parts by weight of surface-modified nano-sized cubic magnesium oxide, per 100 parts by weight of a crosslinked low-density polyethylene base resin.
  2. The insulation material composition for a DC power cable according to claim 1, further comprising:
    per 100 parts by weight of the low-density polyethylene base resin,
    0.1 to 3 parts by weight of a dicumylperoxide crosslinking agent; and
    0.1 to 2 parts by weight of at least one additive selected from the group consisting of an antioxidant and an ion scavenger.
  3. The insulation material composition for a DC power cable according to claim 1 or 2,
    wherein the magnesium oxide has a purity of 99.9% or more and an average particle size of 500 nm or less.
  4. The insulation material composition for a DC power cable according to claim 1 or 2,
    wherein the magnesium oxide is monocrystalline or polycrystalline.
  5. A DC power cable, comprising an insulation made using an insulation material composition for a DC power cable, defined in claim 1 or 2.
PCT/KR2010/005650 2010-04-02 2010-08-24 Insulation material composition for dc power cable and the dc power cable using the same WO2011122742A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201080011002.0A CN102812521B (en) 2010-04-02 2010-08-24 For DC power cable insulation composition and use its DC power cable
EP10849064.0A EP2436014B1 (en) 2010-04-02 2010-08-24 Insulation material composition for dc power cable and the dc power cable using the same
US13/228,566 US8648257B2 (en) 2010-04-02 2011-09-09 Insulation material composition for DC power cable and the DC power cable using the same

Applications Claiming Priority (2)

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KR10-2010-0030232 2010-04-02
KR1020100030232A KR101408922B1 (en) 2010-04-02 2010-04-02 Insulation Material Composition For DC Power Cable And The DC Power Cable Using The Same

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CN102812521B (en) 2015-09-16
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US8648257B2 (en) 2014-02-11
KR20110110928A (en) 2011-10-10

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