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EP2174734B1 - Hammering vibrator in continuous casting - Google Patents

Hammering vibrator in continuous casting Download PDF

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Publication number
EP2174734B1
EP2174734B1 EP08791358.8A EP08791358A EP2174734B1 EP 2174734 B1 EP2174734 B1 EP 2174734B1 EP 08791358 A EP08791358 A EP 08791358A EP 2174734 B1 EP2174734 B1 EP 2174734B1
Authority
EP
European Patent Office
Prior art keywords
slab
impact
block
casting
narrow side
Prior art date
Legal status (The legal status 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 status listed.)
Not-in-force
Application number
EP08791358.8A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP2174734A1 (en
EP2174734A4 (en
Inventor
Toshihiko Murakami
Akihiro Yamanaka
Norikazu Koga
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Steel Corp
Original Assignee
Nippon Steel and Sumitomo Metal Corp
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 Nippon Steel and Sumitomo Metal Corp filed Critical Nippon Steel and Sumitomo Metal Corp
Priority to PL08791358T priority Critical patent/PL2174734T3/pl
Publication of EP2174734A1 publication Critical patent/EP2174734A1/en
Publication of EP2174734A4 publication Critical patent/EP2174734A4/en
Application granted granted Critical
Publication of EP2174734B1 publication Critical patent/EP2174734B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/12—Accessories for subsequent treating or working cast stock in situ
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/10—Supplying or treating molten metal
    • B22D11/11—Treating the molten metal
    • B22D11/114—Treating the molten metal by using agitating or vibrating means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/12—Accessories for subsequent treating or working cast stock in situ
    • B22D11/1206—Accessories for subsequent treating or working cast stock in situ for plastic shaping of strands

Definitions

  • the present invention relates to impact-vibration equipment which impacts the narrow side of a casting slab during continuous casting, so as to prevent the occurrence of center segregation.
  • Macro-segregation in the form of center segregation or V-shape segregation readily occurs in the central region and the vicinity thereof in the direction of thickness in a continually cast slab. Macro-segregation is also referred to below as an internal defect.
  • Center segregation is an internal defect which occurs when solute elements such as C, S, P, Mn, and the like (referred to below as segregation elements), which readily segregate, increase in concentration in the crater end of a casting slab.
  • segregation elements solute elements such as C, S, P, Mn, and the like
  • V-shape segregation is an internal defect which occurs when these segregation elements increase in concentration in a V-shape on the longitudinal section of a casting slab in the vicinity of the crater end of a casting slab.
  • the mechanism of segregation formation in casting slabs is thought to operate in the following manner.
  • segregation elements form between dendrite arms of columnar crystals which make up the solidification structure.
  • Molten steel containing these enriched segregation elements flows out from between the dendrite arms of the columnar crystals as a result of solidification shrinkage of the slab or as a result of expansion of the casting slab. This is known as bulging.
  • the enriched molten steel flows out and moves toward the point of complete solidification of the crater end of the slab, and solidifies to form an enriched zone of segregation elements. Enriched zones of segregation elements formed in this manner result in segregation.
  • Such segregation in casting slabs is effectively prevented by inhibiting the migration of molten steel with enriched segregation elements remaining between the dendrite arms of the columnar crystals, and by preventing the enriched molten steel from accumulating locally.
  • Patent Reference 1 there is disclosed a method of arranging an air hammer between rolls disposed at the wide end of the slab during continuous casting, so as to impart an impact vibration of 10-100 times/min at an amplitude of about 2.0 mm or less to the slab as it moves between the rolls.
  • Patent Reference 1 Japanese Patent Application Kokai Publication No. S51-128631
  • Patent Reference 2 the present applicant disclosed a casting method wherein vibrations are applied to a slab at a position having a rectangular cross section and containing a liquid core while the slab is being reduced by a plurality of paired guide rolls used for reduction. This method provided for continuous impact on at least one site on the surface of the casting slab within the reduction region.
  • Patent Reference 2 Japanese Patent Application Kokai Publication No. 2003-334641
  • Patent Reference 2 causes bulging of the slab at a position containing a liquid core and reduces this bulging slab with at least one pair of reduction rolls until solidification is completed in the central region in the direction of thickness.
  • Patent Reference 2 further discloses a method of casting such that when the foregoing occurs, impact is applied to the slab. According to this method, at least one site on the slab surface is continuously impacted within a region in the direction of casting or within the reduction region in the direction of casting, after bulging starts and before reduction starts.
  • JP 2002-273554 discloses that when the cast slab having a rectangular cross sectional shape is cast, the casting is performed while giving vibration to the cast slab by continuously hitting the short side surface of the cast slab containing unsolidified part with a hit-vibrating device.
  • JP 2006-110620 discloses in a method for continuously casting steel, when casting a cast slab having a rectangular cross-sectional shape, the cast slab is cast while giving vibration to the cast slab by applying continuous blows against at least one part of the short-side surfaces of the cast slab including an unsolidified portion.
  • Patent Reference 1 the following serious problems occur when attempting to achieve a significant decrease in center segregation.
  • Patent Reference 2 effectively prevents segregation in a slab.
  • the inventors have determined that there are cases in which segregation is not sufficiently decreased, depending on the shape of the slab.
  • the problem to be solved by the present invention is that in the case of the prior art, when impact is imparted from the narrow side of the slab during continuous casting, there are cases in which it is impossible to effectively prevent the occurrence of segregation, such as center segregation and V-shape segregation when the slab width becomes large.
  • the present invention provides a continuous casting machine for continuous casting of a metal in which equipment is installed for continuous soft reduction by pinch rolls during continuous casting of a slab having a rectangular transverse cross section when the solid fraction at a center in the direction of thickness f s is at least in a range of 0.1-0.9, and the reduction ratio in the direction of the slab thickness is within 1% per meter of length in the direction of casting, the equipment being for continuously impacting both of the opposing sides of a narrow side of the slab in a direction of slab width in at least one site where a solid fraction at the center of the slab in the direction of thickness f s is within a range of 0.1-0.9 at a vibration frequency of impact of 4-12 Hz, and an impact energy of 30-150 J, the equipment comprising:
  • fs (T L - T) / (T L - T s )
  • T L liquidus temperature
  • f s 0
  • T f s 1.0
  • the temperature at slab thickness center T can be obtained by a simple non-steady state heat transfer calculation in the direction of slab thickness. This calculation takes into consideration the casting speed, slab surface cooling, and the physical properties of the type of steel used in casting.
  • the occurrence of segregation is effectively prevented even when casting a slab with a large slab width, thereby resulting in a cast slab with good internal quality.
  • the present invention overcomes this problem by means of a block structure which is enabled to uniformly impact, in a continuous manner, at least the narrow side of the slab as a single unit between two sets of paired pinch rolls adjacent to each other.
  • the impact vibrations do not sufficiently propagate to the interior of the slab in the vicinity of the central region, as viewed in the widthwise direction.
  • the columnar crystals are not broken up during their growth. This allows the columnar crystals grow, and makes it impossible to form a fine crystal structure and prevents a sufficient segregation decreasing effect from being achieved.
  • the impact does not sufficiently reach the equiaxed crystals formed in the vicinity of the crater end of the slab in the center region in the widthwise direction. Thus, bridging of the equiaxed crystals readily occurs and a sufficient segregation decreasing effect is not achieved.
  • the inventors conducted repeated experiments in applying impact from both of the opposing sides of the narrow side of the slab containing a liquid core, so as to prevent the occurrence of center segregation or V-shape segregation. Using these experiments, the inventors investigated how to apply impact from the narrow side of the slab so that impact vibrations would sufficiently propagate to the interior of the slab in the vicinity of the central region in the direction of slab width.
  • the inventors have also disclosed a method for continuous casting of steel in which soft reduction is carried out when casting slabs having a rectangular transverse cross section, with the solid fraction at the center of the slab in the direction of thickness f s within a range of 0.1-0.9 (Japanese Patent Application No. 2006-53057 ).
  • this method applies a continuous impact in the direction of slab width at least at one site where the solid fraction f s is within this range.
  • This equipment is impact-vibration equipment having a structure that enables it to uniformly impact as a single unit the entire surface of the narrow side of the slab at both of the opposing sides of the narrow side of the slab, respectively, in at least one segment among segments formed by a plurality of guide rolls.
  • the impact-vibration equipment for continuous casting of the present invention is based on the above findings.
  • This equipment continuously performs soft reduction during continuous casting of a slab having a rectangular transverse cross section, so that the solid fraction at the center of the slab in the direction of thickness f s is at least 0.1-0.9 and the reduction ratio in the direction of slab thickness is within 1% per meter of length in the direction of casting.
  • the equipment continuously impacts both of the opposing sides of the narrow side of the slab in the direction of slab width in at least one site where the solid fraction at the center of the slab in the direction of thickness f s is within a range of 0.1-0.9 at a vibration frequency of impact of 4-12 Hz and an impact energy of 30-150 J.
  • This equipment comprises:
  • the impact-vibration equipment for continuous casting of a slab of the present invention includes a casting slab 1, which is solidified and cast in a mold and is disposed on the downstream side in the direction of casting, and a block 3 is disposed between a plurality of sets of paired pinch rolls 2a, 2b, as shown in FIG. 1 .
  • Reference Numeral 3 represents a block which impacts the narrow side of the casting slab 1.
  • This block 3 has a structure possessing an impact plate 3a disposed between at least two adjacent sets of paired pinch rolls 2a, 2b in the plurality of sets of paired pinch rolls 2a, 2b.
  • This structure makes it possible to uniformly and continuously impact at least the narrow side of the slab 1 as a single unit at a position between two sets of paired pinch rolls 2a, 2b disposed adjacent to each other. From the standpoint of durability and heat resistance, it is desirable that this block 3 be cast.
  • Bridging of equiaxed crystals or the like occurs at positions where the solid fraction at the center in the direction of thickness of casting slab 1 is 0.1 or higher.
  • bridging can re-occur if the impact does not completely stop the bridging. Therefore, it is desirable to thoroughly implement continuous impact in a range where the solid fraction at the center in the direction of thickness of casting slab 1 is 0.4 or higher, and it is desirable to impact the entire length between the plurality of sets of paired pinch rolls 2a, 2b.
  • the solid fraction ranging between 0.1 and 0.9 at the center in the direction of thickness of the casting slab is within a relatively broad range, and the position described above constantly changes during the actual casting operation, as described below. Therefore, there are cases where the impact between two adjacent sets of paired pinch rolls 2a, 2b is sufficient. There are also cases where impact is needed between three adjacent sets of paired pinch rolls 2a, 2b, as shown in FIG. 1 .
  • installation costs would be excessive if the equipment was required to operate over the entire range of the solid fraction at the center in the direction of thickness of casting slab and to impact over a lengthy area. Accordingly, impact is implemented between three adjacent sets of paired pinch rolls 2a, 2b, for example, which is considered to be a range that will achieve the impact-vibration effect.
  • the length of the block 3 in the direction of casting be a length that enables impact over the entire region of the plurality of sets of paired pinch rolls 2a, 2b.
  • the paired pinch rolls 2a, 2b are installed in and removed from the continuous casting machine, thus they should be as long as possible to enable impact without interfering with the various elements of the continuous casting machine.
  • the paired pinch rolls 2a, 2b have a structure that makes it possible to adjust the amount of reduction and also to eliminate soft reduction through the use of a hydraulic cylinder 5, which is typically attached to an upper frame 4.
  • Reference Numeral 6 represents an impact device to which the block 3 is attached at the front end.
  • the impact device 6 generates periodic impact and transmits this impact to the block 3.
  • An air cylinder for example, may be used for this purpose.
  • This impact device 6 is disposed, for example, in two places on both of the opposing sides of the narrow side of the slab 1 that contains a liquid core.
  • Reference Numeral 7 represents a position control device, which pushes the block 3 from the standby position shown in FIG. 2 (a) , to the narrow side of the slab 1 [ see FIG. 2 (b) ]. After detecting the pushing position, the position control device sets the gap L (impact amplitude: about 8 mm) between the front end surface of the block 3 and the narrow side of the slab 1, at the pull-back position of the block 3 [ see FIG. 2 (c) ].
  • the position control device 7 is not limited to the structure shown in FIG. 2 , and may also have the structure shown in FIG. 3 .
  • the position control device 7 of FIG. 3 sets the gap L (impact amplitude: about 8 mm) between the front end surface of the block 3 and the narrow side of the slab 1 by causing a pushing guide 8 to move from the standby position shown in FIG. 3 (a) to a position where it makes contact with the narrow side of the slab 1 [ see FIG. 3 (b) ]. While impact is being performed as shown in FIG. 3 (c) , this position control device 7 creates a state in which the pushing guide 8 is pushed against the narrow side of the slab 1.
  • the conditions for installing the pushing guide 8 are set in advance, so that the gap L between the block 3 and the casting slab 1 has a predetermined length.
  • the gap L between the block 3 and the narrow side of the casting slab 1 depends on the width of the slab 1 that is being cast. This gap L affects the stroke of the impact device 6. If the stroke is insufficient, then the impact speed cannot be ensured during impact and sufficient impact energy cannot be produced. Therefore, when impact begins, the relative positions of the block 3 and the narrow side of the slab 1 are adjusted in what is called positioning.
  • the equipment of the present invention when continuously casting the slab 1 having a rectangular transverse cross section, soft reduction is continuously carried out so that the solid fraction at the center in the direction of thickness f s is at least 0.1-0.9, and the reduction ratio in the direction of slab thickness is within 1% per meter of length in the direction of casting, and the equipment continuously impacts both of the opposing sides of the narrow side of the slab 1 in the direction of slab width at least one site where the solid fraction at the center in the direction of thickness f s is within a range of 0.1-0.9 with a vibration frequency of impact of 4-12 Hz and an impact energy of 30-150 J.
  • the solid fraction at the center in the direction of thickness f s in the range of 0.1-0.9 referred to in this invention forms a long region in the direction of casting.
  • the double-headed arrows shown in two places in FIG. 4 illustrate examples of impact plates for imparting impact to the slab being arranged in the respective positions with the distance being taken from the mold output side.
  • the example of the impact plate of FIG. 4 illustrates continuous impact on both of the opposing sides of the narrow side of the slab 1 in the direction of slab width, when the solid fraction at the center in the direction of thickness f s is in the range 0.4-0.8.
  • the double-headed arrows shown in the two places in FIG. 5 illustrate examples of impact plates for imparting impact to the slab being arranged in a position at the distance of these two places from the mold output side.
  • the example of the impact plate of FIG. 5 illustrates continuous impact on both of the opposing sides of the narrow side of the slab 1 in the direction of slab width when the solid fraction at center in the direction of thickness f s is in the range 0.25-1.0, which range also includes the range 0.25-0.9.
  • soft reduction is continuously carried out on the casting slab, so that the solid fraction at the center in the direction of thickness f s is in the range 0.1-0.9 and so that the reduction ratio in the direction of slab thickness is within 1% per meter of length in the direction of casting.
  • the effective range for decreasing center segregation is such that the reduction ratio in the direction of slab thickness is within about 1% per meter of length in the direction of casting.
  • the reduction ratio in the direction of slab thickness greatly exceeding 1% per meter of length in the direction of casting and at a low solid fraction range then strain at the solid-liquid interface greatly increases and internal cracking readily occurs.
  • the reduction ratio in the direction of thickness of the slab 1 is within 1% per meter of length in the direction of casting.
  • the narrow side of the slab is subjected to continuous impact, rather than the wide side of the slab.
  • the slab readily undergoes bulging between the rolls on the wide side, and if impact vibration is applied to a bulging wide side, then fluctuation in the surface level of molten steel in the mold is encouraged on the upstream side.
  • provision of the impact imparting means causes the drawback of interference with the spraying position for secondary cooling of the slab between the rolls, thus making it impossible to continuously apply impact.
  • the site where impact vibration can be applied is 200 mm in the direction of casting.
  • the site where the impact vibration can be applied is on the order of 2,300 mm in the direction of casting, for example, as long as the length of the impact plate is sufficiently maintained. Therefore, if impact vibration is applied to the narrow side of the slab, then the volume change is on the order of 1/11.5.
  • the reason why the vibration frequency of impact is set at 4-12 Hz during impact is that if the vibration frequency of impact is less than 4 Hz, then the impact energy is not sufficiently transmitted to the liquid core of the slab, so there is little center segregation decreasing effect.
  • the impact energy is set at 30 J -150 J. This is because if impact energy exceeding 150 J is applied, then peripheral equipment installed in the continuous casting machine can be damaged. If impact energy is applied above the necessary level, then the durability of the impact device 6 itself can be compromised.
  • the impact energy is less than 30 J, then the impact vibration is not sufficiently propagated from the narrow side of the slab 1 to the slab interior in the vicinity of the center in the direction of slab width.
  • the impact frequency is of particular importance since bridging cannot be completely suppressed, particularly when there is a high solid fraction at the final stage of solidification, even if a high impact energy is applied several times every minute.
  • the range of vibration frequency of impact established for the present invention does not change with blooms or slabs of different slab widths. However, the optimal impact energy changes, since the volumes of liquid held by blooms and slabs can differ.
  • the reduction ratio When soft reduction is performed during continuous casting using the impact-vibration equipment of the present invention, in a range from the upstream side to the downstream side at a position where the surface of the slab 1 is impacted, it is desirable for the reduction ratio to be 0.5-2.5 mm per meter of length in the direction of casting, where the solid fraction at center in the direction of thickness f s of the slab 1 is 0.1-0.9.
  • vibrations due to impact when subjecting the slab 1 to soft reduction, vibrations due to impact can be sufficiently propagated to the interior of the slab 1, by applying to the slab 1 impact vibration which satisfies the optimal impact conditions, thereby making it possible to achieve an even greater segregation decreasing effect.
  • An impact device such as that shown in FIG. 1 was installed in two pairs of pinch rolls in the direction of casting.
  • High carbon steel with a composition shown in Table 2 below was cast into blooms or slabs. The size was 250-310 mm thick and 425 mm or 2,300 mm wide. The casting speed was set at 0.70 m/min or 0.75 m/min.
  • TABLE 2 [C] [Si] [Mn] [P] [S] Residue High carbon steel 0.26-1.00 0.02-2.00 0.10-3.00 0.08 or less 0.02 or less Fe and impurities (Unit: Mass %)
  • the impact conditions were set such that the block weight was 450 kg and the impact speed was about 0.47 m/sec or 0.71 m/sec (the impact energy was 50 J or 114 J).
  • the shape of the surface of the block attached to the front end of the impact device that comes into contact with the bloom or the slab had a width in the direction of slab thickness of about 200 mm, and a length in the direction of casting of about 1,100 mm.
  • the carbon concentration was analyzed by removing chips from 26 sites at positions corresponding to the center in the direction of slab thickness, with a drill blade 2 mm in diameter at a pitch of 7 mm.
  • the resulting carbon concentration was divided by the carbon concentration of molten steel in the ladle, resulting in the ratio C/C0, and the maximum values for this ratio (maximum center segregation ratio) were obtained.
  • test conditions are given in Table 3 below. This test was performed on: an inventive example (high carbon steel C) to which impact vibration was applied between pinch rolls using the impact-vibration equipment of the present invention; a comparative example (high carbon steel B) to which impact vibration was applied at a segment, using impact-vibration equipment disclosed in Japanese Patent Application No. 2006-53057 ; and a comparative example (high carbon steel A) produced without applying impact vibration.
  • test results are shown in FIG. 6 .
  • the maximum center segregation ratio was a favorable 1.15 or less in all cases.
  • the maximum center segregation ratio exceeded 1.15, as the slab width increased.
  • a maximum center segregation ratio of 1.15 or less was considered good, and results exceeding that value were considered poor.
  • an air cylinder was used as the impact device 6.
  • any method may be used, as long as it is able to drive the block 3. Examples include a hydraulic cylinder, a method using a leaned cam, or a method using a spring.
  • the present invention can be applied not only to high carbon steel slabs as described in the examples, but also to continuous casting of other types of steel, such as medium carbon steel slabs and low carbon steel slabs.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Continuous Casting (AREA)
EP08791358.8A 2007-08-08 2008-07-18 Hammering vibrator in continuous casting Not-in-force EP2174734B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL08791358T PL2174734T3 (pl) 2007-08-08 2008-07-18 Wibrator uderzeniowy w procesie odlewania ciągłego

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2007207039 2007-08-08
PCT/JP2008/063049 WO2009019969A1 (ja) 2007-08-08 2008-07-18 連続鋳造時の打撃振動装置

Publications (3)

Publication Number Publication Date
EP2174734A1 EP2174734A1 (en) 2010-04-14
EP2174734A4 EP2174734A4 (en) 2017-02-22
EP2174734B1 true EP2174734B1 (en) 2018-08-22

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EP08791358.8A Not-in-force EP2174734B1 (en) 2007-08-08 2008-07-18 Hammering vibrator in continuous casting

Country Status (7)

Country Link
EP (1) EP2174734B1 (zh)
JP (1) JP5029694B2 (zh)
KR (1) KR101183420B1 (zh)
CN (1) CN101778682B (zh)
ES (1) ES2688943T3 (zh)
PL (1) PL2174734T3 (zh)
WO (1) WO2009019969A1 (zh)

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RU2511130C2 (ru) * 2012-07-24 2014-04-10 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Липецкий государственный технический университет" (ЛГТУ) Способ обжатия непрерывнолитой сортовой заготовки в жидко-твердом состоянии
CN103464704A (zh) * 2013-09-11 2013-12-25 钢铁研究总院 一种连铸坯用的震动锤装置及使用方法
CN109689247B (zh) * 2016-09-21 2021-12-10 杰富意钢铁株式会社 钢的连续铸造方法
WO2019167855A1 (ja) 2018-03-02 2019-09-06 Ｊｆｅスチール株式会社 鋼の連続鋳造方法
CN108500226A (zh) * 2018-03-29 2018-09-07 马鞍山钢铁股份有限公司 一种抑制柱状晶生长的连铸凝固过程控制方法
CN108526423A (zh) * 2018-03-29 2018-09-14 马鞍山钢铁股份有限公司 一种改善连铸过程凝固中后期固液两相区流动性的方法、铸坯质量的控制方法及装置
DE102019206199A1 (de) * 2019-04-30 2020-11-05 Thyssenkrupp Steel Europe Ag Stranggießeinrichtung zur Beeinflussung eines erstarrenden Strangs, insbesondere einer erstarrenden Bramme, und Verfahren zur Beeinflussung eines erstarrenden Strangs
CN110722120A (zh) * 2019-11-05 2020-01-24 中达连铸技术国家工程研究中心有限责任公司 一种带偏心旋转件的连铸振动支撑辊及其设备
CN110695329A (zh) * 2019-11-13 2020-01-17 中达连铸技术国家工程研究中心有限责任公司 一种具有内置偏心旋转机构的连铸振动支撑辊

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Publication number Publication date
KR20100033520A (ko) 2010-03-30
JP5029694B2 (ja) 2012-09-19
WO2009019969A1 (ja) 2009-02-12
ES2688943T3 (es) 2018-11-07
CN101778682B (zh) 2012-11-28
EP2174734A1 (en) 2010-04-14
EP2174734A4 (en) 2017-02-22
PL2174734T3 (pl) 2019-01-31
CN101778682A (zh) 2010-07-14
JPWO2009019969A1 (ja) 2010-10-28
KR101183420B1 (ko) 2012-09-14

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