CN101658905A - Methods for preparing continuous casting crystallizer copper plate surface modified W-Cu alloy layer and application thereof - Google Patents

Methods for preparing continuous casting crystallizer copper plate surface modified W-Cu alloy layer and application thereof Download PDF

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CN101658905A
CN101658905A CN200910308416A CN200910308416A CN101658905A CN 101658905 A CN101658905 A CN 101658905A CN 200910308416 A CN200910308416 A CN 200910308416A CN 200910308416 A CN200910308416 A CN 200910308416A CN 101658905 A CN101658905 A CN 101658905A
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alloy
copper
infiltration
powder
crystallizer
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CN101658905B (en
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马海涛
杨朋
王来
黄文平
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Dalian University of Technology
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Dalian University of Technology
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Abstract

The invention relates to methods for preparing a continuous casting crystallizer copper plate surface modified W-Cu alloy layer and the application thereof, and the W-Cu alloy layer is especially applicable to a steel and nonferrous metal continuous casting crystallizer copper plate modified layer. The modified layer comprises the components by weight percent: 30.0-70.0% of W, 23.0-69.65% of Cu, 0.1-2.0% of Ni, 0.05-2.0% of Ag and 0.2-3.0% of Co. The preparation methods comprise a. hot pressed sintering and b. infiltration method, wherein the hot pressed sintering is characterized by (1) evenly mixing the powder and hot pressed sintering for molding; (2) pouring molten copper on sintered W-Cu alloy or placing a copper plate on the W-Cu alloy, heating and leading copper to be molten and have infiltration together with the W-Cu alloy, and cooling and then obtaining the copper plate product provided with the W-Cu alloy modified layer; and the infiltration method is characterized by (1) evenly mixing the powder, cold pressing into infiltration framework and high temperature sintering; (2) pouring the molten copper on the W-Cu framework for infiltration or placing the copper plate on the W-Cu alloy framework, heating and leading copper to be molten and have infiltration together with the W-Cu alloy framework, and then cooling. The W-Cu alloy layer has the advantages of greatly improving the production efficiency of a crystallizer, solving the problem of electroplating pollution of the crystallizer copper plate and being a high-efficiency and environment-friendly crystallizer surface modification method.

Description

The preparation method of continuous casting crystallizer copper plate surface modified W-Cu alloy-layer and application thereof
Technical field
The present invention relates to a kind of crystallizer copper plate surface modified layer, be applicable to that the metallurgy industry continuous casting uses crystallizer, be particularly useful for iron and steel, non-ferrous metal continuous casting copper plate of crystallizer modified layer.
Background technology
Continuous casting is the abbreviation of continuous casting.Compare with conventional method, continuous casting technology has and significantly improves recovery rate of iron and slab quality, significant advantages such as energy savings.
The idiographic flow (is example with the continuous casting steel machine) of continuous casting is: molten steel pulls straight from the outlet of crystallizer below behind the duricrust that congeals into constantly by water mold, through the water spray cooling, is cut into the foundry technology process of blank after all solidifying.
From the eighties in last century, continuous casting technology is progressively perfect as dominant technology, and mainly produces steel state all over the world and significantly used, and to the early 1990s in last century, each mainly produces the world steel state and realized the continuous casting ratio more than 90%.Chinese then after reform and opening-up, just really begun digestion and transplanting to external continuous casting technology; The continuous casting ratio of China only is 30% to the early 1990s.Through the fast development in more than 10 years, China not only output of steel was sure to occupy first place, the world, and continuous casting ratio also enters the leading ranks that the world produces steel country, and a lot of emphasis iron and steel enterprises have reached 100% continuous casting ratio, have realized the complete continuous casting production of crude steel.
Continuous cast mold is conticaster " head ", and its importance is called " heart " of conticaster.Crystallizer is that a high efficiency heat exchanger, molten steel solidification form device, molten steel field trash clarifier and casting billet surface defective controller.So continuous cast mold is the critical equipment in the continuous casting installation for casting, cost an arm and a leg, its design, manufacturing, operating procedure play conclusive effect to the output of conticaster, the quality of strand and the safety of production.
Copper plate of crystallizer is the working face of crystallizer, directly contacts with molten steel, and there is bosh at the copper coin back side.During work, bosh is taken away the heat of molten steel by water-cooled, with molten steel solidification.The steel billet that solidifies is pulled out from crystallizer by dummy bar, realizes continuous production.In whole process, copper plate of crystallizer not only bears high temperature, and is subjected to the friction of steel billet, molten steel covering slag, its working environment very severe.Often throwing makes the crystallizer serious wear, changes frequently, not only reduces production efficiency, and consumes a large amount of crystallizers.In order to adapt to high efficiency continuous casting development, the copper plate of crystallizer surface must have high rigidity, high-wearing feature, good thermal conductivity and thermophilic corrosion-resistance ability.And copper coin itself does not have wearability and elevated temperature corrosion resistant.Must carry out surface modification.What domestic and international application was maximum at present is at copper plate of crystallizer electroplating surface Cr, Ni, Ni-Co, coating such as Ni Crescent e, Co-Ni, improves the wearability and the corrosion resistance of copper coin.Electroplate the copper plate of crystallizer of modified layer and widely apply aborning,, also have significant disadvantages though this technology can significantly improve the wearability of copper coin:
(1) thermal conductivity factor of coating is lower, only is 1/5 of copper coin generally, has played the effect of thermal resistance at crystallizer surface, has reduced the cooling effectiveness of molten steel;
(2) coating is different with the thermal coefficient of expansion of copper coin, very easily brings out the crackle between coating and copper coin, causes plating exfoliation, so the life-span of crystallizer plating copper coin is generally not high, has directly influenced the efficient that continuous casting is produced.
(3) environmental hazard of plating production is bigger, and a lot of developed countries arrive the such developing country of China with such industry transfer one after another.
The present invention is conceived to just that present continuous casting crystallizer copper plate coating is shorter service life, and the thermal efficiency is low, and environmental hazard is big to wait the present situation of restriction continuous casting production efficiency to propose.
Summary of the invention
Purpose of the present invention and task are that will to overcome the continuous casting crystallizer copper plate modified layer wearability that prior art exists relatively poor, heat transfer efficiency is low, coating easily peels off, electroplate the modified layer production present situation huge to environmental hazard, and provide a kind of and can increase substantially continuous casting crystallizer copper plate surface modified layer wearability, thermal conductivity, outstanding with copper coin matrix bond ability, the production technology and the method for the crystallizer copper plate surface modified layer of environmental protection.
The preparation method of the continuous casting crystallizer copper plate surface modified W-Cu alloy-layer that the present invention proposes and the technical scheme of application thereof are: a kind of weight percent proportioning wt% of continuous casting crystallizer copper plate surface modified W-Cu alloy-layer composition is: W:30.0~70.0%, Cu:23.0~69.65%, Ni:0.1~2.0%, Ag:0.05~2.0%, Co:0.2~3.0%.Wherein, optimum weight per distribution ratio wt% is: W:60%, Cu:38.2%, Ni:0.3%, Ag:0.5%, Co:1.0%.
The preparation method of described continuous casting crystallizer copper plate surface modified W-Cu alloy-layer adopts vacuum heating-press sintering, protective atmosphere hot pressed sintering, vacuum infiltration or protective atmosphere infiltration.Step when described preparation method adopts vacuum heating-press sintering or protective atmosphere hot pressed sintering is as follows:
(1) by the percentage by weight of its each composition, with the W powder, the Cu powder, the Ni powder, the Ag powder, weighing is good respectively for the Co powder, mixes, and is cold-pressed into the block of required form,
(2) the W-Cu block of compression moulding is put into hot press and carries out hot pressed sintering,
(3) cast directly over the fusing of required block copper on the W-Cu alloy that sinters or the copper coin plate is placed on the W-Cu alloy that sinters; heating dissolves copper coin above the fusing point of copper in vacuum or the protective atmosphere; make copper liquid and W-Cu alloy carry out infiltration and combine, cooling at last promptly obtains the copper coin product of W-Cu alloy surface modifying layer.
Or the step when described preparation method adopts vacuum infiltration or protective atmosphere infiltration is as follows:
(1) by the percentage by weight of its each composition, with its W powder, the Cu powder, the Ni powder, the Ag powder, weighing is good respectively for the Co powder, mixes, and is cold-pressed into the infiltration skeleton block of required form,
(2) the infiltration block of compression moulding is put into vacuum or protective atmosphere sinters the infiltration skeleton into,
(3) fusing of required block copper is cast directly on the W-Cu alloy skeleton that sinters infiltration or the copper coin plate placed on the W-Cu alloy skeleton that sinters; heating makes the copper coin fusing above the fusing point of copper in vacuum or the protective atmosphere; make copper liquid and W-Cu alloy skeleton carry out infiltration, cooling at last promptly obtains the copper coin product of W-Cu alloy surface modifying layer.
Wherein, optimised process is the infiltration method preparation, and its concrete technology is:
(1) the preparation porosity of colding pressing is 50% skeleton;
(2) at environmental protection atmosphere 95%N 2+ 5%H 2In (percent by volume), 900 ℃ of sintering 2 hours;
(3) at environmental protection atmosphere 95%N 2+ 5%H 2In (percent by volume), 1250 ℃ of infiltration copper 2 hours.
The W-Cu alloy-layer that utilizes described preparation method to obtain is applied to the metallurgy industry continuous casting and uses crystallizer, is particularly useful for iron and steel and non-ferrous metal continuous casting copper plate of crystallizer modified layer.
The prepared selected W-Cu alloy of crystallizer copper plate surface modified layer of the present invention has high wearability, electric conductivity and thermal conductivity.W-Cu alloy alloy is typical soft matrix+hard particles reinforcing material, and it is the wearability height not only, and stress be difficult for to take place concentrates the cracking that causes and Problem of Failure such as peel off.W-Cu (contains Cu40%, percentage by weight) the room temperature thermal conductivity of sintered alloy is about 200W/ (mk), the room temperature thermal conductivity of the Cu-Ag alloy material that crystallizer is commonly used is about 377W/ (mk), the room temperature thermal conductivity of Ni-Co coating material is 75~84W/ (mk), the room temperature thermal conductivity of Ni-Fe coating material is 63~88W/ (mk), and the room temperature thermal conductivity of Co-Ni coating material is 80~84W/ (mk).More as can be known, the thermal conductivity factor of W-Cu alloy is higher, and more near the thermal conductivity factor of copper plate of crystallizer, this has just guaranteed the heat transfer efficiency of copper coin modified layer, can improve the cooling velocity of molten iron in the crystallizer greatly, improves and walks the steel amount, and then enhance productivity.Cu and copper coin in the modified layer fuse into one in preparation process, are metallurgical binding, and thermal coefficient of expansion is close, have avoided the flaky shortcoming of modified layer; Hot pressing and infiltration process environmental pollution are little.
The invention has the beneficial effects as follows: utilize the continuous casting crystallizer copper plate surface modified W-Cu alloy-layer of powder metallurgic method preparation to have following advantage:
(1) good wearability;
(2) good thermal conductivity;
(3) powder metallurgy modified layer and copper coin are metallurgical binding, and adhesion is strong, and be incrust;
(4) production technology green safety environmental protection.
Therefore, prepare copper-plate surface modifying W-Cu layer and surface electrical coating ratio with powder metallurgic method, conticaster crystallizer can improve more than 2 times service life.
The specific embodiment
The preparation method of continuous casting crystallizer copper plate surface modified W-Cu alloy-layer proposed by the invention and the concrete process program of application thereof are provided in detail by following examples.
Embodiment 1
Certain steel mill's continuous casting square billet copper plate of crystallizer adopts the technology of plating inner surface Ni, and one time steel-passing amount can only reach 50,000 tons, and the Ni coating of inner surface has just rubbed to peel off and caused scrapping.The powder metallurgic method of utilizing the present invention to develop prepares the copper plate of crystallizer of surface reforming layer, has obtained the effect of 250,000 tons of steel-passing amounts, and product quality is outstanding.
Each composition branch that the powder metallurgic method of using prepares crystallizer copper plate surface modified W-Cu alloy-layer sees Table 1.
The composition of the crystallizer copper plate surface modified W-Cu alloy-layer of table 1 (percentage by weight, wt.%)
Composition Scheme one Scheme two Scheme three Scheme four Scheme five Scheme six Scheme seven Scheme eight Scheme nine
??W ??30.0 ??35.0 ??40.0 ??45.0 ??50.0 ??55.0 ??60.0 ??65.0 ??70.0.
??Cu ??67.4 ??61.2 ??56.7 ??52.4 ??48.0 ??42.6 ??37.0 ??30.7 ??27.2
??Ni ??1.40 ??1.60 ??0.25 ??0.30 ??0.10 ??0.60 ??0.80 ??2.00 ??1.20
??Ag ??0.7 ??2.0 ??0.05 ??0.3 ??0.6 ??0.8 ??1.4 ??1.2 ??0.9
??Co ??0.5 ??0.2 ??3.0 ??2.0 ??1.3 ??1.0 ??0.8 ??1.1 ??0.7
Preparation technology: the first step is pressed its percentage by weight, with the W powder, and the Cu powder, the Ni powder, the Ag powder, the weighing of Co powder is good, mixes, and is cold-pressed into the thin plate of thick 5mm; Second step was put into hot press with the cold moudling thin plate, carried out hot pressed sintering under 1300 ℃ in vacuum and 20Mpa pressure condition; The 3rd the step will be unidimensional with the W-Cu latten Cu-Cr-Zr alloy (Cr:1.0%, Zr:0.15%, percentage by weight) plate places on the W-Cu latten that sinters, 1350 ℃ of vacuum heat-preservings 1 hour, make the copper alloy of fusing carry out infiltration with the W-Cu alloy and combine, cooling at last promptly obtains the copper coin product of W-Cu alloy surface modifying layer.Further during machining, the minimum reservation of copper coin surface W-Cu modified layer 3mm carries out production application.
Embodiment 2
Certain steel mill's continuous casting steel billet copper plate of crystallizer adopts the technology of plating inner surface Ni-Fe, and one time steel-passing amount can only reach 100,000 tons, and the Ni-Fe coating of inner surface has just rubbed to peel off and caused scrapping.The powder metallurgic method of utilizing the present invention to develop prepares the copper plate of crystallizer of surface reforming layer, has obtained the effect of 250,000 tons of steel-passing amounts, and product quality is outstanding.
Each composition branch that the powder metallurgic method of using prepares crystallizer copper plate surface modified W-Cu alloy-layer sees Table 2.
The composition of the crystallizer copper plate surface modified W-Cu alloy-layer of table 2 (percentage by weight, wt.%)
Composition Scheme one Scheme two Scheme three Scheme four Scheme five Scheme six Scheme seven Scheme eight Scheme nine
??W ??30.0 ??35.0 ??40.0 ??45.0 ??50.0 ??55.0 ??60.0 ??65.0 ??70.0.
??Cu ??67.4 ??61.2 ??56.7 ??52.4 ??48.0 ??42.6 ??37.0 ??30.7 ??27.2
??Ni ??1.40 ??1.60 ??0.25 ??0.30 ??0.10 ??0.60 ??0.80 ??2.00 ??1.20
??Ag ??0.7 ??2.0 ??0.05 ??0.3 ??0.6 ??0.8 ??1.4 ??1.2 ??0.9
??Co ??0.5 ??0.2 ??3.0 ??2.0 ??1.3 ??1.0 ??0.8 ??1.1 ??0.7
Preparation technology: the first step is pressed its percentage by weight, with the W powder, and the Cu powder, the Ni powder, the Ag powder, the weighing of Co powder is good, mixes, and is cold-pressed into the infiltration skeleton of thick 5mm; Second step was put into sintering furnace with cold moudling infiltration skeleton, under the Ar protection, carried out sintering under 1300 ℃ of conditions; The 3rd step will place on the W-Cu alloy skeleton with unidimensional Cu-Ni-Be alloy (Ni:1.5%, Be:0.4%, the percentage by weight) plate of W-Cu alloy infiltration skeleton, at 1350 ℃, and 95%N 2+ 5%H 2Insulation is 1 hour under (percent by volume) atmosphere, makes the copper alloy of fusing carry out infiltration with W-Cu alloy skeleton and combines, and cools off the copper coin product that promptly obtains W-Cu alloy surface modifying layer at last.Further during machining, the minimum reservation of copper coin surface W-Cu modified layer 3mm carries out production application.
Embodiment 3
Certain steel mill's continuous cast round billets copper plate of crystallizer adopts the technology of plating inner surface Ni-Co, and one time steel-passing amount can only reach 150,000 tons, and the Ni-Co coating of inner surface has just rubbed to peel off and caused scrapping.The powder metallurgic method of utilizing the present invention to develop prepares the copper plate of crystallizer of surface reforming layer, has obtained the effect of 250,000 tons of steel-passing amounts, and product quality is outstanding.
Each composition branch that the powder metallurgic method of using prepares crystallizer copper plate surface modified W-Cu alloy-layer sees Table 3.
The composition of the crystallizer copper plate surface modified W-Cu alloy-layer of table 3 (percentage by weight, wt.%)
Composition Scheme one Scheme two Scheme three Scheme four Scheme five
??W ??30.0 ??40.0 ??50.0 ??60.0 ??70.0.
??Cu ??67.4 ??56.7 ??48.0 ??37.0 ??27.2
??Ni ??1.40 ??0.25 ??0.10 ??0.80 ??1.20
??Ag ??0.7 ??0.05 ??0.6 ??1.4 ??0.9
??Co ??0.5 ??3.0 ??1.3 ??0.8 ??0.7
Preparation technology: the first step is pressed its percentage by weight, with the W powder, and the Cu powder, the Ni powder, the Ag powder, the weighing of Co powder is good, mixes, and is cold-pressed into the cylindrical shape infiltration skeleton of thick 5mm; Second step was put into sintering furnace with cold moudling infiltration skeleton, under the Ar protection, carried out sintering under 1300 ℃ of conditions; The 3rd step was put into the infiltration mould with W-Cu alloy infiltration skeleton, 1350 ℃ of fusion Cu-Ag alloys (Ag:0.1%, P:0.008%, percentage by weight) is cast in the infiltration mould, and at 1350 ℃, 95%N 2+ 5%H 2Insulation is 1 hour under (percent by volume) atmosphere, makes copper alloy carry out infiltration with W-Cu alloy skeleton and combines, and cooling at last promptly obtains the copper pipe product that inner surface has W-Cu alloy surface modifying layer.Further during machining, the minimum reservation of copper pipe inner surface W-Cu modified layer 3mm carries out production application.

Claims (3)

1. continuous casting crystallizer copper plate surface modified W-Cu alloy-layer, it is characterized in that: the weight percent proportioning wt% of described crystallizer copper plate surface modified W-Cu alloy-layer composition is: W:30.0~70.0%, Cu:23.0~69.65%, Ni:0.1~2.0%, Ag:0.05~2.0%, Co:0.2~3.0%.
2. prepare the preparation method of the described continuous casting crystallizer copper plate surface modified W-Cu alloy-layer of claim 1, this preparation method adopts vacuum heating-press sintering, protective atmosphere hot pressed sintering, vacuum infiltration or protective atmosphere infiltration; It is characterized in that: the step when described preparation method adopts vacuum heating-press sintering or protective atmosphere hot pressed sintering is as follows:
(1) by the percentage by weight of its each composition, with the W powder, the Cu powder, the Ni powder, the Ag powder, weighing is good respectively for the Co powder, mixes, and is cold-pressed into the block of required form,
(2) the W-Cu block of compression moulding is put into hot press and carries out hot pressed sintering,
(3) cast directly over the fusing of required block copper on the W-Cu alloy that sinters or the copper coin plate is placed on the W-Cu alloy that sinters, heating dissolves copper coin above the fusing point of copper in vacuum or the protective atmosphere, make copper liquid and W-Cu alloy carry out infiltration and combine, cooling at last promptly obtains the copper coin product of W-Cu alloy surface modifying layer;
Or the step when described preparation method adopts vacuum infiltration or protective atmosphere infiltration is as follows:
(1) by the percentage by weight of its each composition, with its W powder, the Cu powder, the Ni powder, the Ag powder, weighing is good respectively for the Co powder, mixes, and is cold-pressed into the infiltration skeleton block of required form,
(2) the infiltration block of compression moulding is put into vacuum or protective atmosphere sinters the infiltration skeleton into,
(3) fusing of required block copper is cast directly on the W-Cu alloy skeleton that sinters infiltration or the copper coin plate placed on the W-Cu alloy skeleton that sinters; heating makes the copper coin fusing above the fusing point of copper in vacuum or the protective atmosphere; make copper liquid and W-Cu alloy skeleton carry out infiltration, cooling at last promptly obtains the copper coin product of W-Cu alloy surface modifying layer.
3. utilize the application of the W-Cu alloy-layer that the described preparation method of claim 2 obtains, it is characterized in that: described W-Cu alloy-layer is applied to the metallurgy industry continuous casting and uses crystallizer, is particularly useful for iron and steel and non-ferrous metal continuous casting copper plate of crystallizer modified layer.
CN2009103084169A 2009-10-16 2009-10-16 Methods for preparing continuous casting crystallizer copper plate surface modified W-Cu alloy layer and application thereof Expired - Fee Related CN101658905B (en)

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CN102031411A (en) * 2010-12-01 2011-04-27 武汉理工大学 Method for preparing compact W-Cu composite material at low temperature
CN102237204A (en) * 2010-04-27 2011-11-09 上海电科电工材料有限公司 High-voltage tungsten-base composite contact material and method for making same
CN103911637A (en) * 2014-03-28 2014-07-09 马鞍山马钢表面工程技术有限公司 Ni-Co-W alloy electroplating solution for working surface of copper plate of continuous casting crystallizer and preparation method of Ni-Co-W alloy electroplating solution
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CN102237204A (en) * 2010-04-27 2011-11-09 上海电科电工材料有限公司 High-voltage tungsten-base composite contact material and method for making same
CN102031411B (en) * 2010-12-01 2012-07-04 武汉理工大学 Method for preparing compact W-Cu composite material at low temperature
CN102031411A (en) * 2010-12-01 2011-04-27 武汉理工大学 Method for preparing compact W-Cu composite material at low temperature
CN103911637A (en) * 2014-03-28 2014-07-09 马鞍山马钢表面工程技术有限公司 Ni-Co-W alloy electroplating solution for working surface of copper plate of continuous casting crystallizer and preparation method of Ni-Co-W alloy electroplating solution
CN103911637B (en) * 2014-03-28 2016-08-17 马鞍山马钢表面工程技术有限公司 Copper plate working surface of continuously casting crystallizer Ni-Co-W alloy plating liquid and preparation method thereof
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CN107052350A (en) * 2017-06-16 2017-08-18 大连理工大学 A kind of method for connecting tungsten material and copper material
CN111417477A (en) * 2018-02-13 2020-07-14 福田金属箔粉工业株式会社 Copper-based powder for infiltration
CN109529861A (en) * 2018-12-12 2019-03-29 万华化学集团股份有限公司 A kind of skeletal Co catalysts and its preparation method and application
CN109529861B (en) * 2018-12-12 2021-07-23 万华化学集团股份有限公司 Skeletal cobalt catalyst and preparation method and application thereof
CN113789456A (en) * 2021-09-17 2021-12-14 中国科学院空天信息创新研究院 Method and device for soaking copper in tungsten sponge matrix
CN113789456B (en) * 2021-09-17 2022-06-10 中国科学院空天信息创新研究院 Method and device for soaking copper in tungsten sponge matrix
CN114231812A (en) * 2021-12-21 2022-03-25 合肥工业大学 AlN-W-Cu composite material and preparation method thereof
CN114628179A (en) * 2022-04-12 2022-06-14 西安西电开关电气有限公司 Method for connecting copper-tungsten alloy and copper alloy
CN114628179B (en) * 2022-04-12 2023-09-29 西安西电开关电气有限公司 Copper-tungsten alloy and copper alloy connecting method
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