CN104232967A - Method for preparing low binder phase wolfram carbide hard alloy - Google Patents
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Abstract
The invention provides a method for preparing a low binder phase wolfram carbide hard alloy. The method is the preparation of wolfram carbide-cobalt composite powder coated with low content of cobalt through electroless plating by sintering the powder in a spark plasma sintering furnace and includes the steps of vacuumizing to a vacuum degree of over 8Pa, pressurizing to 50MPa, heating to 1500 DEG C-1700 DEG C, depressurizing after incubation, and cooling to obtain low binder phase wolfram carbide. According to the method for preparing the low binder phase tungsten carbide hard alloy, the wolfram carbide-cobalt composite powder with low cobalt content is prepared through electroless plating, the preparation period of the powder is short, and cobalt in the form of a thin film is coated on the surface of wolfram carbide particles to be uniformly distributed and avoid local gathering of cobalt; the spark plasma sintering is used, and cobalt in liquid phase exists among all wolfram carbide particles, the bonding strength between particles is enhanced, the toughness of the alloy is improved, and the obtained hard alloy is good in material performance.
Description
Technical field
The present invention relates to Wimet technical field, specifically, relate to a kind of preparation method of few Binder Phase carboloy.
Background technology
WC-Co hard alloy has higher intensity, hardness, toughness and excellent wear resistance and corrosion resistance nature, has a wide range of applications in the fields such as metal cutting process, mine probing and wear-resisting spare part.Wherein, Co has the function promoting the full densification of sintering cemented carbide as Binder Phase, and give the higher toughness of alloy and intensity, but, the raising of Co content, low-alloyed corrosion resistance nature, resistance to elevated temperatures, wear resisting property and thermal conductivity can be fallen, thus limit its application in some field.Compared with common WC-Co hard alloy, few Binder Phase carboloy had both possessed " two high " mechanical property of high strength and high hardness specific to ultra-fine cemented carbide, there is again excellent wear resistance and corrosion resistance, become an important development direction of high-anti-friction hard alloy.
In the prior art, the research of the few Binder Phase WC Wimet of preparation is mainly concentrated in the following areas: one is prepare the pure WC Wimet not adding any binding agent; Two is WC Wimet that a small amount of Co is added in preparation.But mainly there are the following problems for the preparation process of few Binder Phase WC Wimet: in the process of the pure WC Wimet of preparation, because sintering temperature is too high and sintering time is longer, thus Wimet is difficult to full densification, and toughness is poor; And preparation adds the WC Wimet of a small amount of Co mainly through high energy ball mill method in prior art, the powder preparation cycle of the method is long, powder mixing is uneven, Co component segregation, thus cause WC grain local anomaly in sintering process to be grown up, uneven microstructure, make alloy material mechanical property unstable, impact uses.Therefore, the preparation method of few Binder Phase carboloy that a kind of Binder Phase of exploitation is evenly distributed is badly in need of.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, provide a kind of preparation method of few Binder Phase carboloy, carboloy Binder Phase tissue distribution prepared by the method is even, has good toughness.To achieve these goals, the present invention adopts following technical scheme:
A preparation method for few Binder Phase carboloy, comprises the steps:
Step one: WC powder is added in chemical activation liquid, ultrasonic agitation process under room temperature, separation chemistry activation solution after quiescent settling, then use washed with de-ionized water WC powder;
Step 2: WC powder step one obtained is added in chemical plating fluid, in 70 ~ 85 DEG C of water-bath insulations to there being bubble to produce, then proceed to 40 ~ 60 DEG C of ultrasonic ponds and carry out ultrasonic agitation electroless cobalt plating, separation chemistry plating solution after quiescent settling, use washed with de-ionized water powder, after drying, obtain low cobalt content WC-Co composite powder body;
Step 3: low cobalt content WC-Co composite powder body step 2 obtained is placed in discharge plasma sintering system, vacuumize and make vacuum tightness reach more than 8Pa, be forced into 50MPa, be warming up to 1500 ~ 1700 DEG C of insulations, after release cooling, obtain few Binder Phase carboloy.
Preferably, the grain-size of described WC powder is 0.2 ~ 0.4um.
Preferably, the ultrasonic frequency for ultrasonic agitation is 40KHz, and ultrasonic power is 300 ~ 400W.
Preferably, described chemical activation liquid comprises following compositions:
Preferably, the loading capacity of WC powder by 1kg/L is added in chemical activation liquid.
Preferably, described chemical plating fluid comprises following component:
Wherein, the pH value of described chemical plating fluid is 9 ~ 11.
Preferably, WC powder step one obtained is added in chemical plating fluid by the loading capacity of 150g/L ~ 1500g/L.
Preferably, in described step 2, drying is specially:
By powder freeze-day with constant temperature 6h at 60 ~ 80 DEG C.
Preferably, the mass percent of the Co comprised in described WC-Co composite powder body adopts Shimadzu (Shimadzu) high precision (× 10
-5g) analytical balance weighs and measures.
Preferably, the speed heated up in described step 3 is 200 DEG C/min, is 5 minutes in the time of 1500 ~ 1700 DEG C of insulations.
The invention provides a kind of preparation method of few Binder Phase carboloy, comprising: WC powder is added in chemical activation liquid, ultrasonic agitation process under room temperature, separation chemistry activation solution after quiescent settling, then use washed with de-ionized water WC powder; WC powder is added in chemical plating fluid, in 70 ~ 85 DEG C of water-bath insulations to there being bubble to produce, then proceed to 40 ~ 60 DEG C of ultrasonic ponds and carry out ultrasonic agitation electroless cobalt plating, separation chemistry plating solution after quiescent settling, use washed with de-ionized water powder, low cobalt content WC-Co composite powder body is obtained after drying, then discharge plasma sintering system is placed in, vacuumize and make vacuum tightness reach more than 8Pa, be forced into 50MPa, be warming up to 1500 ~ 1700 DEG C of insulations, after release cooling, obtain few Binder Phase ultrafine tungsten carbide Wimet.Compared with prior art, the present invention adopts electroless plating method to prepare low cobalt content WC-Co composite powder body, and powder preparation cycle is short, and Co is coated on WC particle surface with the form of knitting knitting wool film, is evenly distributed, and there is not Local C o enrichment phenomenon; In SPS discharge plasma sintering process, owing to there is liquid phase Co between WC particle, thus strengthen intergranular strength of joint, improve the toughness of alloy, ensure that few Binder Phase carboloy of preparation has good performance.
Accompanying drawing explanation
Fig. 1 is the original powder surface stereoscan photograph of WC;
Fig. 2 is the original powder transmission electron microscope photo of WC: (a) WC particle transmission electron microscope bright field image; The selected area electron diffraction figure of (b) [1-210] tape spool; C high resolution photo that () is corresponding;
Fig. 3 is the stereoscan photograph of the pretreated WC powder surface of chemical activation;
Fig. 4 is chemical activation pretreated WC powder transmission electron microscope photo: (a) WC particle transmission electron microscope bright field image; The selected area electron diffraction figure of (b) [1-210] tape spool; C transmission electron microscope macrograph that () is corresponding; The high resolution photo of a-quadrant in (d) figure (c); The high resolution photo in B region in (e) figure (c); The high resolution photo in C region in (f) figure (c);
Fig. 5 is WC-Co composite powder surface stereoscan photograph.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
The embodiment of the invention discloses a kind of preparation method of few Binder Phase carboloy, comprise the steps:
Step one: WC powder is added in chemical activation liquid, ultrasonic agitation process under room temperature, separation chemistry activation solution after quiescent settling, then use washed with de-ionized water WC powder;
Step 2: WC powder step one obtained is added in chemical plating fluid, in 70 ~ 85 DEG C of water-bath insulations to there being bubble to produce, then proceed to 40 ~ 60 DEG C of ultrasonic ponds and carry out ultrasonic agitation electroless cobalt plating, separation chemistry plating solution after quiescent settling, use washed with de-ionized water powder, after drying, obtain low cobalt content WC-Co composite powder body;
Step 3: low cobalt content WC-Co composite powder body step 2 obtained is placed in discharge plasma sintering system, vacuumize and make vacuum tightness reach more than 8Pa, be forced into 50MPa, be warming up to 1500 ~ 1700 DEG C of insulations, after release cooling, obtain few Binder Phase carboloy.
According to the present invention, the grain-size of described WC powder is preferably 0.2 ~ 0.4um, is more preferably 0.2 ~ 0.3um, is more preferably 0.2um.Preferably, the loading capacity of WC powder by 1kg/L is added in chemical activation liquid.In step one and step 2, include the step of ultrasonic agitation, the ultrasonic frequency for ultrasonic agitation is preferably 40KHz, and ultrasonic power is preferably 300 ~ 400W, is more preferably 350 ~ 400W, is more preferably 400W.For described step one, the time of ultrasonic agitation is preferably 15 ~ 30min, is more preferably 20 ~ 30min.By with washed with de-ionized water WC powder, reach clean object, wash number is preferably 2 ~ 5 times, is more preferably 3 times.
According to the present invention, described chemical activation liquid preferably includes following compositions:
Preferred, described chemical activation liquid comprises following compositions:
Preferred, described chemical activation liquid comprises following compositions:
WC powder is placed in chemical activation liquid and carries out chemical activation pre-treatment, object is to make WC powder granule surface presentation micro-rough, produces manyly to have the defects such as active fault and dislocation, induces and carries out electroless cobalt plating at active surface and strengthen bonding force.
Then, WC powder step one obtained is added in chemical plating fluid, and described chemical plating fluid preferably includes following component:
Wherein, the pH value of described chemical plating fluid is 9 ~ 11.
It is preferred,
Wherein, the pH value of described chemical plating fluid is 10.
In mentioned component, rose vitriol is main salt, and inferior sodium phosphate is reductive agent, and trisodium citrate is complexing agent, and boric acid is stablizer.
Preferably, WC powder step one obtained is added in chemical plating fluid by the loading capacity of 150g/L ~ 1500g/L.In electroless cobalt plating reaction process, there is bubble to produce, treat that bubble-free produces electroless cobalt plating complete.In step 2, by reaching clean object with washed with de-ionized water powder, wash number is preferably 2 ~ 5 times, is more preferably 3 times.Described drying is specially: by powder freeze-day with constant temperature 6h at 60 ~ 80 DEG C.
In low cobalt content WC-Co composite powder body prepared by this step, the mass percent of cobalt contents≤1wt%, the Co that described WC-Co composite powder body comprises adopts Shimadzu (Shimadzu) high precision (× 10
-5g) analytical balance weighs and measures, be specially: taking original dry WC powder is W1, to this WC powder carry out electroless plating coated WC-Co composite powder body, weighing dry composite powder is W2, in composite granule, the quality of Co is W=W2-W1, then in composite granule, the mass percentage of Co is Co wt%=(W/W2) × 100%.
The speed heated up in described step 3 is 200 DEG C/min, is 5 minutes in the time of 1500 ~ 1700 DEG C of insulations.Described cooling step is specially: cool to less than 100 DEG C with the furnace, takes out air cooling.
The present invention adopts electroless plating method to prepare low cobalt content WC-Co composite powder body, and powder preparation cycle is short, and Co is coated on WC particle surface with the form of knitting knitting wool film, is evenly distributed, and there is not Local C o enrichment phenomenon; In SPS discharge plasma sintering process, owing to there is liquid phase Co between WC particle, thus strengthen intergranular strength of joint, improve the toughness of alloy, ensure that few Binder Phase carboloy of preparation.
Few Binder Phase carboloy prepared by the present invention, with conventional rigid alloy phase ratio, there is high hardness, excellent wear resistance, erosion resistance and antioxidant property, compared with existing few bonding phase cemented carbide, Binder Phase tissue distribution evenly, there is good toughness, thus greatly extend alloy in the work-ing life of traditional field, the substitute of other field traditional material can be become simultaneously.
In order to understand the present invention further, be described in detail to technical scheme provided by the invention below in conjunction with embodiment, protection scope of the present invention is not limited by the following examples.
The raw material that the embodiment of the present invention adopts and chemical reagent are commercial.
Embodiment 1
Step one: be that the WC powder of 0.2um joins chemical activation liquid (HF40ml/L of 40%, NH by the loading capacity of 1kg/L by average grain size
4f3g/L, the HNO of 65%
330ml/L, 36%HCl20ml/L) in, ultrasonic (40KHz, 400W) stir process 15 ~ 30min under room temperature; Separation chemistry activation solution after quiescent settling, then use the pretreated WC powder of washed with de-ionized water chemical activation 3 times;
Step 2: the pure WC powder not containing the chemical activation of Co that step one is obtained, be placed in SPS discharge plasma sintering system sintering: vacuumize and make vacuum tightness reach more than 8Pa, be forced into 50MPa, with the temperature rise rate to 1700 DEG C of 200 DEG C/min, be incubated 5 minutes, release, cools to less than 100 DEG C with the furnace and takes out air cooling.After measured, the relative density of this sample is 98.7%, and hardness is 2712HV10, and fracture toughness property is 8.4MPa ﹒ m
1/2.
Embodiment 2
Step one: be that the WC powder of 0.2um joins chemical activation liquid (HF40ml/L of 40%, NH by the loading capacity of 1kg/L by average grain size
4f3g/L, the HNO of 65%
330ml/L, 36%HCl20ml/L) in, ultrasonic (40KHz, 400W) stir process 15 ~ 30min under room temperature; Separation chemistry activation solution after quiescent settling, then use the pretreated WC powder of washed with de-ionized water chemical activation 3 times;
Step 2: pretreated for step one chemical activation WC powder is joined in chemical plating fluid by the loading capacity of 500g/L, prior to 70 ~ 85 DEG C of water-bath insulations, produce to there being bubble, proceed to 40 ~ 60 DEG C of ultrasonic ponds and carry out ultrasonic (40KHz, 400W) stir electroless cobalt plating, bubble is had to produce in reaction process, treat that bubble-free produces electroless cobalt plating complete, separation chemistry plating solution after quiescent settling, use washed with de-ionized water powder again 3 times, powder is put into the dry 6h of 60 ~ 80 DEG C of thermostatic drying chambers, according to Shimadzu high accuracy analysis balance, the weighing of powder before and after electroless plating is measured, the mass percentage obtaining Co in WC-Co composite powder body is 0.33wt%.
Described chemical plating fluid formula is as follows:
Step 3: cobalt contents step 2 obtained is the WC-Co composite powder body of 0.33wt%, be placed in SPS discharge plasma sintering system sintering: vacuumize and make vacuum tightness reach more than 8Pa, be forced into 50MPa, with the temperature rise rate to 1500 DEG C of 200 DEG C/min, be incubated 5 minutes, release, cools to less than 100 DEG C with the furnace and takes out air cooling.After measured, the relative density of this sample is 99.5%, and hardness is 2655HV10, and fracture toughness property is 9.2MPa ﹒ m
1/2.
Respectively surface sweeping Electronic Speculum and TEM (transmission electron microscope) analysis are carried out to original powder, the pretreated WC powder of chemical activation, scanning electron microscope analysis is carried out to WC-Co composite powder body.Wherein, Fig. 1 is the original powder surface stereoscan photograph of WC, and original powder surface is more smooth; Fig. 2 is the original powder transmission electron microscope photo of WC: (a) WC particle transmission electron microscope bright field image; The selected area electron diffraction figure of (b) [1-210] tape spool; C high resolution photo that () is corresponding.Transmission electron microscope results shows, in original WC, without microstructural flaws in most of particle (80%); Fig. 3 is the stereoscan photograph of the pretreated WC powder surface of chemical activation, and powder surface is micro-rough, has step dress defect; Fig. 4 is chemical activation pretreated WC powder transmission electron microscope photo: (a) WC particle transmission electron microscope bright field image; The selected area electron diffraction figure of (b) [1-210] tape spool; C transmission electron microscope macrograph that () is corresponding; The high resolution photo of a-quadrant in (d) figure (c); The high resolution photo in B region in (e) figure (c); The high resolution photo in C region in (f) figure (c).Transmission electron microscope results shows, in the pretreated sample of chemical activation, the particle of 70% is with microstructural flaws.Its defect type is fault and dislocation mainly.As can be seen from Fig. 4 (c), there is fault horizontal and vertical in a large number in this particle.Clearly can find out that in the enlarged view of correspondence longitudinal fault is for { slippage of 0001} face causes, and horizontal fault is for { slippage of 10-10} face causes.Fig. 5 is WC-Co composite powder surface stereoscan photograph, and Co is coated on WC particle surface with the form of knitting knitting wool film, is evenly distributed.
Embodiment 3
Step one: be that the WC powder of 0.2um joins chemical activation liquid (HF40ml/L of 40%, NH by the loading capacity of 1kg/L by average grain size
4f3g/L, the HNO of 65%
330ml/L, 36%HCl20ml/L) in, ultrasonic (40KHz, 400W) stir process 15 ~ 30min under room temperature; Separation chemistry activation solution after quiescent settling, then use the pretreated WC powder of washed with de-ionized water chemical activation 3 times;
Step 2: pretreated for step one chemical activation WC powder is joined in chemical plating fluid by the loading capacity of 250g/L, prior to 70 ~ 85 DEG C of water-bath insulations, produce to there being bubble, proceed to 40 ~ 60 DEG C of ultrasonic ponds and carry out ultrasonic (40KHz, 400W) stir electroless cobalt plating, bubble is had to produce in reaction process, treat that bubble-free produces electroless cobalt plating complete, separation chemistry plating solution after quiescent settling, use washed with de-ionized water powder again 3 times, powder is put into the dry 6h of 60 ~ 80 DEG C of thermostatic drying chambers, according to Shimadzu high accuracy analysis balance, the weighing of powder before and after electroless plating is measured, the mass percentage obtaining Co in WC-Co composite powder body is about 0.61wt%.
Described chemical plating fluid formula is as follows:
Step 3: cobalt contents step 2 obtained is the WC-Co composite powder body of 0.3wt%, be placed in SPS discharge plasma sintering system sintering: vacuumize and make vacuum tightness reach more than 8Pa, be forced into 50MPa, with the temperature rise rate to 1500 DEG C of 200 DEG C/min, be incubated 5 minutes, release, cools to less than 100 DEG C with the furnace and takes out air cooling.After measured, the relative density of this sample is 99.7%, and hardness is 2468HV10, and fracture toughness property is 9.6MPa ﹒ m
1/2.
Embodiment 4
Step one: be that the WC powder of 0.2um joins chemical activation liquid (HF40ml/L of 40%, NH by the loading capacity of 1kg/L by average grain size
4f3g/L, the HNO of 65%
330ml/L, 36%HCl20ml/L) in, ultrasonic (40KHz, 400W) stir process 15 ~ 30min under room temperature; Separation chemistry activation solution after quiescent settling, then use the pretreated WC powder of washed with de-ionized water chemical activation 3 times;
Step 2: pretreated for step one chemical activation WC powder is joined in chemical plating fluid by the loading capacity of 150g/L, prior to 70 ~ 85 DEG C of water-bath insulations, produce to there being bubble, proceed to 40 ~ 60 DEG C of ultrasonic ponds and carry out ultrasonic (40KHz, 400W) stir electroless cobalt plating, bubble is had to produce in reaction process, treat that bubble-free produces electroless cobalt plating complete, separation chemistry plating solution after quiescent settling, use washed with de-ionized water powder again 3 times, powder is put into the dry 6h of 60 ~ 80 DEG C of thermostatic drying chambers, according to Shimadzu high accuracy analysis balance, the weighing of powder before and after electroless plating is measured, the mass percentage obtaining Co in WC-Co composite powder body is 0.98wt%.
Described chemical plating fluid formula is as follows:
Step 3: cobalt contents step 2 obtained is the WC-Co composite powder body of 0.98wt%, be placed in SPS discharge plasma sintering system sintering: vacuumize and make vacuum tightness reach more than 8Pa, be forced into 50MPa, with the temperature rise rate to 1500 DEG C of 100 DEG C/min, be incubated 5 minutes, release, cools to less than 100 DEG C with the furnace and takes out air cooling.After measured, the relative density of this sample is 99.9%, and hardness is 2409HV10, and fracture toughness property is 10.4MPa ﹒ m
1/2.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
Claims (10)
1. a preparation method for few Binder Phase carboloy, is characterized in that, comprise the steps:
Step one: WC powder is added in chemical activation liquid, ultrasonic agitation process under room temperature, separation chemistry activation solution after quiescent settling, then use washed with de-ionized water WC powder;
Step 2: WC powder step one obtained is added in chemical plating fluid, in 70 ~ 85 DEG C of water-bath insulations to there being bubble to produce, then proceed to 40 ~ 60 DEG C of ultrasonic ponds and carry out ultrasonic agitation electroless cobalt plating, separation chemistry plating solution after quiescent settling, use washed with de-ionized water powder, after drying, obtain low cobalt content WC-Co composite powder body;
Step 3: low cobalt content WC-Co composite powder body step 2 obtained is placed in discharge plasma sintering system, vacuumize and make vacuum tightness reach more than 8Pa, be forced into 50MPa, be warming up to 1500 ~ 1700 DEG C of insulations, after release cooling, obtain few Binder Phase carboloy.
2. preparation method according to claim 1, is characterized in that, the grain-size of described WC powder is 0.2 ~ 0.4um.
3. preparation method according to claim 1, is characterized in that, the ultrasonic frequency for ultrasonic agitation is 40KHz, and ultrasonic power is 300 ~ 400W.
4. preparation method according to claim 1, is characterized in that, described chemical activation liquid comprises following composition:
5. preparation method according to claim 1, is characterized in that, the loading capacity of WC powder by 1kg/L is added in chemical activation liquid.
6. preparation method according to claim 1, is characterized in that, described chemical plating fluid comprises following component:
Wherein, the pH value of described chemical plating fluid is 9 ~ 11.
7. the preparation method according to claim 1 ~ 6 any one, is characterized in that, WC powder step one obtained is added in chemical plating fluid by the loading capacity of 150g/L ~ 1500g/L.
8. the preparation method according to claim 1 ~ 6 any one, is characterized in that, in described step 2, drying is specially:
By powder freeze-day with constant temperature 6h at 60 ~ 80 DEG C.
9. the preparation method according to claim 1 ~ 6 any one, is characterized in that, the mass percent of the Co comprised in described WC-Co composite powder body adopts Shimadzu high accuracy analysis balance to measure.
10. the preparation method according to claim 1 ~ 6 any one, is characterized in that, the speed heated up in described step 3 is 200 DEG C/min, is 5 minutes in the time of 1500 ~ 1700 DEG C of insulations.
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| CN106891011A (en) * | 2017-03-23 | 2017-06-27 | 洛阳理工学院 | A kind of lamination complex cutter material and preparation method |
| CN106956007A (en) * | 2017-03-23 | 2017-07-18 | 洛阳理工学院 | A kind of graded composite cutter material and preparation method |
| CN106956007B (en) * | 2017-03-23 | 2019-04-30 | 洛阳理工学院 | A kind of graded composite cutter material and preparation method |
| CN106891011B (en) * | 2017-03-23 | 2019-08-02 | 洛阳理工学院 | A kind of lamination complex cutter material and preparation method |
| CN107868948A (en) * | 2017-12-01 | 2018-04-03 | 河海大学 | A kind of method of the chemical plating cobalt coated tungsten carbide based on cobalt salt activation |
| CN108165791A (en) * | 2017-12-06 | 2018-06-15 | 台州学院 | A kind of preparation method of soap-free emulsion polymeization phase ultrafine tungsten carbide hard alloy |
| CN108165791B (en) * | 2017-12-06 | 2020-01-17 | 台州学院 | Preparation method of binderless superfine tungsten carbide hard alloy |
| CN109338197A (en) * | 2018-11-06 | 2019-02-15 | 河海大学 | A kind of preparation method of high-compactness WC/Co composite material hard alloy |
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Application publication date: 20141224 Assignee: ZHEJIANG SGSO TECHNOLOGY CO.,LTD. Assignor: TAIZHOU University Contract record no.: X2022990000377 Denomination of invention: A preparation method of tungsten carbide with less bonding phase Granted publication date: 20170118 License type: Common License Record date: 20220712 |
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