Advanced
Fabrication of isotropic bulk graphite using artificial graphite scrap
Fabrication of isotropic bulk graphite using artificial graphite scrap
Carbon letters. 2014. Apr, 15(2): 142-145
Copyright © 2014, Korean Carbon Society
This is an Open Access article distributed under the terms of the Creative Commons Attribution Non-Commercial License (http://creativecommons.org/licenses/by-nc/3.0/) which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited.
  • Received : January 01, 2014
  • Accepted : April 04, 2014
  • Published : April 30, 2014
Download
PDF
e-PUB
PubReader
PPT
Export by style
Share
Article
Author
Metrics
Cited by
TagCloud
About the Authors
Sang-Min Lee
School of Advanced Materials and Systems Engineering, Kumoh National Institute of Technology, Gumi 730-701, Korea
Dong-Su Kang
School of Advanced Materials and Systems Engineering, Kumoh National Institute of Technology, Gumi 730-701, Korea
Woo-Seok Kim
Carbolab Co., Ltd., Gumi 730-701, Korea
Jea-Seung Roh
School of Advanced Materials and Systems Engineering, Kumoh National Institute of Technology, Gumi 730-701, Korea
jsroh@kumoh.ac.kr
Abstract
Isotropic synthetic graphite scrap and phenolic resin were mixed, and the mixed powder was formed at 300 MPa to produce a green body. New bulk graphite was produced by carbonizing the green body at 700℃, and the bulk graphite thus produced was impregnated with resin and re-carbonized at 700℃. The bulk density of the bulk graphite was 1.29 g/cm 3 , and the porosity of the open pores was 29.8%. After one impregnation, the density increased to 1.44 g/cm 3 while the porosity decreased to 25.2%. Differences in the pore distribution before and after impregnation were easily confirmed by observing the microstructure. In addition, by using an X-ray diffractometer, the degrees-of-alignment (Da) were obtained for one side perpendicular to the direction of compression molding of the bulk graphite (the “top-face”), and one side parallel to the direction of compression molding (the “side-face”). The anisotropy ratio calculated from the Da-values obtained was 1.13, which indicates comparatively good isotropy.
Keywords
1. Introduction
Because graphite has an anisotropic crystal structure and boasts far better heat resistance, corrosion resistance, electric conductivity, high-temperature strength, and lubricity than other materials, it is used in diverse fields. These include use in high-temperature structural materials such as electrodes, carbon brushes, mechanical seals and special mechanical parts [1 - 3] . When graphite with such an anisotropic structure is formed using the cold isostatic pressing method, graphite particles are arranged in a disorderly manner, exhibit isotropy, have a dense structure, and are high in density and strength. In addition, because the green body has no directionality, its physical and electrical characteristics are uniform in all directions (isotropic) [4 , 5] .
In the general production process for an isotropic, synthetic, graphite block; petroleum- or tar-pitch-derived coke powder is evenly mixed with a binder such as pitch or resin, after which it is formed and then carbonized. At this stage, because of the volatilization of the binder due to carbonization, pores are generated inside the green body, and the green body is impregnated with pitch or resin to fill the pores. After filling the pores by several impregnation cycles, the green body is graphitized by thermal treatment at 2500℃ or above [6 - 8] .
After being produced through such a complicated process, the isotropic, synthetic, graphite block is processed for a specific usage, and a large amount of scrap (ISGS) is generated. The graphite scrap generated during the process is added to molten iron to increase the carbon content at steel mills or used to produce graphite-added refractory materials. In particular, when producing carbon-magnesite bricks, approximately 15-25% graphite scrap is added. However, the overall amount of graphite scrap used is not large, and most of it is discarded [9 - 11] .
Consequently, the present study sought to produce isotropic bulk graphite using ISGS. Phenolic resin was used as the binder, and changes in the density and porosity were measured after a single impregnation of the recycled isotropic bulk graphite. In addition, using X-ray diffractometer (XRD), the degrees-ofalignment (Da) and microstructure according to the direction of compression molding were measured, and the anisotropy ratio was obtained from the Da. The results of the present study were used to evaluate the potential of producing isotropic bulk-graphite from ISGS, and to provide data for future production of highdensity, isotropic bulk-graphite.
2. Experimental Procedure
- 2.1. Raw materials and preparation
The raw powder used in the present study was ISGS remaining after processing of isotropic bulk graphite for machining [12] . The particle size of the raw powder was measured using a particle size analyzer (Malvern Ins. GB/Mastersizer 2000). The binder was phenolic resin produced by Kangnam Chemical Co., Ltd. The mixture of the raw material and the binder was subjected to uniaxial press-forming at a pressure of 300 MPa, thus producing a green body with a diameter of 10 mm. The green body thus formed was carbonized for one hour at 700℃ in nitrogen gas. The pores generated by the carbonization process were re-carbonized after being resin-impregnated one time.
- 2.2. Density and porosity measurement
Changes in the density and porosity of the recycled bulk graphite, before and after impregnation, were measured using the Archimedes method (ISO 18754: 2003). The density measured in the present study is volumetric density, which includes both open and closed pores; and the porosity was obtained from measurement of the volume of open pores. Here, ‘open pores’ refers to penetrating pores and ink-bottle pores through which fluids can infiltrate [13 , 14] .
- 2.3. Observations of microstructure
The bulk graphite produced was ground using sandpaper (#1200-#2400) and ultimately micro-ground at 0.25 μm. An optical microscope (Nikon Eclipse, LV150) was used to examine the microstructure of the bulk graphite before and after impregnation. One side perpendicular to the direction of compression molding (henceforth “top-face”), and one side parallel to the direction of compression molding (henceforth “side-face”), was examined.
- 2.4. XRD analysis
To confirm the Da of the recycled bulk graphite, an XRD (SWXD, X-MAX/2000-PC, Rigaku) analysis was conducted. The wavelength (Cu-Kα 1 ) of the X-ray target used was 1.5406 Å, and XRD spectra were obtained using the 2θ continuous scanning method at a scanning rate of 1°/min, within a scanning range of 10-60°. Using the XRD data, the top-face and the side-face were measured, and the Da values were compared. The Da values were calculated according to the following equation, using the values of relative strength divided by the height at the (100)-peak and at the (002)-peak. Below, I 002 and I 100 are the height at the (002)-peak and the (100)-peak, respectively [15 , 16] :
Da = I 100 /(I 100 + I 002 )
In addition, the anisotropy ratio was obtained from the Da ratio (Da Top /Da Side ) of the top-face and the side-face [17 - 19] .
3. Results and Discussion
- 3.1. ISGS powder analysis
Fig. 1 shows the results of the particle-size analysis of ISGS and the XRD spectra. The average particle size in the raw powder was approximately 50 μm. In the XRD spectra, the strength of the (002)-peak is very great, and the (100)-peak and the (101)-peak observed at the 2θ positions of 42.22 and 44.39 (JCPDS-ICDD #411487) are clearly distinguished. This shows the outstanding crystallinity of ISGS.
PPT Slide
Lager Image
Isotropic synthetic graphite scrap results: (a) particle-size analysis and (b) X-ray diffractometer spectrum.
- 3.2. Density and porosity
Table 1 shows the density and the porosity of the bulk graphite before and after impregnation, of the three samples measured. The density of the pre-impregnation bulk graphite and the post-impregnation density were 1.29 g/cm 3 and 1.44 g/cm 3 , respectively, thus exhibiting an increase of 11.1% after impregnation. The pre-impregnation porosity was 29.8%, and the postimpregnation porosity was 25.2%, respectively, thus showing a decrease of 4.6%. This decrease in the porosity can be seen as the result of infiltration and impregnation of resin into the open pores. Consequently, if the iteration of impregnation is increased, it is expected that high-density bulk-graphite using recycled ISGS can be produced.
Result of bulk density and porosity (open pore) measurement
PPT Slide
Lager Image
Result of bulk density and porosity (open pore) measurement
- 3.3. Microstructures
Fig. 2 shows the microstructure of the bulk graphite before and after impregnation. In the microstructure of the top-face and the side-face, it was possible to observe the directionality of the particles. Consequently, the possibility of producing isotropic bulk graphite using ISGS was confirmed. It was also possible to confirm a decrease in the pore distribution of the microstructures after impregnation and, as indicated by the data on density and porosity, to confirm an impregnation effect.
PPT Slide
Lager Image
Optical microscopy images (×100) of bulk graphite before and after impregnation.
- 3.4. Anisotropy ratio
Fig. 3 shows the top-face and side-face XRD spectra of bulk graphite. It clearly shows the (002)-peak, and a distinction between the (100)-peak and the (101)-peak was confirmed. Differences in the XRD spectra between the top-face and the side-face were not observed. Table 2 shows the Da and the anisotropy ratio from the strength of the (002)-peak and the (100)-peak of the XRD spectra. The Da values of the top-face and the side-face were 0.071 and 0.063, respectively, and the difference between them was 0.008, thus confirming that there was no alignment in a particular direction. This also agreed with the earlier results of study of the microstructure. In addition, the anisotropy ratio calculated with the Da of the top-face and the side-face was 1.13, thus confirming the production of comparatively good, new, isotropic bulk-graphite [20] .
PPT Slide
Lager Image
X-ray diffractometer spectra of manufactured bulk graphite.
Degree of alignment and anisotropy ratio from X-ray diffractometer
PPT Slide
Lager Image
Degree of alignment and anisotropy ratio from X-ray diffractometer
4. Conclusions
The present study sought to produce isotropic bulk graphite using recycled ISGS, and the characteristics of the bulk graphite thus produced were studied, leading to the following conclusions:
The density and porosity of the new bulk graphite produced were 1.29 g/cm 3 and 29.8%, respectively. After a single resin impregnation, the density rose to 1.44 g/cm 3 (11.1% increase) and the porosity fell to 25.2% (4.6% decrease).
According to the results from examination of the microstructure, the pores in the new bulk graphite were confirmed to decrease after impregnation, but directionality of particles exposed on the top-face and side-face was not observed.
According to the results from calculations obtained using XRD spectra, the Da values were 0.071 for the top-face and 0.063 for the side-face: a difference of 0.008, and the anisotropy ratio was 1.13: confirming that the newly produced bulk graphite was isotropic.
Consequently, the present study confirmed that it is possible to produce isotropic bulk graphite using recycled ISGS. It is expected that it will be possible in the future to produce highdensity, isotropic bulk-graphite by increasing the number of impregnation cycles.
Acknowledgements
This work was supported by the Kumoh National Institute of Technology.
References
Park SM , Yasuda E , Park YD 1996 The influence of graphitic structure on oxidation reaction of carbon materials J Korean Ceram Soc http://koix.ksci.re.kr/KISTI1.1003/JNL.JAKO199611920040047 33 (7) 816 - 822
Liu Z , Guo Q , Shi J , Zhai G , Liu L 2008 Graphite blocks with high thermal conductivity derived from natural graphite flake Carbon http://dx.doi.org/10.1016/j.carbon.2007.11.050 46 414 -
Youm HN , Kim KJ , Lee JM , Chung YJ 1993 Effects of impregnation on the manufacture of high density carbon materials J Korean Ceram Soc http://koix.ksci.re.kr/KISTI1.1003/JNL.JAKO199311920037008 30 (10) 852 - 858
Choi WK , Kim BJ , Chi SH , Park SJ 2009 Nuclear graphites (I): oxidation behaviors Carbon Lett http://dx.doi.org/10.5714/CL.2009.10.3.239 10 (3) 239 - 249
Jung JW , Kim KT 1998 Effect of rubber mold on densification behavior of metal powder during cold isostatic pressing Trans Korean Soc Mech Eng A http://koix.ksci.re.kr/KISTI1.1003/JNL.JAKO199811919541620 22 (2) 330 - 342
Chung SH , Kim KW , Kim MS , Lim YS 1999 Analysis on raw materials for graphite electrode J Res Inst Ind Technol 18 365 -
Wissler M 2006 Graphite and carbon powders for electrochemical applications J Power Sources http://dx.doi.org/10.1016/j.jpowsour.2006.02.064 156 142 -
Park YD 1997 Production technology of artificial graphite electrodes for arc furnace Polym Sci Technol 8 155 -
Janerka K , Bartocha D 2008 The sort of carburization and the quality of obtained cast iron Arch Foundry Eng 8 55 -
Roessler A , Crettenand D 2004 Direct electrochemical reduction of vat dyes in a fixed bed of graphite granules Dyes Pigments http://dx.doi.org/10.1016/j.dyepig.2004.01.005 63 29 -
Fan Cl , Chen H 2011 Preparation, structure, and electrochemical performance of anodes from artificial graphite scrap for lithium ion batteries J Mater Sci http://dx.doi.org/10.1007/s10853-010-5050-y 46 2140 -
Aas KL 2004 Performance of two graphite electrode qualities in EDM of seal slots in a jet engine turbine vane J Mater Process Technol http://dx.doi.org/10.1016/j.jmatprotec.2004.02.005 149 152 -
Han Yo-Sep , Kim Hyun-Jung , Shin Young-Seop , Park Jai-Koo , Ko Jae-Churl 2009 Silver Coating on the Porous Pellets from Porphyry Rock and Application to an Antibacterial Media Journal of the Korean Ceramic Society http://dx.doi.org/10.4191/KCERS.2009.46.1.016 46 (1) 16 - 23
Ishizaki KZ , Komarneni S , Nanko M 1998 Porous Materials: Process Technology and Applications Kluwer Academic Publishers Dordrecht
Cao A , Xu C , Liang J , Wu D , Wei B 2001 X-ray diffraction characterization on the alignment degree of carbon nanotubes Chem Phys Lett http://dx.doi.org/10.1016/S0009-2614(01)00671-6 344 13 -
Roh JS 2004 A structural study of the oxidized high modulus pitch based carbon fibers by oxidation in carbon dioxide Carbon Lett http://koix.ksci.re.kr/KISTI1.1003/JNL.JAKO200422463505506 5 (1) 27 - 33
Seehra MS , Pavlovic AS , Babu VS , Zondlo JW , Stansberry PG , Stiller AH 1994 Measurements and control of anisotropy in ten coal-based graphites Carbon http://dx.doi.org/10.1016/0008-6223(94)90163-5 32 431 -
Weller TE , Ellerby M , Saxena SS , Smith RP , Skipper NT 2005 Superconductivity in the intercalated graphite compounds C6Yb and C6Ca Nat Phys http://dx.doi.org/10.1038/nphys0010 1 39 -
Slack GA 1962 Anisotropic thermal conductivity of pyrolytic graphite Phys Rev http://dx.doi.org/10.1103/PhysRev.127.694 127 694 -
Oh JK , Lee SW , Park KW 1991 Preparation of Isotropic Carbon with High Density J Korean Ceram Soc http://koix.ksci.re.kr/KISTI1.1003/JNL.JAKO199111920024975 28 (11) 908 - 916