Synthesis and Properties of Nanocrystalline Diamond

1. Synthesis and Properties of Nanocrystalline Diamond Y. Tzeng Auburn University Alabama, USA (Part of this set of slides were presented by YK Liu for ELEC 7970 instructed by Y. Tzeng in Summer 2003)

2. Why nanocrystalline diamond?

3. Pure nanodiamond is produced by detonation of diamond blend and subsequently by chemical purification.Nanodiamond is a unique product combining:- diamond hardness core chemical inertia- nanosize (4-6 nm)- rounded shape- active surface Average monocrystal size: 5 nm Average size of grains: 20-50 nm Pycnometric density: 3.1-3.2 g/cm3 Specific surface: ~300 m2/g Bulk weight: 0.4-0.6 g/cm3 Constant of crystal lattice: 0.3573 +/- 0.0005 nm Beginning of air oxidation: ~450C Beginning of vacuum graphitization: ~1100C http://www.nanodiamond.com/4498.html

4. Pure rare nanodiamond (nanometric ultradispersive detonational diamond) in the form of dry powder. For small quantities the prices are: Less than 100 grams                              7 USD for 1 gram Between 100 grams and 1000 grams    5 USD for 1 gram Between 1 Kg and 5 Kg                           4.5 USD for 1 gram http://www.nanodiamond.com/4498.html

5. Carbon phase diagram • Graphite to Diamond Recrystallization catalyzed by metals at High Pressure and High Temperatures • Chemical Vapor Deposition (CVD) at lower pressure and temperatures ”Diamond Films And Coatings”, Noyes, 1992.

6. Crystalline carbon Diamond sp3 bonded carbon Graphite sp2 bonded carbon Pressure 2.16 A 3.35 A Temperature James E. Butler, CVD Diamond Nucleation, Growth, Properties and Applications (ADC/FCT 2001 Short Course)

7. Nanodiamond powders synthesis Shock-induced transformation setup D.G. Morris, J. Appl. Phys. 51 (4), 1980, p2059

8. Nanodiamond powders synthesis Shock-induced transformation D.G. Morris, J. Appl. Phys. 51 (4), 1980, p2059

9. Nanodiamond powders synthesis Diamond in detonation soot • The first report on detonation synthesis of powder was by the Russian scientists Pashkov, et al in 1979. • TNT mixed with solids composed of C,H,N,O atoms was fired. • The explosion yields a product composition mainly of N2,H2O, CO2 and solid carbon, because the equilibrium favors the reaction • 2CO→CO2+C (solid) at the very high pressure ~300 kbar • The solid carbon is a mixture of different kinds of carbon, micrographite, carbon black, ultradispersed diamond (UDD) etc. • The UDD generated with this method has a narrow (typically 5 Å) distribution of particle sizes centered around 50 Å N.R. Greiner, D.S. Phillips, J.D. Johnson and F. Volk, Nature, p440

10. Detonation setup Nanodiamond powders synthesis 1-case, 3-capsule, 4-mix of 40%RDX and 60%TNT,7-electric detonators Source: http://web.vru.ru/diamond/opisanie_e.htm

11. Nanodiamond powders synthesis Detonation synthesis Dry, Wet represents the detonation is in a CO2, water medium, respectively. K.Iakoubovskii, M.V. Baidakova, B.H. Wouters, A.Stesmans and P.J. Grobet, Diamond and Related Materials 9 (2000), p861

12. Nanodiamond powders synthesis Purification of nanodiamond powder • Two kinds of liquid phase oxidizing agent to remove the non-diamond • carbon and other impurities • Step1. Boiled 18% HCl for 1 hour (remove metallic impurities) • Step2. Mixture of 6 HClO4 (71%) and 1 HNO3(65%) with stirring for 2 hrs • at 200°C • Step3. Washed with distilled water • Step1. Mixture of 2 H2SO4(98%), 1 fuming H2SO4 (with SO3 content • >50%) and 1 HNO3 (65%) boiled at 270°C for 2 hrs • Step2. Washed with distilled water T. Jiang and K.Xu, Carbon Vol.33 No. 12 (1995), p1663

13. Nanodiamond powders synthesis Nanodiamond particles • Nanodiamond particles • Size: • spherical particles of 3- 10 • nm in diameter(TEM) • Structure: • cubic diamond(electron • diffraction pattern) HR-TEM micrograph of the explosive detonated nanodiamond powders D.He, L. Shao, W. Gong, E. Xie, K. Xu and G. Chen, Diamond and Related Materials 9 (2000), p1600

14. Nanodiamond powders synthesis Nanodiamond particle conductivity Sample preparations: 1. Nanodiamond particle slurry 2. Coated on quartz 3. Two electrodes are 1 cm in length and separate a space of 0.5 cm Results: 1. Conductivity decreases with increasing annealing temp. 2. In the higher temp. range, the samples show a semi-conducting conduction as described by Arrhenius law J.J. Wang, E.S. Lambers, Solid-State Electronics Vol.42 No.5(1998), 743-747

15. in vacuum in air Why nanocrystalline diamond? Nanodiamond used in anti-friction 10um size Al powders were sintered with N.D. particles HB:98.3 HB:132 Left:Y.Xiang, J.Zhang, C.Jin and Y.Liu, Wear 242 (2000), p202 Right: Q. Ouyang and K. Okada, J. Vac. Sci. Technol. A. 12 (4) 1994, p2577

16. http://nano.materials.drexel.edu/NATOARW/NATOPapers/Chapter3/Kuznet.pdfhttp://nano.materials.drexel.edu/NATOARW/NATOPapers/Chapter3/Kuznet.pdf

17. Why nanocrystalline diamond? Nanodiamond used in biology and medicine The nanocomposite materials, NDC, comprise nanodiamond particles bonded by a graphite-like matrix. Physical adsorption of ferment Electric field enhance adsorption Adsorption (1-4) and desorption (6) of “trypsin” (2.2-2.5 nm) and “glucose oxidase” (5 nm in size, curve 5) for NDC samples. Adsorption (1-3) and desorption (4) of “trypsin” for a NDC sample in electric field. The intensities are (1) 50, (2) 40, (3,4) 30 V/cm. Time needed to reach an equilibrium state in other carbon materials, is about 0.5 to 1 hour. G.U.Ostrovidova, A.V. Makeev, A.V. Biryukov and S.K. Gordeev, Materials science and engineering C 23 (2003),p377

18. Why nanocrystalline diamond? Nanodiamond used in biology and medicine With the presence of active functional groups, adsorption capacity can be much higher. However, the contact with high-energy surface agents lead to a change of conformation and the probability of ferment inactivation is increased. G.U.Ostrovidova, A.V. Makeev, A.V. Biryukov and S.K. Gordeev, Materials science and engineering C 23 (2003),p377

19. Nanodiamond powders synthesis Field Emission of Nanodiamond particle Measurement setup: 1. Planar diode configuration with spacing of 100 micrometer 2. The nanodiamond coated on Si was used as the cathode 3. A tungsten wire of 2 mm in diameter was used as anode Results: 1. A low turn on electric field (emit current reach 1uA) of 3.2 V/um 2. A high current density of ~95 mA/cm2 under applied field 5 V/um J.J. Wang, E.S. Lambers, Solid-State Electronics Vol.42 No.5(1998), 743-747

20. Nanodiamond is unique in the particle size and shape. The diameter of diamond crystals is in the average 5 nanometers. The unique rounded shape offers superior lubricity characteristics with the hardness and wear resistance of diamond.Nanodiamond has many applications and generates improvements in many aspects:- wear resistance, useful life, and mean time between failure- corrosion resistance of steel- angstrom finishes of polished surfaces- physical properties of rubber- strength of PTFE (Teflon-like materials)- lubricating power of oils http://www.nanodiamond.com/4498.html

21. Nanodiamond is cheap. Specific consumption of nanodiamond is on average 0,3-0,5 percent (weight) and 1 mm coating makes up 0,2 grams (1 carat) per 1 square meter. • Some applications: • Electrochemical and chemical deposition • Metal Matrix Composite with aluminium and copper • Additive for PTFE (Teflon) • Polishing Pastes and Suspensions • Additive to rubber • Abrasive Tools • Lubrificating oils, greases and coolants • Systems of Magnetic Recording • Intermetallic on the basis of copper, zin and tin • Biology and medicine • XADC-Armoloy TDC chrome coating • CVD Diamond Films • Fuel cells electrodes http://www.nanodiamond.com/4498.html

22. Electrochemical Coatings on metal by base metals or by noble metals:Cr, Ni, Cu, Au, Ag, Zn, Sn, Al, NiB • A standard galvanic equipment is used. Add to the coating bath. • Intrusion into boundary area of a state of the substance. • Average 0,3-0,5 weight %, 1 micron makes up 0,2 g (1 carat) for 1 sq. meter ot about 1 US$ / sq. meter. Advantages: • Reduces order in crystal packing of coating • Service life of products is increased 2-10 times • Decrease in coating thickness by a factor of 2-3 • Increase in capacity of galvanic, less time for precipitation with reduction in thickness coating • Attractive appearance • Reduces release problems during molding • Increase in wear-resistance • Increase microhardness • Sharp fall in friction coefficient • Decrease in corrosion resistance and porosity • Improvement of adhesion and cohesion • Unporositive coating • Reduces grain size of coating, savings http://www.nanodiamond.com/4498.html

23. Metal Matrix Composite with Aluminum and Copper A light metal with mechanical properties close to those of low-grade steel. • Mix with metal powder • Melt, in vacuum of 1 - 5 torr, or sinterisation • Alters crystal structure, changes crystallization process, changing crystal block size. Intrusion into boundary area of a state of the substance. • increase in wear resistance • increase hardness • reduces density http://www.nanodiamond.com/4498.html

24. Additive to PTFE (Teflon) Intrusion into boundary area of a state of the substance. • reduces wear as much as 25 times • coefficient of friction as much as 50% • stiffness • reduction of material added to PTFE http://www.nanodiamond.com/4498.html

25. Polishing Pastes and Suspensions • Nanodiamond finishes high precisely materials for radio engineering, electronics, optics, medicine and machine building. • Nanodiamond reduces roughness to a few nanometers, or less. • Specific consumption of nanodiamond - 1-10 g per 1 sq. m. of processable surface. 1,1 - 1,9 US $ / carat. • Intrusion into boundary area of a state of the substance. • Perfect unruffled (mirror) surface of any solids, free of defects and dislocations with relief roughness of 2-8 nm • Increases hardness http://www.nanodiamond.com/4498.html

26. Additive to Polymers and Rubber Polymerization from solutions and melts, chemical curing, electron- beam, gas-flame, electrostatic spraying. 1-5 kg per 1000 kg of rubber (polymer) and 1-5 kg per 1000 sq. meters of polymer coating or film. Price is 0,1 - 0,5 US $ for 1 kg of rubber or 0,1 - 0,3 US $ for 1 sq. m. coating at thickness of 1 mm. • Resistance to ageing and to abrasive effect • Effective stabilizers of thermal ageing of polymers • Low friction coefficient of polyfluoroelastomers and perfluoropolymers • High friction coefficient of plyisoprenes  • Increase breaking temperature 15% • Decrease attrition wear 3-5 times • Opportunity of replacement of an expensive polymeric raw material by this cheap one • Save expensive and deficient components and materials • Polymer compositions have a reinforced complex of elastic-strength properties 1,5 -2,5 times. • Fluoroelastomers with nanodiamond have the increase in abrasive resistance 2-4 times. • Diamond films have dry friction coefficient less than 0,01. • Epoxy adhesives on the basis of nanodiamond have high adhesion and cohesion properties. • Increases elastic strength and rupture strength by 30% • Increase in wear resistance http://www.nanodiamond.com/4498.html

27. Lubricating Oils, Greases, and Lubricant-coolant Liquids • Additive to motor and transmission oils, to consistent lubrificants and lubrificant-coolant liquids. • Nanodiamond provides high quality sedimentation stable and ecological safe system with size of superhard particles less than 0,5 microns. • It's an alternative to expensive oils and special lubrificants. • Add 10-200 grams for 1000 kg of oil. Price is up to 125 US $ for 1000 kg of oil or up to 50 US $ for 1000 kg of LCL. • Obtain sedimentation stable oils • Increase service life of engine • Saving in combustible lubrificant materials • Increases engine efficiency • Decrease friction torque by 20-40% • Decrease in wear of rubbed surfaces by 30-40% • Fast run-in of pairs of friction http://www.nanodiamond.com/4498.html

28. Abrasive Tools Compact polycrystalline product by sintering - for polished, grinding and cutting tools Amplifier of polymeric binder for elastic abrasive tool In compacts up to 10 US $/g, in polymer matrixes up to 0,5 US $/g. • Compact sinters (sintering) • Diamond-oxide compositions with oxide of glass-forming type (diamond ceramics). • Nanodiamond metallized by clusters of transition metals http://www.nanodiamond.com/4498.html

29. Systems of Magnetic Recording • Intrusion into boundary area of a state of the substance. • Decreases ferro-magnetic grain • Decreases abrasive wear and friction coefficient • Increases recording density http://www.nanodiamond.com/4498.html

30. Intermetallic on the Basis of Copper, Zinc, and Tin Nanodiamond is an ideal composite material for intermetallics on the basis of copper with zinc or tin for very hard working conditions of friction units when plastic and liquid lubricating materials are displaced. no more than 15 volume % Intrusion into boundary area of a state of the substance. Decreases frictional coefficient 2-6 times http://www.nanodiamond.com/4498.html

31. Biological and Medicine Applications • Nanodiamond are super-active sorbents, immobilizers of biologically active substances, they are able to intensify action of medicinal preparations and can be used for oncology, gastroenterology, dermatology and etc. It does not have mutahenious and cancer properties. • Nanodiamond applicated as an aqueos and oil suspension at cancer patients. • Significant amount of unpaired electrons on nanodiamond surface makes each diamond crystal powerful multicharge radical donor, able to extinguish intensive radical processes, which accompany practically all serous illness of the patient. • Individual nanodiamond crystals have the ability to: • penetrate through walls of live cells • interact with active radicals • neutralize pathogenic viruses and bacteria • Nanodiamonds have extremely high activity to pathogenic viruses and bacteria, absorbing and destroying them. Nanodiamond is a new generation of antiseptics of specific action. http://www.nanodiamond.com/4498.html

32. Properties and Advantages of Nanodiamond for Biological and Medical Applications For example, Nanodiamond is applicated as an aqueos and oil suspension for cancer patients. • Superactive sorbent • Immobilizator of biologically active substances • Able to strenghten action of medicinal preparations • Normalizes blood pressure • Effective at gastric intestinal diseases • Effective means for struggle with burns, skin deseases, internal intoxication • No mutahenious or cancer properties • Untoxic http://www.nanodiamond.com/4498.html

33. Armology Coating for Metals • Thickness of coating (0.0001 - 0.0003 inches [2.5 - 7.5 microns] per surface, 1 mm makes up 0,2 g (1 carat) per 1 m2 • Decreases wear corrosion • Decreases friction • Increases microhardness and surface hardness (to 92rc plus) • Increases abrasion resistance to ceramic-like material • Increases adhesion • Coating-to-substrate bond - absolute adhesion (will not fracture from substrate, unless substrate fractures or fatigues) • Plastic mold life - increased (has shown increase in life of 300 % plus with 30 - 50 % filled materials) http://www.nanodiamond.com/4498.html

34. Other Applications: CVD Diamond: Seeding for diamond nucleation Fuel Cell Electrodes: Long life and good electrochemical properties. http://www.nanodiamond.com/4498.html

35. Crystalline carbon Diamond sp3 bonded carbon Graphite sp2 bonded carbon Pressure 2.16 A 3.35 A Temperature James E. Butler, CVD Diamond Nucleation, Growth, Properties and Applications (ADC/FCT 2001 Short Course)

36. Carbon Onion HRTEM micrographs of the nanodiamond sample annealed under vacuum at (1) 1170, (2) 1600, (3) 1900, (4) 2140 K. The dark straight contrast lines in (2) correspond to the (111) crystallographic diamond layers. The distance between these lines is 2.06 A. The dark lines in Figs. (3) and (4) correspond to crystallographic graphite layers. The distance between these lines is 3.5A. The diamond weight fractions (x) of the samples are also presented within each image. http://nano.materials.drexel.edu/NATOARW/NATOPapers/Chapter3/Kuznet.pdf

37. Onion Like Carbon http://nano.materials.drexel.edu/NATOARW/NATOPapers/Chapter3/Kuznet.pdf

38. Nanodiamond film deposition Nucleation of diamond particles

39. http://www.conferences.unimelb.edu.au/icndst-8/Presentations/6-2.pdfhttp://www.conferences.unimelb.edu.au/icndst-8/Presentations/6-2.pdf

40. Nanodiamond film deposition ACTIVATION Gaseous Processes e-, heat H2 2H CH4 + H CH3 + H2 FLOW AND REACTION Diffusion CVD process for diamond film deposition REACTANTS Gaseous Reagents H2 + CH4 Surface Processes SUBSTRATE James E. Butler, CVD Diamond Nucleation, Growth, Properties and Applications (ADC/FCT 2001 Short Course)

41. http://www.conferences.unimelb.edu.au/icndst-8/Presentations/p2-02-2.pdfhttp://www.conferences.unimelb.edu.au/icndst-8/Presentations/p2-02-2.pdf

42. http://www.conferences.unimelb.edu.au/icndst-8/Presentations/p2-02-2.pdfhttp://www.conferences.unimelb.edu.au/icndst-8/Presentations/p2-02-2.pdf

43. Diamond Properties ”Diamond Films And Coatings”, Noyes, 1992.

44. Diamond properties High Young’s modulus Fundamental resonant frequency Mass sensitivity Sm (Image after B. Prorok) (The ratio of diamond and Si3N4 are 5.4 and 2.9) P.G.Datskos and T.Thundat, Journal of Nanoscience and Nanotechnology 2, 2002, p369

45. Diamond properties High SAW velocity Fine-pattern lithography or high-speed material are thus the alternatives for obtaining high frequency devices. Source: http://www.sei.co.jp

46. Why nanocrystalline diamond? Nanocrystalline diamond Nanodiamond powders: • Nano-scale crystalline • Quasi-spherical morphology Diamond tools Nanodiamond films: • Surface smoothness • Optical transparency • Electrical conductivity Diamond membrane (250 nm) Top and bottom pictures: http://www.CVD-diamond.com ; middle one: www.conference.unimelb.edu.au/icndst-8 /presentations/6-2.pdf diamond lens

47. Nanodiamond film deposition Nucleation of diamond particles http://www.conference.unimelb.edu.au/icndst-8/presentations/6-2.pdf

48. Nanodiamond film deposition Nanocrystalline diamond deposition • Replacing the H2 with Ar results in the growth of nanocrystalline diamond • Atomic hydrogen plays an important role in suppressing secondary nucleation by regasifying small or nondiamond phase nuclei. • The radicals in plasma change from methyl (CH3‧) to dimer (C2) D. Zhou, D.M. Gruen, L. C. Qin, T. G. McCauley, and A. R. Krauss, J. Appl. Phys. 84(1998), p1981

49. Nanodiamond film deposition Nanodiamond growth model D. A. Horner, L. A. Curtiss and D.M. Gruen, Chemical Physics Letters 233 (1995), p243

50. Nanodiamond film deposition Micro- V.S. Nano-crystalline diamond 2%CH4 + 98%H2 1%CH4 +5%H2 + 94% Ar