Particle size analysis and characterization of nanodiamond dispersions in water and dimethylformamide by various scattering and diffraction methods

  • Tomáš KováříkEmail author
  • Petr Bělský
  • David Rieger
  • Jan Ilavsky
  • Věra Jandová
  • Michael Maas
  • Pavol Šutta
  • Michal Pola
  • Rostislav Medlín
Research Paper


Over the past few decades, detonation nanodiamonds (NDs) have gained increased attention due to their unique physicochemical properties. Various methods for preparation of ND suspensions have been introduced. This paper presents thermally annealed nanodiamonds dispersed via sonication and separated by centrifugation in deionized water and dimethylformamide in five weight concentrations ranging from 0.05 to 1 wt%. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) were applied to study the thermal behavior of NDs. Crystallographic properties of air-annealed and dispersed NDs were examined by means of X-ray diffraction (XRD). Nanodiamond dispersions were analyzed by static light scattering (SLS), dynamic light scattering (DLS), ultra-small- and small-angle X-ray scattering (USAXS/SAXS), and high-resolution transmission electron microscopy (HRTEM). SLS and DLS give similar results of ND aggregates mean size between ~ 61 and 73 nm, regardless of solvent type and nanoparticle concentration. For dispersions with increasing concentrations of NDs, neither increased aggregate size nor different kinetics of separation during sonication and centrifugation were observed. USAXS/SAXS provided the aggregates size (2Rg) in the range from 57 to 65 nm and size of primary particles from 5.4 to 5.8 nm. HRTEM also showed presence of larger aggregates with tens of nanometers in size in both water and DMF dispersions, and size of primary particles ranging from 5.5 to 6 nm in very good agreement with SAXS.

Graphical abstract



Nanodiamonds Nanodispersions X-ray diffraction Static light scattering Dynamic light scattering Ultra-small-angle X-ray scattering Nanoscale instrumentation 


Funding information

The result was developed within the CENTEM project, reg. no. CZ.1.05/2.1.00/03.0088, cofunded by the ERDF as part of the Ministry of Education, Youth and Sports OP RDI programme and, in the follow-up sustainability stage, supported through CENTEM PLUS (LO1402) by financial means from the Ministry of Education, Youth and Sports under the National Sustainability Programme I.

This work was supported by the European Regional Development Fund (ERDF), project CEDAMNF, reg. no. CZ.02.1.01/0.0/0.0/15_003/0000358.

This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357.

Supplementary material

11051_2020_4755_MOESM1_ESM.docx (20 kb)
ESM 1 (DOCX 20 kb)


  1. Akinfiev NN, Zotov AV (2016) Solubility of chlorargyrite (AgCl(cr./l.)) in water: new experimental data and a predictive model valid for a wide range of temperatures (273–873K) and water densities (0.01–1g·cm−3). Geochim Cosmochim Acta 178:178–194. CrossRefGoogle Scholar
  2. Aqel A, Abou El-Nour KMM, Ammar RAA, Al-Warthan A (2012) Carbon nanotubes, science and technology part (I) structure, synthesis and characterization. Arab J Chem 5:1–23. CrossRefGoogle Scholar
  3. Beaucage G (1995) Approximations leading to a unified exponential/power-law approach to small-angle scattering. J Appl Crystallogr 28:717–728. CrossRefGoogle Scholar
  4. Chantooni MK, Kolthoff IM (1973) Solubility product and anionic complexation constants of silver halides, benzoate, and acetate in acetonitrile, N,N-dimethylformamide, and dimethyl sulfoxide. J Phys Chem 77(1):1–7. CrossRefGoogle Scholar
  5. Dolmatov VY, Lapchuk NM, Lapchuk TM, Nguyen BTT, Myllymäki V, Vehanen A, Yakovlev RY (2016) A study of defects and impurities in doped detonation nanodiamonds by EPR, Raman scattering, and XRD methods. J Superhard Mater 38(4):219–229. CrossRefGoogle Scholar
  6. Huang H, Dai L, Wang DH, Tan L-S, Osawa E (2008) Large-scale self-assembly of dispersed nanodiamonds. J Mater Chem 18:1347–1352. CrossRefGoogle Scholar
  7. Ilavsky J, Jemian PR (2009) Irena: tool suite for modeling and analysis of small-angle scattering. J Appl Crystallogr 42:347–353. CrossRefGoogle Scholar
  8. Ilavsky J, Zhang F, Andrews RN, Kuzmenko I, Jemian PR, Levine LE, Allen AJ (2018) Development of combined microstructure and structure characterization facility for in situ and operando studies at the advanced photon source. J Appl Crystallogr 51(3):867–882. CrossRefGoogle Scholar
  9. Ioni YV, Tkachev SV, Bulychev NA, Gubin SP (2011) Preparation of finely dispersed nanographite. Inorg Mater 47(6):597–602. CrossRefGoogle Scholar
  10. Kaur R, Badea I (2013) Nanodiamonds as novel nanomaterials for biomedical applications: drug delivery and imaging systems. Int J Nanomedicine 8:203–220. CrossRefGoogle Scholar
  11. Khan M, Shahzad N, Xiong C, Zhao TK, Li T, Siddique F, Ali N, Shahzad M, Ullah H, Rakha SA (2016) Dispersion behavior and the influences of ball milling technique on functionalization of detonated nano-diamonds. Diam Relat Mater 61:32–40. CrossRefGoogle Scholar
  12. Kloprogge JT, Ruan HD, Frost RL (2002) Thermal decomposition of bauxite minerals: infrared emission spectroscopy of gibbsite, boehmite and diaspore. J Mater Sci 37:1121–1129. CrossRefGoogle Scholar
  13. Kondo T, Neitzel I, Mochalin VN, Urai J, Yuasa M, Gogotsi Y (2013) Electrical conductivity of thermally hydrogenated nanodiamond powders. J Appl Physiol 113:214307. CrossRefGoogle Scholar
  14. Koniakhin SV, Besedina N, Kirilenko DA, Shvidchenko A (2017) Ultracentrifugation for ultrafine nanodiamond fractionation. Superlattice Microst 113:201–212. CrossRefGoogle Scholar
  15. Krueger A (2008) The structure and reactivity of nanoscale diamond. J Mater Chem 18:1485–1492. CrossRefGoogle Scholar
  16. Krueger A, Kataoka F, Ozawa M, Fujino T, Suzuki Y, Aleksenskij AE, Vul AY, Ōsawa E (2005) Unusually tight aggregation in detonation nanodiamond: identification and disintegration. Carbon 43(8):1722–1730. CrossRefGoogle Scholar
  17. Krueger A, Liang Y, Jarre G, Stegk J (2006) Surface functionalisation of detonation diamond suitable for biological applications. J Mater Chem 16:2322–2328. CrossRefGoogle Scholar
  18. Lamouri S (2017) Control of the γ-alumina to α-alumina phase transformation for an optimized alumina densification. Boletín de La Sociedad Española de Cerámica y Vidrio 56:47–54. CrossRefGoogle Scholar
  19. Li C-C, Huang C-L (2010) Preparation of clear colloidal solutions of detonation nanodiamond in organic solvents. Colloid Surface A 353:52–56. CrossRefGoogle Scholar
  20. Liang Y, Meinhardt T, Jarre G, Ozawa M, Vrdoljak P, Schöll A, Reinert F, Krueger A (2011) Deagglomeration and surface modification of thermally annealed nanoscale diamond. J Colloid Interface Sci 354:23–30. CrossRefGoogle Scholar
  21. Liu Y, Gu Z, Margrave JL, Khabashesku VN (2004) Functionalization of nanoscale diamond powder: fluoro-, alkyl-, amino-, and amino acid-nanodiamond derivatives. Chem Mater 16(20):3924–3930. CrossRefGoogle Scholar
  22. Ma T (2014) Oxidant generation on photolysis of silver chloride suspensions: implications to organic contaminant degradation. Ph.D thesis. University of New South Wales. Accessed August 2019
  23. Maas M (2016) Carbon nanomaterials as antibacterial colloids. Materials 9(8):617. CrossRefGoogle Scholar
  24. Mandelbrot BB (1977) Fractals: form, chance, and dimension. CA: WH Freeman and Company, San FranciscoGoogle Scholar
  25. Migdisov AA, Williams-Jones AE, Suleimenov OM (1999) Solubility of chlorargyrite (AgCl) in water vapor at elevated temperatures and pressures. Geochim Cosmochim Acta 63(22):3817–3827. CrossRefGoogle Scholar
  26. Mitev DP, Townsend AT, Paull B, Nesterenko PN (2014) Screening of elemental impurities in commercial detonation nanodiamond using sector field inductively coupled plasma-mass spectrometry. J Mater Sci 49:3573–3591. CrossRefGoogle Scholar
  27. Mochalin VN, Shenderova O, Ho D, Gogotsi Y (2012) The properties and applications of nanodiamonds. Nat Nanotechnol 7(1):11–23. CrossRefGoogle Scholar
  28. Oliver A, Williams OA, Hees J, Dieker C, Jager W, Kirste L, Nebel CE (2010) Size-dependent reactivity of diamond nanoparticles. ACS Nano 4(8):824–4830. CrossRefGoogle Scholar
  29. Osawa E (2008) Monodisperse single nanodiamond particulates. Pure Appl Chem 80(7):1365–1379. CrossRefGoogle Scholar
  30. Osswald S, Havel M, Mochalin V, Yushin G, Gogotsi Y (2008) Increase of nanodiamond crystal size by selective oxidation. Diam Relat Mater 17(7–10):1122–1126. CrossRefGoogle Scholar
  31. Osswald S, Yushin G, Mochalin V, Kucheyev SO, Gogotsi Y (2006) Control of sp2/sp3 carbon ratio and surface chemistry of nanodiamond powders by selective oxidation in air. J Am Chem Soc 128(35):11635–11642. CrossRefGoogle Scholar
  32. Ozawa M, Inaguma M, Takahashi M, Kataoka F, Krüger A, Osawa E (2007) Preparation and behavior of brownish, clear nanodiamond colloids. Adv Mater 19:1201–1206. CrossRefGoogle Scholar
  33. Paci JT, Man HB, Saha B, Ho D, Schatz GC (2013) Understanding the surfaces of nanodiamonds. J Phys Chem C 117(33):17256–17267. CrossRefGoogle Scholar
  34. Pedroso-Santana S, Sarabia-Saínz A, Fleitas-Salazar N, Santacruz-Gómez K, Acosta-Elías M, Pedroza-Montero M, Riera R (2017) Deagglomeration and characterization of detonation nanodiamonds for biomedical applications. J Appl Biomed 15(1):15–21. CrossRefGoogle Scholar
  35. Petit T, Arnault J-C, Girard HA, Sennour M, Kang T-Y, Cheng C-L, Bergonzo P (2012) Oxygen hole doping of nanodiamond. Nanoscale 4:6792–6799. CrossRefGoogle Scholar
  36. Phiri J, Gane P, Maloney TC (2017) General overview of graphene: production, properties and application in polymer composites. Mater Sci Eng B 215:9–28. CrossRefGoogle Scholar
  37. Pichot V, Risse B, Schnell F, Mory J, Spitzer D (2013) Understanding ultrafine nanodiamond formation using nanostructured explosives. Sci Rep 3:2159. CrossRefGoogle Scholar
  38. Rai DK, Beaucage G, Vogt K, Ilavsky J, Kammler HK (2018) In situ study of aggregate topology during growth of pyrolytic silica. J Aerosol Sci 118:34–44. CrossRefGoogle Scholar
  39. Ray MA, Tyler T, Hook B, Martin A, Cunningham G, Shenderova JL (2007) Cool plasma functionalization of nano-crys-talline diamond films. Diam Relat Mater 16:2087–2089. CrossRefGoogle Scholar
  40. Schaefer DW, Martin JE, Wiltzius P, Cannell DS (1984) Fractal geometry of colloidal aggregates. Phys Rev Lett 52(26):2371–2374. CrossRefGoogle Scholar
  41. Shakun A, Vuorinen J, Hoikkanen M, Poikelispää M, Das A (2014) Hard nanodiamonds in soft rubbers: past, present and future—a review. Compos Part A Appl Sci Manuf 64:49–69. CrossRefGoogle Scholar
  42. Shames AI, Panich AM, Kempiński W, Alexenskii AE, Baidakova MV, Dideikin AT, Osipov VY, Siklitski VI, Osawa E, Ozawa M, Vul AY (2002) Defects and impurities in nanodiamonds: EPR, NMR and TEM study. J Phys Chem Solids 63(11):1993–2001. CrossRefGoogle Scholar
  43. Shenderova O, Panich AM, Moseenkov S, Hens SC, Kuznetsov V, Vieth HM (2011) Hydroxylated detonation nanodiamond: FTIR, XPS, and NMR studies. J Phys Chem C 115(39):19005–19011. CrossRefGoogle Scholar
  44. Shenderova OA, Zhirnov VV, Brenner DW (2002) Carbon nanostructures. Crit Rev Solid State Mater Sci 27:227–356. CrossRefGoogle Scholar
  45. Singh B, Smith SJ, Jensen DS, Jones HF, Dadson AE, Farnsworth PB, Vanfleet R, Farrer JK, Linford MR (2016) Multi-instrument characterization of five nanodiamond samples: a thorough example of nanomaterial characterization. Anal Bioanal Chem 408(4):1107–1124. CrossRefGoogle Scholar
  46. Song J, Roh J, Lee I, Jang J (2013) Low temperature aqueous phase synthesis of silver/silver chloride plasmonic nanoparticles as visible light photocatalysts. Dalton Trans 42(38):13897–13904. CrossRefGoogle Scholar
  47. Sotowa K-I, Amamoto T, Sobana A, Kusakabe K, Imato T (2004) Effect of treatment temperature on the amination of chlorinated diamond. Diam Relat Mater 13(1):145–150. CrossRefGoogle Scholar
  48. Stehlik S, Glatzel T, Pichot V, Pawlak R, Meyer E, Spitzer D, Rezek B (2015) Water interaction with hydrogenated and oxidized detonation nanodiamonds—microscopic and spectroscopic analyses. Diam Relat Mater 63:97–102. CrossRefGoogle Scholar
  49. Stehlik S, Varga M, Ledinsky M, Miliaieva D, Kozak H, Skakalova V, Mangler C, Pennycook TJ, Meyer JC, Kromka A, Rezek B (2016) High-yield fabrication and properties of 1.4 nm nanodiamonds with narrow size distribution. Sci Rep 6:38419. CrossRefGoogle Scholar
  50. Stevenson K, McVey AF, Clark IBN, Swain PS, Pilizota T (2016) General calibration of microbial growth in microplate readers. Sci Rep 6:38828. CrossRefGoogle Scholar
  51. Ten KA, Pruuel ER, Titov VM (2012) SAXS measurement and dynamics of condensed carbon growth at detonation of condensed high explosives. J Fuller Nanotub Car N 20:587–593. CrossRefGoogle Scholar
  52. Tomchuk OV, Volkov DS, Bulavin LA, Rogachev AV, Proskurnin MA, Korobov MV, Avdeev MV (2015) Structural characteristics of aqueous dispersions of detonation nanodiamond and their aggregate fractions as revealed by small-angle neutron scattering. J Phys Chem C 119(1):794–802. CrossRefGoogle Scholar
  53. Turner S, Lebedev OI, Shenderova O, Vlasov II, Verbeeck J, Tendeloo GV (2009) Determination of size, morphology, and nitrogen impurity location in treated detonation nanodiamond by transmission electron microscopy. Adv Funct Mater 19(13):2116–2124. CrossRefGoogle Scholar
  54. Volkov DS, Proskurnin MA, Korobov MV (2014) Elemental analysis of nanodiamonds by inductively-coupled plasma atomic emission spectroscopy. Carbon 74:1–13. CrossRefGoogle Scholar
  55. Vul A, Shenderova O (2014) Detonation nanodiamonds: science and applications. Pan Stanford Publishing, SingaporeCrossRefGoogle Scholar
  56. Xu XY, Zhu Y, Wang B, Yu Z, Xie S (2005) Mechanochemical dispersion of NDs aggregates in aqueous media. J Mater Sci Technol 21:109–112Google Scholar
  57. Zeiger M, Jackel N, Mochalin VN, Volker P (2016) Review: carbon onions for electrochemical energy storage. J Mater Chem A 4:3172–3196. CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2020

Authors and Affiliations

  1. 1.New Technologies – Research CentreUniversity of West BohemiaPilsenCzech Republic
  2. 2.Advanced Photon SourceArgonne National LaboratoryArgonneUSA
  3. 3.Institute of Chemical Process Fundamentals, ASCR, v.v.iPragueCzech Republic
  4. 4.Advanced CeramicsUniversity of BremenBremenGermany
  5. 5.MAPEX–Center for Materials and ProcessesUniversity of BremenBremenGermany

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