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WO2007102753A1 - Substances synthétiques diamantées et procédé de fabrication - Google Patents

Substances synthétiques diamantées et procédé de fabrication Download PDF

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Publication number
WO2007102753A1
WO2007102753A1 PCT/RU2007/000110 RU2007000110W WO2007102753A1 WO 2007102753 A1 WO2007102753 A1 WO 2007102753A1 RU 2007000110 W RU2007000110 W RU 2007000110W WO 2007102753 A1 WO2007102753 A1 WO 2007102753A1
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mass
diamond
carbon
nitrogen
oxygen
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Russian (ru)
Inventor
Alexey Petrovich Puzyr
Valery Borisovich Vorobyov
Vladimir Stanislavovich Bondar
Ludmila Konstantinovna Popitchenko
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/25—Diamond

Definitions

  • the invention relates to the field of inorganic chemistry of carbon, namely, to nanosized carbon materials and a method for their isolation and can be used in various fields of industry and science, where detonation nanodiamonds powders or their sols are used.
  • Synthetic carbon diamond-containing material is known [p. RF
  • the specified material contains elements in the following ratio, mass. %: carbon 65 - 80, hydrogen 0.6 - 3.3, nitrogen 1.4 - 3.4, oxygen 13.3 - 33.0, while carbon contains 8 - 40 mass. % non-diamond forms. Closest to the claimed is a diamond-carbon substance [p. RF
  • This substance contains elements in the following ratio, mass. %: carbon 89 - 93, particles of silicon, metals up to 1.5, hydrogen, oxygen and nitrogen - the rest, while 96.0 - 99.6 mass. % of carbon is contained in diamond form, and the specific surface of the powder of the obtained substance is in the range of 400 - 500 m / g.
  • the closest way to the claimed is a method [p. RF, 2183583 IPC ⁇ 01 ⁇ 31/06, publ. 06/20/2002, bull. Na 22], where a diamond-containing substance of high purity is obtained by additional purification of the primary powder, which is carried out in several stages by sequential treatment with solutions of alkali, hydrochloric or nitric acid with washing the precipitate with distilled water to pH 7 after each stage and subsequent washing in perchloric acid. Further the precipitate is washed with distilled water to a pH of 6.5 - 7.0, the water is drained by decantation, the precipitate is concentrated in a centrifuge and dried at a temperature of +100 - 120 ° C to a moisture content of 1 - 2%.
  • the objective of the invention is to obtain synthetic diamond-containing substances with the properties of repeatedly reproducing stable colloidal systems and the ability to fractionate.
  • the main objective of the invention is to obtain synthetic diamond-containing substances of high purity, forming free-dispersed systems with high colloidal stability and the ability to fractionate. Another goal is to use dry matter as raw material.
  • the aim of the invention is also the economy and convenience in the transportation of raw materials and obtained from it diamond-containing substances.
  • Other objectives, advantages and advantages of this invention in addition to those mentioned above will be clearer when considering a detailed description of the invention and the accompanying drawings (illustrations).
  • a synthetic diamond-containing substance containing in wt.%: Carbon 97.5 - 98.5, hydrogen 0.09 - 0.2, nitrogen 0.3 - 0.5, oxygen 0.6 - 1,0, including non-diamond carbon in the range 0.2 - 5, as well as impurities of metals 0.5 - 0.8, having a zeta potential from 0 to -75 mB. And which has the ability to form free-dispersed systems with high colloidal stability of the particles and is capable of fractionation with a narrow particle size distribution from 3 to 8000 nm.
  • the inventive method allows to obtain well-purified diamond-containing substances with high zeta potential, possessing the ability to form free-dispersed systems, which, with the simple addition of water (without the use of ultrasonic treatment) form hydrosols with increased colloidal stability of nanoparticles, allowing fractionation by any known method, for example, centrifugation. Repeated drying and simple addition of water both to non-fractionated powders and to individual fractions allows us to obtain stable hydrosols again, which indicates that nanoparticles are capable of forming free-dispersed systems.
  • the obtained diamond-containing substances that retain dry characteristics (powder) are convenient and economical in transportation.
  • the use of nanodiamonds as raw materials obtained both during the synthesis of TNT-G and G-G in the form of the initial dry matter, rather than a hydrosol of nanoparticles, is also very convenient and economical for transportation.
  • Figure 1 shows the sizes of nanoparticles and their clusters, determined by the scattering indicatrix in the hydrosols forming free-dispersed systems for the TNT-G synthesis mode: 1 - not fractionated substance; 2 - simple addition of water to the fraction of large particles; 3 - simple addition of water to the fraction of fine particles; 4 - ultrasonic treatment of the fraction of fine particles; 5 - lyosol, size less than 100 nm (additional fractionation of the fraction of small particles).
  • Figure 2 shows the sizes of nanoparticles and their clusters forming free-dispersed systems, determined by the scattering indicatrix in hydrosols (device — ⁇ oulter N ° 5), for the synthesis mode G-D: 1 - non-fractionated substance; 2 - fraction of small particles; 3 - fraction of large particles.
  • the distribution of non-fractionated nanoparticles and their clusters forming free-dispersed systems is given for the synthesis mode G-G recorded on the VideoTexture system.
  • Figure 4 presents the Auger spectrum of the fraction of small particles forming free-dispersed systems for the synthesis regime of TNT-G.
  • Figure 5 shows the x-ray (device DRON-3) of the feedstock (1) and the fractions of small (2) and large (3) nanoparticles separated from it forming free-dispersed systems.
  • Figure 6 presents the EPR spectra (RE 1307 radio spectrometer) of the feedstock (1) and the fractions of large (2, 4) and small (3, 5) nanoparticles separated from it forming free-dispersed systems.
  • Figure 7 presents the IR spectra (spectrometer company Bruker) of raw materials (1) and the substance obtained from it, forming free-dispersed systems (2).
  • Fig presents the IR spectrum (spectrometer company Bruker) of impurities that are removed by this method from the surface of the nanoparticles.
  • Figure 9 shows a histogram reflecting the change in the optical density of hydrosols during ten cycles of their drying and the subsequent addition of water to a dry powder (UV-300 spectrophotometer from Shimadzu).
  • the method for isolating synthetic diamond-containing substances is carried out in several stages, successively washing the diamond-containing substance powder with organic solvents, for example: in a Soxhlet apparatus, in a glass flask made of heat-resistant glass, with a reflux condenser.
  • organic solvents for example: in a Soxhlet apparatus, in a glass flask made of heat-resistant glass, with a reflux condenser.
  • the sequence of solvents must be from hydrophobic to hydrophilic; the previous liquid should dissolve well (mix with the next, for example: chloroform, benzene, acetone, alcohol).
  • other combinations of other organic solvents can be used, for example, 1, 2-dichloroethane, benzene, dimethylformamide, dimethyl sulfoxide.
  • Example 1 Raw materials (powder of nanodiamonds synthesized according to the TNT-G method in Krasnoyarsk) in an amount of 3g are placed in a glass flask of heat-resistant glass with a volume of 100-150 ml, 50 ml of chloroform are poured, the reflux condenser is installed and the mixture is brought to a sand bath boil and boil for 10-15 minutes. After the mixture has cooled, the liquid is removed by decantation, and 50 ml of benzene is poured into the flask. The process of heating, boiling and removing the benzene solution is repeated. Similar procedures are carried out sequentially with acetone and alcohol.
  • the solvent is removed by decantation, the powder is dried at a temperature of 100 ° C, to a moisture content of 1-2%.
  • a gray powder is obtained in an amount of 2.76 tons (weight loss 8%) with the following ratio of elements, mass%: carbon 82-91, including non-diamond carbon in the range of 2-25; hydrogen 0.8-1.5; nitrogen 1.1-2.2; oxygen 6.0-13.0 and metal impurities 1.1-1.3.
  • a hydrosol is obtained, allowing fractionation to be carried out by any known method (in this case, centrifugation).
  • Example 2 The powder of polycrystalline nanodiamonds produced by LLC "Peal-Dzherzhinsk", obtained by blasting GG, which is a raw material, in the amount of 5 g is placed in a glass flask made of heat-resistant glass, filled with an organic solvent in an amount of 50 - 100 ml and in a sand bath reflux for 10-15 minutes. After the mixture has cooled, the liquid is removed by any method (other than evaporation) and replaced with the next solvent. The sequence from hydrophobic to hydrophilic is observed. Recommended liquids and their sequence are chloroform, benzene, acetone, dimethylformamide, alcohol.
  • a gray powder is obtained in an amount of 4.75 g (weight loss 5%) with the following ratio of elements, wt.%: Carbon 97.5-98.5, including non-diamond carbon in the range of 0.2-5; hydrogen 0.09-0.2-; nitrogen 0.3-0.5; oxygen 0.6-1.0; and metal impurities 0.51-0.8.
  • a hydrosol is obtained, which allows fractionation by any known method (in this case, centrifugation).
  • Example 3 The powder of nanodiamonds of batch N ° 11, synthesized in Krasnoyarsk with TNT-G blast, which is a raw material, in an amount of 2 g is placed in a Soxhlet apparatus. A sequential washing of the powder with organic solvents (chloroform, benzene, acetone, alcohol) is carried out for 10 cycles of each solvent in an amount of 100 ml. After the cleaning process, the solvent is removed by decantation, the powder is dried at a temperature of 100 ° C, to a moisture content of 1-2%. After this treatment, a gray powder is obtained in an amount of 1.86 g.
  • organic solvents chloroform, benzene, acetone, alcohol
  • Example 4 The powder of nanodiamonds produced by LLC "Peal-Dzherzhinsk” obtained by blasting GG, which is the raw material, in an amount of 2 g is placed in Soxhlet apparatus. The powder is sequentially washed with organic solvents (1,2-dichloroethane, benzene, dimethylformamide, dimethyl sulfoxide) for 10 cycles of changing each solvent in an amount of 100 ml. After the cleaning process, the solvent is removed by decantation, the powder is dried at a temperature of 80 ° C, to a moisture content of 1-2%.
  • organic solvents (1,2-dichloroethane, benzene, dimethylformamide, dimethyl sulfoxide
  • a gray powder is obtained in an amount of l, 93 g (weight loss 3.5%) with the following ratio of elements, wt%: carbon 97.5-98.5, including non-diamond carbon in the range 0.2-5; hydrogen 0.09-0.2; nitrogen 0.3-0.5; oxygen 0.6-1.0; and metal impurities 0.51-0.8.
  • a hydrosol is obtained, which allows fractionation by any known method (in this case, centrifugation).
  • centrifugation powders are obtained with characteristics depending on the fractional composition, which are given in table l (batches of substances 4,5,6). Repeated drying and simple addition of water both to the non-fractionated powder and to individual fractions makes it possible to obtain stable hydrosols again, which indicates that the nanoparticles are free-dispersed.
  • a synthetic diamond-containing substance obtained by the claimed method from TNT-G synthesis products is a powder from light gray to black, depending on the fractional composition and has the following elemental composition in mass. %: carbon 82 - 91; hydrogen 0.8-1.5; nitrogen 1.1 to 2.2; oxygen 6.0 - 13.0 and non-diamond carbon in the range 2 - 25, as well as metal impurities 1.1 - 1.3, zeta potential from -40 to -85 mB (measured in the region of the positive electrode, KCl electrolyte).
  • the sizes of non-fractionated nanoparticles and their clusters in hydrosols, determined by the scattering indicatrix or by the sedimentation method, for the TNT-G synthesis mode lie in the range 3 - 1700 nm (Fig. 1, curve 1), cluster sizes of fractionated particles in hydrosols make it possible to obtain lyosols with sizes less than 100 nm (Fig. 1, curve 5), and the range of values of the specific surface area, determined by the adsorption of argon on the GX-1 gas meter, is from 300 m 2 / g with an average cluster size of 300 - 400 nm (Fig. 1) , curve 2) and up to 420 m 2 / g with an average values of clusters 30–50 nm (Fig.
  • the synthetic diamond-containing substance obtained by the claimed method from the products of synthesis GG is also a powder from light gray to black, depending on the fractional composition and has the following elemental composition, mass. %: carbon 97.5 - 98.5; hydrogen 0.09 - 0.2; nitrogen 0.3 to 0.5; oxygen 0.6 - 1.0, and non-diamond carbon within 0.2 - 5, as well as metal impurities 0.5 - 0.8, zeta potential from 0 to -75 mV (measured in the region of the positive electrode, KCl electrolyte )
  • diamond-containing substances isolated by this method from the synthesis products of TNT-G or G-G have a number of common properties and characteristics.
  • the parameters of the crystal lattices and the sizes of the primary particles correspond to the parameters of the crystal lattices and the sizes of the primary particles of the raw materials used and are independent of the fractional composition.
  • the X-ray diffraction pattern (Fig. 5) obtained on the DRON-3 device, the separated fractions of nanoparticles forming free-dispersed systems are diamonds (peaks (111), (220), (311). Comparative X-ray diffraction studies of the diamond component suggest that the raw materials and the isolated fractions consist of identical diamond nanocrystallites.For the samples shown in Fig.
  • the characteristic nanocrystallite size determined by the Hall-Williamson method [Williamsop GK, HaIl W.N. X-line line broadening filum alumipium apd wolfram. 1, 22-31.], Equal to 3.5 nm, and the level of microdeformations is insignificant and does not exceed 0.06%.
  • the crystal lattice parameter is 0.3561 ⁇ 0.0007 nm, which corresponds to a theoretical nanodiamond density of 3.56 g / cm 3.
  • the Kvant-2a atomic absorption spectrometer contains (mg / kg): Fe - 23960; Ca - 21180; Na - 19020; K - 1650; Cu - 1241.02; Mg 1170; Cr 509.18; Zn - 328.69; Ni - 283.61; Mn - 7.526; Co - 5.38. Volumetric titration is used to determine S - 10800 mg / kg. According to the data obtained using emission spectroscopy (spectrograph PGS-2 Karl Zeis Jepa), contains (%): Ti - 4.7; Al -1.28; Sr -0.46; V-0.07; Mo -0.0152; B -0.0034.
  • the zeta potential values are usually in the range of -30 ⁇ -38 mV [G.A. Chiganova. Colloid Journal 1994, 56, 2, 266. G.A. Chiganova. Colloid Journal 2000, 62, 2, 272).].
  • the zeta potential is in the range of -40 ⁇ -85 mV, and for particles of the synthesis of G-G the zeta potential is determined in the range from 0 to -75 mB.
  • the observed low value of the zeta potential (for batches of substances 5-6, Table l) is associated with large sizes of nanodiamond clusters, for which calculations according to the theory of DFLO and additional counteraction of gravitational forces due to the large mass of clusters are not applicable.
  • a high value of the zeta potential indicates an increase in the energy of electrostatic repulsion of particles, proportional to the square of the potential of the diffuse layer, which is equivalent to the electrokinetic potential in dilute electrolyte solutions, and in combination with increased surface purity contributes to the claimed diamond-containing substances properties to the formation of free-dispersed systems. This property is illustrated by the histogram in Fig.9. INDUSTRIAL APPLICABILITY
  • inventive diamond-containing substances with the ability to form free-dispersed systems can be used in biomedical research for the preparation of stable sterile sols with a strictly defined weight concentration of particles intended for oral administration and all types of injections. After freezing and thawing them, the hydrosol nanoparticles do not form aggregates, the nanoparticles can be evenly distributed on an agar gel.
  • synthetic diamond-containing substances with the ability to form free-dispersed systems can be used to produce colloidal systems with enhanced nanoparticle stability in oils, organic solvents, and other liquids, which makes it possible to use them in lubricating oils to improve the performance of engines and polishing pastes for processing substrates information media, polishing precious stones, etc.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

L'invention vise la fabrication de matériaux composites et peut s'utiliser notamment en médecine. La substance diamantée présente un rapport de composants suivant : 82-91 % en masse de carbone, 0,8-1,5 % en masse d'azote, 6,0-13,0 % en masse d'oxygène, 2-25 % en masse de carbone non diamanté et 1,1-1,3 % en masse d'impuretés de métaux. Elle a un potentiel zêta de -40 à -85 mV et est capable d'être fractionnée avec une répartition étroite des particules suivant leurs dimensions, de 3 à 1700 nm. Dans une autre variante la substance diamantée présente un rapport de composants suivant : 97,5-98,5 % en masse de carbone, 0,09-0,2 % en masse d'hydrogène, 0,3-0,5 % en masse d'azote, 0,6-1,0 % en masse d'oxygène, 0,2-25 % en masse de carbone non diamanté, 0,5-0,8 % en masse d'impuretés de métaux. Elle a un potentiel zêta de 0 à -75 mV et est capable d'être fractionnée avec une répartition étroite des particules suivant leurs dimensions, de 3 à 8000 nm. Dans les deux variantes, les substances sont capables de former des systèmes à dispersion libre présentant une stabilité colloïdale élevée. Le procédé de fabrication de substances synthétiques diamantées comprend le traitement consécutif d'une poudre sèche de nano-diamant avec des solvants organiques bouillants, des hydrophobes jusqu'aux hydrophiles, effectué de façon que le solvant précédent soit dissous dans le solvant suivant, après quoi les solvants sont évacués et la poudre est séchée.
PCT/RU2007/000110 2006-03-06 2007-03-01 Substances synthétiques diamantées et procédé de fabrication Ceased WO2007102753A1 (fr)

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RU2485047C1 (ru) * 2011-11-03 2013-06-20 Федеральное государственное бюджетное научное учреждение "Технологический институт сверхтвердых и новых углеродных материалов" (ФГБНУ ТИСНУМ) Способ получения углерод-азотного материала
RU2569510C2 (ru) * 2013-04-17 2015-11-27 федеральное государственное бюджетное учреждение "Федеральный научно-исследовательский центр эпидемиологии и микробиологии имени почетного академика Н.Ф. Гамалеи" Министерства здравохранения Российской Федерации Сорбент, представляющий собой наноалмазный материал (варианты), способы получения и использования.

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2041165C1 (ru) * 1993-02-12 1995-08-09 Научно-производственное объединение "Алтай" Алмазоуглеродное вещество и способ его получения
RU2046094C1 (ru) * 1993-05-26 1995-10-20 Татьяна Михайловна Губаревич Синтетический углеродный алмазсодержащий материал
RU2051092C1 (ru) * 1991-12-25 1995-12-27 Научно-производственное объединение "Алтай" Алмазсодержащее вещество и способ его получения
RU2183583C2 (ru) * 1999-10-07 2002-06-20 Комбинат "Электрохимприбор" Алмазоуглеродное вещество и способ его получения

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2051092C1 (ru) * 1991-12-25 1995-12-27 Научно-производственное объединение "Алтай" Алмазсодержащее вещество и способ его получения
RU2041165C1 (ru) * 1993-02-12 1995-08-09 Научно-производственное объединение "Алтай" Алмазоуглеродное вещество и способ его получения
RU2046094C1 (ru) * 1993-05-26 1995-10-20 Татьяна Михайловна Губаревич Синтетический углеродный алмазсодержащий материал
RU2183583C2 (ru) * 1999-10-07 2002-06-20 Комбинат "Электрохимприбор" Алмазоуглеродное вещество и способ его получения

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DOLMATOV V.Y.: "Ultradispersnye almazy detonatsionnogo sinteza: svoistva i primenenie", USPEKHI KHIMII, vol. 70, no. 7, 2001, pages 689 - 690, 698 - 699, XP008149169, DOI: doi:10.1 070jRCZOO I v07On07 ABEH000665 *

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