WO2012175462A1 - Procédé pour obtenir des nanoparticules contenant du bore et du silicium - Google Patents

Procédé pour obtenir des nanoparticules contenant du bore et du silicium Download PDF

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Publication number
WO2012175462A1
WO2012175462A1 PCT/EP2012/061628 EP2012061628W WO2012175462A1 WO 2012175462 A1 WO2012175462 A1 WO 2012175462A1 EP 2012061628 W EP2012061628 W EP 2012061628W WO 2012175462 A1 WO2012175462 A1 WO 2012175462A1
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WIPO (PCT)
Prior art keywords
boron
nanoparticles
silicon
laser
gas mixture
Prior art date
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Ceased
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PCT/EP2012/061628
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English (en)
Inventor
Ara Arshavirovich Abramyan
Viacheslav Ivanovich Beklemyshev
Sergey Borisovich KOROVIN
Igor Ivanovich Makhonin
Umberto Orazio Giuseppe Maugeri
Vladimir Ivanovich Pustovoy
Vladimir Aleksandrovich Solodovnikov
Aleksey Gennadievich VLADIMIROV
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fondazione Salvatore Maugeri Clinica del Lavora e della Riabilitazione
SIB LABORATORIES Ltd
CLOSED STOCK Co "INSTITUTE OF APPLIED NANOTECHNOLOGY"
Original Assignee
Fondazione Salvatore Maugeri Clinica del Lavora e della Riabilitazione
SIB LABORATORIES Ltd
CLOSED STOCK Co "INSTITUTE OF APPLIED NANOTECHNOLOGY"
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Application filed by Fondazione Salvatore Maugeri Clinica del Lavora e della Riabilitazione, SIB LABORATORIES Ltd, CLOSED STOCK Co "INSTITUTE OF APPLIED NANOTECHNOLOGY" filed Critical Fondazione Salvatore Maugeri Clinica del Lavora e della Riabilitazione
Publication of WO2012175462A1 publication Critical patent/WO2012175462A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C01B35/00—Boron; Compounds thereof
    • C01B35/02—Boron; Borides
    • C01B35/04—Metal borides

Definitions

  • the invention concerns nanotechnology, in particular processes for obtaining nanoparticles and specifically a process for obtaining boron- silicon containing nanoparticles.
  • Boron containing compounds and their nanostructures are widely used for structural composite materials and surface coatings.
  • boron containing compounds are used in biology and medicine, including in the diagnosis and treatment of cancer.
  • Application of effective boron containing compounds, including boron-containing nanoparticles, is perspective to Boron Neutron Capture Therapy (BNCT) of cancer.
  • BNCT Boron Neutron Capture Therapy
  • silicon containing nanoparticles possess biocompatibility and penetrating ability and that can be used as functional agents of drugs. It was also ascertained that the silicon nanoparticles have a high quantum yield of luminescence and that can be applied in medicine and biology as fluorescent markers in the diagnosis of diseases.
  • a process for obtaining boron containing compounds on the basis of boron silicide, by means of plasma-chemical synthesis, consisting in the use of gas reagents: boron trichloride (BC1 3 ), silicomethane (SiH 4 ) and hydrogen (H 2 ) at a concentration in mole , respectively, as follows: 10-40; 0,1 - 1,5; 55-90.
  • gas reagents boron trichloride (BC1 3 ), silicomethane (SiH 4 ) and hydrogen (H 2 ) at a concentration in mole , respectively, as follows: 10-40; 0,1 - 1,5; 55-90.
  • the process is carried out at the temperature of 1000 - 1300°C.
  • films of boron silicide in the form of monofilament, with a diameter about 12-50 microns, deposited on surfaces see patent US No. 3607367 «High-strenght, hight- modulus, low density, boron silicide monofilaments, and method of making same » published 21 September 1971).
  • the use of the reagent hydrogen leads to complication of the process and of the hardware.
  • the obtained structures of boron silicide are not nanoscale, what limits the technological possibilities of their use in biology and medicine.
  • boron (B) particles and titanium diboride (TiB 2 ), by laser-induced pyrolysis are also known.
  • the particles of boron and titanium diboride were obtained by inducing the reaction of pyrolysis in the mixture of reacting gases, by means of infrared continues radiation of C0 2 - laser (power 150 W, wave length 10.591 ⁇ ).
  • Boron particles (B) were obtained from the reaction of boron trichloride and hydrogen (BCI 3 +H 2 ) or from diborane (B 2 H 6 ).
  • Particles of titanium diboride (TiB 2 ) were obtained from the reaction of a gas mixture consisting of T1CI 4 +B 2 H 6 .
  • nanoparticles of silicon and silicon-containing nanoparticles were obtained on the basis of the method of laser-induced pyrolysis of silicomethane (S1H 4 ).
  • the method for obtaining silicon nanoparticles consists in supplying the reaction gas mixture containing monosilane (SiH4) with a reagent "B” and a buffer gas into the flow reactor; and in the induction of the pyrolysis reaction of gas mixture by continuous radiation of C0 2 - laser, at pressure of the gas mixture in the reactor, below atmospheric pressure.
  • Ammonia (NH 4 ) or methane (CH 4 ) is used as the agent “B” in this technical solution.
  • a buffer gas in particular argon (Ar), is used for realization of exothermic reactions of pyrolysis of the gas mixture.
  • the obtained nanoparticles were examined by the methods of transmission electron microscopy, dynamic light scattering, electron diffraction and infrared spectroscopy.
  • the nanoparticles have composite structure with presence of bonds Si-N and Si-C and a narrow dispersion in the sizes.
  • the process described allows adjusting parameters of synthesis of nanoparticles: density of the power of radiation of C0 2 - laser in the zone of reaction; the pressure in the flow reactor; the flow rates of gas reagents which makes it possible to control the sizes of particles and a degree of dispersiveness in a narrow range.
  • boron containing compounds and nanoparticles can effectively be used in boron neutron capture therapy (BNCT)) for diagnostics and therapies of various oncological diseases (see application US No. 2005/0180917 Al "Delivery of neutron capture elements for neutron capture therapy", published on 18 August 2005; application WO 2005/094884 A2 "Boron containing nanoparticles targeted to T-cells", published on 13 October 2005; the article "Boron neutron capture therapy of cancer. Chemical aspect”, Russian chemical journal, The Russian chemical society named D.I.Mendeleyev, 2004, v. XLVIII, N.4, p. 109-125).
  • BNCT boron neutron capture therapy
  • These compounds are obtained by a multi-stage procedure using a sol-gel process involving hydrolysis of boron alkoxides (B-(OR)n) and silicon alkoxides (Si-(OR)n); obtaining oxides of boron and silicon; sintering products of the reaction (sol-gel process) at temperatures 100° - 1000° C; distillation of organic residues; completion of the hydrolysis and reaction of compaction of the products.
  • B-(OR)n boron alkoxides
  • Si-(OR)n silicon alkoxides
  • the implemented process does not allow controlling the dimension of the particles and the degree of their dispersion.
  • Multistep process is associated with significant costs including for cleaning obtained products from impurities of chemical reactions.
  • the new technical result of the invention consists in expanding the technological capabilities of the method of laser-induced pyrolysis for obtaining boron-silicon containing nanoparticles, with high concentration of boron in them.
  • the present process of obtaining boron-silicon containing nanoparticles consists in: filling a flow reactor with a reactive gas mixture containing silicomethane (SiH 4 ) with a reagent «B» and a buffer gas; in the induction of the pyrolysis of the gas mixture by continuous radiation of C0 2 -laser, under pressure of the gas mixture below the atmospheric one.
  • Boron trichloride (BCI 3 ) is used as the reagent «B».
  • the process is carried out at a ratio of consumption of the gases as follows - silicomethane : reagent B : buffer gas as 1 : (1,2-1,5) : (45-55), and at a density of the power of laser radiation of 6000-8000 W/cm . Nanoparticles are obtained with contents of boron of 55-65 (at. %) and silicon as the rest.
  • the reaction is carried out under pressure of the gas mixture in the reactor of 400-650 torr.
  • helium He is used as a buffer gas.
  • boron-silicon containing nanoparticles with the size of 5- 30 nm are obtained.
  • boron-silicon containing nanoparticles are obtained in laser-induced pyrolysis of the reaction gas mixture, on the basis of compounds of boron and compounds of silicon.
  • the declared invention can be realized with use of equipment and materials used in known technological processes for obtaining nanoparticles.
  • Fig.l is a chematic diagram of the equipment for obtaining boron-silicon containing nanoparticles.
  • Fig. 2 shows images of boron-silicon containing nanoparticles (method of transmission electron microscopy).
  • Fig. 3 shows X-ray photoelectron spectra of boron contained in nanoparticles (method of X-ray photoelectron spectroscopy).
  • Fig. 4 shows X-ray photoelectron spectra of silicon contained in nanoparticles (method of X-ray photoelectron spectroscopy).
  • the equipment for obtaining boron-silicon containing nanoparticles (Fig. 1) used for realization of the invention, contains the following devices:
  • C0 2 -laser radiator 1 of continuous action ILGN-802, output power 70 W, wave length ⁇ 10,6 ⁇ , beam diameter in the waist - 1 mm (Federal State Unitary Enterprise, Scientific-Production Enterprise «Istok», Russia); a flow reactor 2 with a reaction quartz tube with a capillary for supplying gas mixture (Institute of General Physics named A.M.Prohorov of RAS, Russia); lens system 3 from NaCl and ZnSe (Company «Electroglass», Russia); the gas inlet panel 4 with rotameters RMA-0,063 and control of gas flow RRG-12 (Company «Rotameter», Russia; Company «Eltochpribor», Russia); the filter unit 5 with replaceable filter cells for accumulation of nanoparticles (Institute of General Physics named A.M.Prohorov of RAS, Russia); the cylinder 6 with silicomethane - SiH 4 ; the cylinder 7 with the reagent «B» (boron
  • TEM transmission electron microscope
  • LE0912 AB OMEGA Company «Carl Zeiss», Germany
  • X-ray photoelectron spectrometer Company «Quantera SXM» (Company «Physical Electronics* (ULV AC-PHI), USA).
  • He buffer gas - helium
  • the method of obtaining boron- silicon containing nanoparticles is carried out as follows.
  • the reaction gas mixture is supplied in the flow reactor 2 from the cylinder 6 with silicomethane and from the cylinder 7 with the reagent "B" (boron trichloride) through the panel of gas inlet 4.
  • the buffer gas from the cylinder 8 is supplied in the flow reactor 2 through the panel gas inlet 4.
  • the Panel 4 allows adjusting consumption of gas reagents and of the buffer gas, due to the presence of rotameters and gas flow regulators in its design.
  • the vacuum pump 9 maintains the necessary pressure in the flow reactor 2.
  • Feed of the reaction gas mixture in the reactor 2 into the quartz tube is carried out through a capillary.
  • a reaction of pyrolysis induced (stimulated) by a continuous radiation of CO 2 - laser 1 is carried out in the tube; the pressure of the gas mixture in the reactor is below atmospheric one.
  • Helium (He) is preferably used as the buffer gas.
  • Pyrolysis reaction takes place inside a quartz tube for formation of a reaction stream and prevention of the deposition of obtained nanoparticles in the walls and optical glass of the reactor 2.
  • Lens system 3 is used for focusing the laser radiation. It provides the required diameter of the waist of the radiation in the reaction zone in order to increase the power density of laser radiation.
  • the diameter of the constriction depends on the diameter of the incoming laser beam, the values of the lens focus and wave length.
  • Synthesis of boron-silicon containing nanoparticles is carried out in the flow reactor 2, in the stream of the reagent mixture of gases, under influence of radiation of the C0 2 - laser, where there is a decomposition of molecules of silicomethane (SiH 4 ) into active precipitates SiH x , and decomposition of molecules of boron trichloride (BC1 3 ) with formation of bonds of boron-silicon (B-Si).
  • Accumulation of formed nanoparticles is carried out in the filter unit 5 in an atmosphere of the buffer gas.
  • the realization of the invention process is carried out at the ratio of gas consumption as follows silicomethane (SiH 4 ) : reagent «B» (boron trichloride BCI 3 ) : buffer gas, as 1: (1,2-1,5) : (45-55).
  • Specified proportion of gas consumptions is optimal; pyrolysis process for obtaining boron-silicon containing nanoparticles with required dimensions and with the required content of boron is destabilized if the specified ratio is changed.
  • the power density of the laser radiation in the reaction zone is 6000-8000 W/cm 2 . That is optimal.
  • BNCT boron neutron capture therapy
  • the pressure of the gas mixture in the reactor of 400-650 torr., as specified in the invention, is optimum for realization of the process of pyrolysis. Change of the given modality leads to change of the charge of reagents, modification of the temperature conditions of the process, complication of hardware maintenance, decrease in efficiency of formation of nanoparticles.
  • the pressure of the gas mixture in the flow reactor is 600 torr.
  • the productivity of the process was 650 mg/hour of nanoparticles; boron-silicon containing nanoparticles with the size of 5-30 nm were obtained.
  • boron-silicon containing nanoparticles with sizes 5-30 nm, with high boron content (more than 60 at. ), are obtained with laser- induced pyrolysis of the reaction mixture of gases silicomethane and boron trichloride.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Silicon Compounds (AREA)

Abstract

L'invention concerne la nanotechnologie, en particulier un procédé pour obtenir des nanoparticules contenant du bore et du silicium, avec un pourcentage élevé de bore. Le procédé pour obtenir des nanoparticules contenant du bore et du silicium consiste à remplir un réacteur à écoulement avec un mélange gazeux réactif contenant du silicométhane (SiH4) avec un réactif «B» qui est un sel de bore et un gaz tampon puis à induire la pyrolyse du mélange gazeux par le rayonnement continu d'un laser CO2, sous la pression du mélange gazeux qui est inférieure à la pression atmosphérique. La présente invention permet d'obtenir des nanoparticules contenant du bore et du silicium, qui présentent une teneur élevée en bore et une taille de 5 à 30 nm et qui conviennent à la thérapie par capture de neutrons par le bore.
PCT/EP2012/061628 2011-06-21 2012-06-19 Procédé pour obtenir des nanoparticules contenant du bore et du silicium Ceased WO2012175462A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
RU2011125141 2011-06-21
RU2011125141/02A RU2460689C1 (ru) 2011-06-21 2011-06-21 Способ получения бор-кремнийсодержащих наночастиц

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WO2012175462A1 true WO2012175462A1 (fr) 2012-12-27

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017062624A1 (fr) * 2015-10-06 2017-04-13 The Research Foundation For The State University Of New York Compositions de nanoparticules de bore et procédé pour la fabrication et l'utilisation de ces dernières

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015183122A1 (fr) * 2014-05-26 2015-12-03 Общество с ограниченной ответственностью "Уникат" Unité de four tubulaire pour la pyrolyse d'alcanes légers

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3607367A (en) 1968-04-01 1971-09-21 Gen Technologies Corp High-strength, high-modulus, low density, boron silicide monofilaments, and method of making same
US20040229447A1 (en) 2003-03-12 2004-11-18 Swihart Mark T. Process for producing luminescent silicon nanoparticles
US20050180917A1 (en) 2001-12-28 2005-08-18 Bipin Chandra Muljibhai Patel Delivery of neutron capture elements for neutron capture therapy
WO2005094884A2 (fr) 2004-03-02 2005-10-13 T-Cellic A/S Nanoparticules contenant du bore
FR2916193A1 (fr) * 2007-05-18 2008-11-21 Commissariat Energie Atomique Synthese par pyrolyse laser de nanocristaux de silicium.
WO2010125149A1 (fr) * 2009-04-29 2010-11-04 Commissariat à l'énergie atomique et aux énergies alternatives Procede d'elaboration d'une poudre comprenant du carbone, du silicium et du bore

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10353996A1 (de) * 2003-11-19 2005-06-09 Degussa Ag Nanoskaliges, kristallines Siliciumpulver

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3607367A (en) 1968-04-01 1971-09-21 Gen Technologies Corp High-strength, high-modulus, low density, boron silicide monofilaments, and method of making same
US20050180917A1 (en) 2001-12-28 2005-08-18 Bipin Chandra Muljibhai Patel Delivery of neutron capture elements for neutron capture therapy
US20040229447A1 (en) 2003-03-12 2004-11-18 Swihart Mark T. Process for producing luminescent silicon nanoparticles
WO2005094884A2 (fr) 2004-03-02 2005-10-13 T-Cellic A/S Nanoparticules contenant du bore
FR2916193A1 (fr) * 2007-05-18 2008-11-21 Commissariat Energie Atomique Synthese par pyrolyse laser de nanocristaux de silicium.
US20100147675A1 (en) 2007-05-18 2010-06-17 Commissarat A L'energie Atomique Synthesis of Silicon Nanocrystals by Laser Pyrolysis
WO2010125149A1 (fr) * 2009-04-29 2010-11-04 Commissariat à l'énergie atomique et aux énergies alternatives Procede d'elaboration d'une poudre comprenant du carbone, du silicium et du bore

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
"Laser-induced vapour-phase syntheses of boron and titanium diboride powders", JOURNAL OF MATERIALS SCIENCE, vol. 22, no. 2, 1987, pages 737 - 744
"Synthesis of Luminescent Si Nanoparticles Using the Laser-Induced Pyrolysis", LASER PHYSICS, vol. 21, no. 4, 2011, pages 830 - 835
"The catalogue - directory", 2007, pages: 1358
"The catalogue - directory", 2007, pages: 2176 - 2177
"The catalogue - directory", 2007, pages: 429
D.I.MENDELEYEV: "Boron neutron capture therapy of cancer. Chemical aspect", RUSSIAN CHEMICAL JOURNAL, THE RUSSIAN CHEMICAL SOCIETY, vol. XLVIII, no. 4, 2004, pages 109 - 125
S. N. BAGAYEV ; G. N. GRACHEV ; A. G. PONOMARENKO ; A. L. SMIRNOV ; V. N. DEMIN ; A. V. OKOTRUB ; A. M. BAKLANOV ; A. A. ONISCHUK: "A new method of laser-plasma synthesis of nanomaterials: first results and prospects", SPIE PROCEEDINGS VOLUME 6732 INTERNATIONAL CONFERENCE ON LASERS, APPLICATIONS, AND TECHNOLOGIES 2007: LASER-ASSISTED MICRO- AND NANOTECHNOLOGIES, vol. 6732, 28 June 2007 (2007-06-28), pages 673206, XP040246614, DOI: 10.1117/12.751881 *
VLADIMIROV A ET AL: "Synthesis of luminescent Si Nanoparticles using the laser-induced pyrolysis", LASER PHYSICS, NAUKA/INTERPERIODICA, MO, vol. 21, no. 4, 8 April 2011 (2011-04-08), pages 830 - 835, XP019895142, ISSN: 1555-6611, DOI: 10.1134/S1054660X11080032 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017062624A1 (fr) * 2015-10-06 2017-04-13 The Research Foundation For The State University Of New York Compositions de nanoparticules de bore et procédé pour la fabrication et l'utilisation de ces dernières

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