Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
  • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01V—GEOPHYSICS; GRAVITATIONAL MEASUREMENTS; DETECTING MASSES OR OBJECTS; TAGS
  • G01V8/00—Prospecting or detecting by optical means
  • G01V8/02—Prospecting
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
  • C09K8/60—Compositions for stimulating production by acting on the underground formation
  • C09K8/62—Compositions for forming crevices or fractures
  • C09K8/70—Compositions for forming crevices or fractures characterised by their form or by the form of their components, e.g. foams
• • E—FIXED CONSTRUCTIONS
  • E21—EARTH OR ROCK DRILLING; MINING
  • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
  • E21B47/00—Survey of boreholes or wells
  • E21B47/10—Locating fluid leaks, intrusions or movements
  • E21B47/11—Locating fluid leaks, intrusions or movements using tracers; using radioactivity
• • E—FIXED CONSTRUCTIONS
  • E21—EARTH OR ROCK DRILLING; MINING
  • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
  • E21B49/00—Testing the nature of borehole walls; Formation testing; Methods or apparatus for obtaining samples of soil or well fluids, specially adapted to earth drilling or wells
• • E—FIXED CONSTRUCTIONS
  • E21—EARTH OR ROCK DRILLING; MINING
  • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
  • E21B49/00—Testing the nature of borehole walls; Formation testing; Methods or apparatus for obtaining samples of soil or well fluids, specially adapted to earth drilling or wells
  • E21B49/008—Testing the nature of borehole walls; Formation testing; Methods or apparatus for obtaining samples of soil or well fluids, specially adapted to earth drilling or wells by injection test; by analysing pressure variations in an injection or production test, e.g. for estimating the skin factor
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
  • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
  • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
  • G01N21/64—Fluorescence; Phosphorescence
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
  • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
  • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
  • G01N21/64—Fluorescence; Phosphorescence
  • G01N2021/6497—Miscellaneous applications

Definitions

• the field of this invention is that of the exploration and exploitation of oil deposits. More specifically, this invention relates to the development of nanoparticles and tracer fluids containing them, intended to be injected into a well, and collected by inversion of the fluid flow by the same well.
• the tracer fluids according to the invention have the advantage of producing a fluorescent signal with a memory effect, that is to say a signal modified according to the physicochemical conditions encountered in the medium traversed by the nanoparticles after injection into the subsoil. geological.
• the analysis of the fluorescent signals in the fluids collected after diffusion makes it possible to deduce information on the characteristics of the oil reservoir.
• tracers it is well known in the prior art to use tracers to obtain information on a petroleum deposit or more generally on a resource of a geological subsoil, a hydrocarbon deposit, water, gas, oil or oil. Techniques using, for example, tracers with different partition coefficients have been described. The principle is based in particular on chromatography. One of the tracers interacts more specifically with certain fluids contained in the rock, for example, the oil, and its diffusion will be curbed in the presence of oil. By quantifying the diffusion delay with respect to a tracer which interacts little or nothing with its environment (stealth tracer), we deduce the amount of oil contained in the deposit.
• US Pat. No. 3,623,842 describes a method for measuring oil saturation in the vicinity of a well ("Single Well Tracer Test") of injecting a first tracer. partitioning (water / oil), the latter releasing a stealth tracer after a certain time of diffusion in the porous medium.
• the Institute for Energy Technology (IFE) website features a power point presentation entitled SIP 2007 - 2009 "New functional tracers based on nanotechnology and radiator generators Department for Reservoir and Exploration Technology” (last modification dated March 7, 2011 ).
• this paper suggests the use of surface-modified nanoparticles as a tracer for flow control in oilfields and oil wells and in process studies. More precisely, this presentation also describes functionalized tracers capable of emitting a modulated signal depending on the physicochemical conditions traversed.
• the French patent application FR2867180-A1 describes hybrid nanoparticles comprising, on the one hand, a core consisting of a rare earth oxide, possibly doped with a rare earth or an actinide or a mixture of grounds. rare or a mixture of rare earths and actinide and, secondly, a coating around this core, said coating consisting mainly of polysiloxane functionalized with at least one biological ligand grafted by covalent bonding.
• the heart may be based Gd 2 0 3 doped with Tb or uranium and the coating of polysiloxane can be obtained by reacting aminopropyltriethoxysilane, a tetraethyl and triethylamine.
• nanoparticles are used as probes for the detection, monitoring, and quantification of biological systems.
• fluorescent objects often have a fluorescence closely related to the physicochemical conditions encountered with a very strong possible variation of their emission spectra, their excitation spectra, their emission lifetime or their quantum yields.
• fluorescein and its derivatives are in turn very sensitive to pH conditions and may have an emission intensity that varies by several orders of magnitude between an acidic and basic pH (N. Clonis, WH Sawyer, " Spectral properties of the prototropic forms of fluorescein in acqueous solution ", J. Fluorescence, 1996, 6, 147).
• the degradation of the fluorescence signal can nevertheless give information on the medium encountered and could then be used as a "memory effect" signal of the conditions encountered.
• the inventors have had to develop new tracers having a modified fluorescence detectable by time resolved (related to the lanthanide emission in particular), even in the presence of a strong background related to the organic compounds present in them. different oils.
• the present invention aims to satisfy at least one of the following objectives: proposing a new method of studying a solid medium, for example a petroleum deposit, by diffusion of a liquid through said solid medium, which is simple to implement and economical;
• nanoparticles having a memory effect fluorescence signal that is to say whose emission and / or excitation spectrum is modified according to the physico-chemical conditions of the medium through;
• a new tracer fluid comprising these nanoparticles that can be used in particular in a method for studying a solid medium, for example a petroleum deposit by diffusion of said liquid through said solid medium and recovery by the same well by inversion of the flow.
• the invention concerns in the first place a method of studying a geological subsoil, such as a petroleum deposit, by diffusion of an injection liquid into said basement, characterized in that it comprises the following steps:
• o injection liquid is injected into the subsoil to be studied, comprising nanoparticles:
• ⁇ at least a portion of which consists of a heart and, where appropriate, a matrix coating the heart;
• the matrix comprises at least one or more fluorescent entities capable (s) to produce at least one memory effect fluorescence signal, i.e. a signal fluorescence irreversibly modified according to the physicochemical conditions encountered in the subsoil;
• the injected injection liquid is collected at different times following the injection period
• the nanoparticles comprises
• At least one organic fluorophore At least one organic fluorophore, and
• the combination of the two types of fluorophores being chosen so that the nanoparticle produces at least one memory effect fluorescence signal.
• the invention also relates to a tracer fluid that can be used in particular in the process according to the invention, and characterized in that it comprises nanoparticles:
• the matrix comprises at least one organic fluorophore and at least one organometallic fluorophore
• the combination of the two types of fluorophores being chosen so that the nanoparticle produces at least one memory effect fluorescence signal, said signal being detectable by time resolved fluorescence.
• the nanoparticles are capable of emitting at least one memory effect fluorescence signal, and at least one stable fluorescence signal, that is to say which does not vary as a function of the physicochemical conditions. encountered or whose variation is not irreversible.
• the studied subsoil e.g. rocks
• the studied subsoil may be of varied geological nature.
• it is a question of studying a hydrocarbon underground deposit, and more particularly a petroleum deposit.
• it involves measuring the proportion of oil and water around a well as well as characterizing the physicochemical properties such as pH or redox potential.
• They have a mean diameter of between 20 and 200 nm; They are capable of forming a stable colloidal suspension in a saline medium;
• the core and / or, where appropriate, the matrix comprise at least one or more fluorescent entities capable of producing at least one memory effect fluorescence signal, that is to say a modified fluorescence signal irreversibly depending on the physico-chemical conditions encountered in the subsoil.
• These nanoparticles are detectable, that is to say that one can identify their presence or not in the medium beyond a certain concentration and that one can even quantify their concentration as soon as they are present in the middle.
• nanoparticles are capable of forming a stable colloidal suspension in a saline medium, which sediments little. For example, this suspension shows no precipitation or agglomeration over time, e.g. after 6 months at room temperature.
• the core of the nanoparticles contains at least one material chosen from the group comprising: semiconductors, noble metals (eg Au, Ag, Pt), fluorides, vanadates or oxides of earths rare and their mixtures and / or alloys; preferably a lanthanide; their alloys and mixtures thereof and, more preferably still, a lanthanide chosen from the subgroup consisting of: Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm and Yb, and their mixtures and / or alloys .
• noble metals eg Au, Ag, Pt
• fluorides vanadates or oxides of earths rare and their mixtures and / or alloys
• a lanthanide their alloys and mixtures thereof and, more preferably still, a lanthanide chosen from the subgroup consisting of: Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm and Yb, and their mixtures and / or alloys .
• the nanoparticles furthermore contain a preferably transparent matrix chosen from the group of materials comprising: silicas, polysiloxanes, aluminas, zirconiums, aluminates, aluminophosphates, metal oxides (for example ⁇ 2 , ZnO, CeO 2 , Fe 2 0 3, ...) and their mixtures and / or alloys, this matrix including therein and / or thereon:
• luminescent entities selected from the group consisting of rare earth semiconductors, oxides, fluorides or vanadates, organic fluorescent molecules (preferably fluorescein and / or rhodamine), transition metal ions, rare earths, whether bound to complexing molecules and / or to molecules for improving their absorption and their mixtures and / or alloys, ii. optionally other entities allowing a modification of the luminescence properties and chosen from the group comprising: noble metal particles and their mixtures and / or alloys; iii. and the mixtures of these entities (i) and (ii).
• the nanoparticles preferably have a matrix functionalized on the surface, that is to say which comprises R radicals grafted, preferably covalently, preferably based on silane Si-R bonds at the surface and issued from:
• hydrophilic compounds preferably hydrophilic organic compounds, with molar masses of less than 5000 g / mol and more preferably less than 450 g / mol, preferably chosen from organic compounds comprising at least one of the following functions: : alcohol, carboxylic acid, amine, amide, ester, ether-oxide, sulphonate, phosphonate and phosphinate, and the mixtures of these hydrophilic compounds possibly charged,
• neutral hydrophilic compounds preferably a polyalkylene glycol, more preferably a polyethylene glycol, diethylene-triamine pentaacetic acid (DTP A), dithiol DTP A (DTDTPA) or a succinic acid, and mixtures of these neutral hydrophilic compounds,
• the matrix may comprise, if appropriate, other materials chosen from the group consisting of silicas, aluminas, zirconiums, aluminates, aluminophosphates, metal oxides, or metals (example: Fe, Cu, Ni , Co ...) passivated at the surface by a layer of the oxidized metal or other oxide and their mixtures and alloys.
• said nanoparticles comprise:
• the matrix of the nanoparticles comprises radicals -R grafted at a rate
• the solid medium to be studied namely for example the geological subsoil (eg rocks) containing the oil reservoir and, on the other hand, the nanoparticles
• the nanoparticles according to the invention have an average diameter of preferably between 20 nm and 100 nm, for example between 20 nm and 50 nm.
• the nanoparticles according to the invention have a polydispersity index of less than 0.3, preferably less than 0.2, for example less than 0.1.
• the size distribution of the nanoparticles is for example measured using a commercial particle size analyzer, such as a Malvern Zeta sizer Nano-S granulometer based on the PCS (Photon Correlation Spectroscopy). This distribution is characterized by a mean diameter and a polydispersity index.
• a commercial particle size analyzer such as a Malvern Zeta sizer Nano-S granulometer based on the PCS (Photon Correlation Spectroscopy). This distribution is characterized by a mean diameter and a polydispersity index.
• mean diameter means the harmonic mean of the diameters of the particles.
• the polydispersity index refers to the width of the size distribution derived from the cumulant analysis according to ISO 13321: 1996.
• an essential characteristic of the study method according to the invention lies in the use of nanoparticles capable of producing a memory effect signal.
• the term "fluorescent signal with a memory effect” is used, a signal whose characteristics, for example the fluorescence intensity of the emission spectrum, the excitation spectrum, the emission lifetime, or the quantum yields, are irreversibly modified according to certain physico-chemical conditions encountered in the subsoil traversed.
• the nature and / or intensity of the alteration of the fluorescent signal makes it possible to deduce certain physicochemical conditions from the environment traversed.
• the physico-chemical conditions studied include, for example, the temperature of the subsoil, the pH, the hydrocarbon content or the redox potential of the subsoil traversed.
• use will be made of nanoparticles comprising at least one or more fluorescent entities making it possible to produce at least one memory effect fluorescence signal and one or more fluorescent entities producing a stable signal, that is to say, unlike the memory effect, a signal that is not irreversibly modified depending on the physicochemical conditions encountered.
• At least a part of the nanoparticles comprises:
• the combination of the two types of fluorophores being chosen so that the nanoparticle produces at least one memory effect fluorescence signal.
• an organic fluorophore that can be used, in combination with an organometallic fluorophore, to obtain a fluorescent signal with a memory effect
• fluorescein for example fluorescein isothiocyanate FITC
• rhodamine for example Rhodamine B isothiocyanate RBITC
• other fluorescent species that have emission spectra in the same area as fluorescein or rhodamine, for example products with the trade names Alexa Fluor, Cy Dyes, Atto, FluoProbes.
• the organometallic fluorophores of the nanoparticles are chosen from vanadates or oxides of rare earths, or mixtures thereof.
• they are chosen from lanthanides, their alloys and their mixtures, linked to complexing molecules.
• the organometallic fluorophores are detectable by time-resolved fluorescence. Lanthanides linked to complexing molecules are then particularly preferred.
• the metals of the lanthanide series include atomic number elements from 57 (lanthanum) to 71 (lutetium).
• lanthanides will be selected from the group consisting of: Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm and Yb and mixtures and / or alloys thereof, linked to complexing molecules, and preferably europium and terbium.
• complexing molecules or "chelating agent” is meant any molecule capable of forming with a metal agent, a complex comprising at least two coordination bonds.
• a complexing agent having a coordination of at least 6, for example at least 8, and a dissociation constant of the complex, pKd, greater than 10 and preferably greater than 15, with a lanthanide, will be chosen. .
• dissociation constant pKd is understood to mean the measurement of the equilibrium between the ions in the complexed state by the ligands and those free dissociated in the solvent. Precisely, it is less the logarithm in the base of the dissociation product (- log (Kd)), defined as the equilibrium constant of the reaction which translates the transition from the complexed state to the ionic state.
• complexing agents are preferably polydentate chelating molecules chosen from families of polyamine-type polycarboxylic acid molecules and having a high potential number of coordination sites, preferably greater than 6, such as certain macrocycles.
• DOTA or 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid, of the following formula, will be chosen:
• cyclic agent an organic molecule, comprising at least one aromatic ring or heterocycle, preferably selected from benzene, pyridine or their derivatives, and capable of amplifying the fluorescent signal emitted by the organometallic fluorophore and / or the organic fluorophore, for example a complexing agent bound to lanthanide.
• cyclic agents interesting if they are characterized by a high absorbance, are used in particular to amplify the fluorescent signal emitted by the fluorophores (antenna effect by transfer of the excitation of the agent towards the fluorophore).
• the cyclic agent may be grafted covalently either directly to the polysiloxanes of the matrix or to the organometallic and / or organic fluorophore.
• the organometallic fluorophores consisting of a lanthanide with a complexing agent are grafted to the polysiloxanes of the matrix of the nanoparticles covalently via an amide function.
• Organic fluorophore and organometallic fluorophore contained in the same nanoparticle are chosen so as to produce a fluorescence signal with a memory effect, preferably detectable by fluorescence in time resolved.
• the nanoparticles comprise at least one organic fluorophore chosen from fluorescein or one of its derivatives and at least one organometallic fluorophore chosen from europium (Eu) or terbium (Tb), linked to a complexing agent.
• the nanoparticles comprise at least one organic fluorophore chosen from rhodamine or one of its derivatives, and at least one organometallic fluorophore selected from Eu or Tb, linked to a complexing agent.
• the injection liquid may comprise a mixture of nanoparticles, each type of nanoparticle being characterized by the emission of one or more specific fluorescence signals, and in that said emitted signals by each type of nanoparticles are detectable by multiplex detection means.
• the multiplex detection makes it possible to analyze several fluorescence signals (characterized for example by different wavelengths) in parallel on the same sample. Also, fluorescent entities of different emission and / or excitation wavelengths will be used according to each type of nanoparticle.
• the injection liquid comprises at least two types of nanoparticles which are distinguished by their hydrophilic / lipophilic balance and / or their zeta potential, so that some nanoparticles have a fluorescent signal delayed relative to the other part of the nanoparticles because of their interaction with the subsoil.
• nanoparticles interacting with certain rocks of the subsoil will see their memory effect signal more strongly modulated compared to the nanoparticles interacting little or not at all with these same rocks.
• Nanoparticles that can be used in the process of the invention and their preparation are presented in the Examples below.
• the injection liquid is injected and collected in the same well (the injection well and the production well are identical) by reversing the flow of the injected liquid.
• At least one fluorescence detection is carried out in time resolved, that is to say triggered the detection with delay (eg a few microseconds) after an excitation pulse on one or more fluorescent entities contained in the nanoparticle and likely to emit a "stable" signal, that is to say which has not been irreversibly modulated according to the physicochemical conditions encountered.
• the fluorescent signal (s) with memory effect is measured, preferably as a function of the time following the injection, again, preferably by time resolved fluorescence.
• the method of the invention makes it possible to obtain information on the temperature variations experienced by the tracer fluid in the subsoil traversed.
• the pH variations are deduced in the subsoil traversed.
• the rate of exposure to certain hydrocarbons is deduced therefrom.
• the invention relates to an injection liquid (or tracer fluid) in a petroleum reservoir that can be used in particular in the process defined above, characterized in that it comprises nanoparticles:
• the matrix comprises at least one organic fluorophore and at least one organometallic fluorophore
• the combination of the two types of fluorophores being chosen so that the nanoparticle produces at least a memory effect fluorescence signal, said signal being detectable by time resolved fluorescence.
• this liquid comprises water and nanoparticles (or mixture of nanoparticles) as defined above.
• the invention relates to a new use of the nanoparticles as defined above as tracers in injection waters of a petroleum deposit intended for the study of said deposit by diffusion of these injection waters. through this deposit, in particular to evaluate the volumes of oil in reserve in the deposit.
• FIG. 1 shows the emission spectra of the three solutions according to Preparation 1, brought to room temperature with the excitation wavelength 330 nm (FIG La), and 395 nm (FIG Ib) measured with a delay of 0.1 ms and an acquisition time of 5 ms
• FIG. 2 shows the emission spectrum of the three solutions according to Preparation 3 brought back to ambient temperature with excitation wavelength 285 nm (delay 0.1 ms, acquisition time 5 ms).
• FIG. 3 shows the emission spectrum of the two solutions according to Preparation 2 brought back to ambient temperature with excitation wavelength 330 nm (delay 0.1 ms, acquisition time 5 ms).
• FIG. 4 shows the emission spectrum of the three solutions according to Preparation 4 brought back to ambient temperature with the excitation wavelength 285 nm (delay
• FIG. 5 shows the excitation spectrum at a fixed emission for europium at 615 nm of the three solutions according to Preparation 1 at different pH (0.1 ms delay, 5 ms acquisition time).
• FIG. 6 shows the excitation spectrum at a fixed emission for europium at 615 nm of the two nanoparticle solutions according to Preparation 1 in the DEG and a DEG / water mixture (delay 0.1 ms, acquisition time 5 ms).
• FIG. 7 shows the excitation spectrum of the three colloid solutions prepared according to Preparation 1 brought to room temperature with the emission wavelength of 615 nm, 0.1 ms delay, 5 ms acquisition time.
• Preparation 1 Colloidal solution of nanoparticles with a gold core and a silica matrix encapsulating fluorescein-derived organic fluorophores and europium (DTPA) complexes.
• DTPABA diethylenetriaminepentaaceticbisanhydride
• APTES 0.065 ml of triethylamine
• DMSO dimethylsulfoxide
• EuCl 3 , 6H 2 O 200 mg of EuCl 3 , 6H 2 O
• FITC fluorescein isothiocyanate
• APTES (3-aminopropyl) triethoxysilane
• the polymerization reaction of the silica is completed by the addition of 0.800 ml of NH 4 OH after 10 minutes.
• the microemulsion is left stirring for 24 h at room temperature.
• silane-gluconamide N- (3-Triethoxysilylpropyl) gluconamide
• ethanol aqueous ethanol
• 190 ⁇ l of Silane-gluconamide is again added to the solution still stirring at room temperature.
• microemulsion is destabilized in a separatory funnel by adding a mixture of 250 ml of distilled water and 250 ml of isopropanol. The solution is allowed to settle at least 15 minutes and the lower phase containing the particles is recovered.
• the colloidal solution recovered is then placed in a 300 kDa VIVASPIN® tangential filtration system and centrifuged at 4000 rpm until a purification rate of greater than 500 is obtained.
• the solution thus obtained is then filtered at 0.2 ⁇ and diluted by 5 in DEG (diethylene glycol).
• DEG diethylene glycol
• the solution obtained is composed of particles of average size 50.25 nm and polydispersity index 0.091 with very good colloidal stability in a salty aqueous medium (up to 100 g of salts / L)
• Preparation 2 Colloidal solution of nanoparticles with a gold core and a silica matrix encapsulating organic fluorophores derived from rhodamine B and complexes (DTPA) of europium.
• the synthesis is similar to that described for Preparation 1 with the difference that the 20 mg of fluorescein isothiocyanate is replaced by 20 mg of rhodamine B isothiocyanate (RBITC). The rest of the synthesis is identical.
• the solution thus obtained is composed of particles having a mean size of 48 nm and a polydispersity index of 0.072.
• Preparation 3 Colloidal solution of nanoparticles with a gold core and a silica matrix encapsulating organic fluorophores derived from fluorescein and complexes (DTPA) of terbium.
• the synthesis is similar to that described for Preparation 1 except that the 200 mg of EuCl 3 , 6H 2 O are replaced by 200 mg of TbCl 3 , 6H 2 0. The rest of the synthesis is identical.
• the solution thus obtained is composed of particles of average size 43 nm and polydispersity index 0.069.
• Preparation 4 Colloidal solution of nanoparticles with a gold core and a silica matrix encapsulating organic fluorophores derived from rhodamine B and complexes (DTPA) of terbium.
• the synthesis is similar to that described for Preparation 1 with the difference that the 20 mg of fluorescein isothiocyanate is replaced by 20 mg of rhodamine B isothiocyanate (RBITC) and that the 200 mg of EuCl 3 , 6H 2 0 is replaced by 200 mg of mg of TbCl 3 , 6H 2 0.
• RBITC rhodamine B isothiocyanate
• the solution thus obtained is composed of particles of average size 46 nm and polydispersity index 0.073.
• FIG. 1 shows the emission spectrum of the three solutions brought back to room temperature with excitation wavelength 330 nm (Fig. La), and 395 nm (Fig. Lb).
• the luminescence curves (Fig. La) show a clear increase in the emission intensity of the particles (peak at 615 nm, specific for europium) in relation to the heat treatment time at 80 ° C. when the excitation is performed at 330 nm, while at 395 nm no variation is observed (Fig. lb).
• the ratio of the emission peaks between these different excitations can thus serve as probes to measure the exposure time of the particles at the temperature 80 ° C.
• Example 3 Detection of a fluorescent signal with memory effect as a function of the temperature of the environment using nanoparticles according to Preparation 2
• FIG. 3 shows the emission spectrum of the two solutions brought back to ambient temperature with 330 nm excitation wavelength.
• the luminescence curves show a clear decrease in the emission intensity of the particles (peak at 550 nm, specific for terbium) in relation to the heat treatment time at 80 ° C.
• the intensity of the emission peaks can therefore be used as probes to measure the exposure time of the particles at the temperature 80 ° C, with a decrease in the intensity as a function of the exposure time.
• Example 4 Detection of a fluorescent signal with memory effect as a function of the temperature of the environment using nanoparticles according to Preparation 4
• FIG. 4 shows the emission spectrum of the three solutions brought to room temperature with excitation wavelength 285 nm.
• the luminescence curves show a clear decrease in the emission intensity of the particles (peak at 550 nm, specific for terbium) in relation to the heat treatment time at 80 ° C.
• the intensity of the emission peaks can therefore be used as probes to measure the exposure time of the particles at the temperature 80 ° C, with a decrease in the intensity as a function of the exposure time.
• the luminescence curves show a clear increase in the excitation spectrum of the particles in relation to the increase in pH.
• the intensity of the emission peaks (or excitation) can therefore be used as probes to measure the exposure pH of the particles.
• the luminescence curves show a clear degradation of the excitation spectrum of the particles in relation to the increasing water content.
• the intensity of emission peaks (or excitation) can therefore be used as probes to measure the rate of exposure of particles to different water contents.
• FIG. 7 shows the excitation spectrum of the three solutions brought back to ambient temperature with the emission wavelength of 615 nm.
• the luminescence curves show a clear variation in the excitation intensity of the 330 nm component of the particles in relation to the temperature of the treatment.
• the intensity of the excitation peaks can therefore serve as probes for measuring the exposure temperature of the particles, with a decrease in the intensity as a function of the exposure temperature.

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