TW201512252A - Method of recovering nanoparticles from a silicone material - Google Patents

Abstract

A method of recovering nanoparticles from a silicone material comprises providing a nanoparticle composition comprising a silicone material and nanoparticles. The method also comprises depolymerizing the silicone material of the nanoparticle composition to form volatile silicon compounds. Finally, the method comprises substantially separating the volatile silicon compounds and the nanoparticles to recover the nanoparticles.

Description

Method for recovering nano particles from decane materials

The present invention is generally directed to a method of recovering nanoparticles, and more particularly to a method of recovering nanoparticles from a decane material.

Nanoparticles are known in the art and can be prepared by a variety of methods. By way of example, a nanoparticle is generally defined as a particle having at least one size less than 100 nanometers and is derived from a bulk material (which is initially larger than nanoparticle) or from particles smaller than nanoparticle, such as ions and/or atoms. produce. Nanoparticles are particularly unique because they can have properties that are significantly different from the bulk material or smaller particles from which they are derived. For example, a bulk material that acts as an insulator or semiconductor can conduct electricity when in the form of nanoparticle.

Nanoparticles can also be produced by means of a plasma process. For example, nanoparticle can be produced from a precursor gas in a plasma reactor. In certain plasma processes, nanoparticle produced in a plasma reactor is captured or collected in a fluid such as a helium oxide fluid. It is often difficult to recover or separate the nanoparticles from the decane fluid. Furthermore, even if a helium-containing fluid comprising nanoparticle is utilized in certain applications, the nanoparticle generally has a long service life, wherein the nanoparticle exhibits the desired physical properties, but the nanoparticle is usually used for the first time. Discard afterwards. This is undesirable because the production of nanoparticle can be time consuming and expensive.

The present invention provides a method of recovering nanoparticles from a decyl alkane material. Method package A nanoparticle composition comprising a naphthenic material and nanoparticle is provided. The method also includes depolymerizing the rhodium oxide material of the nanoparticle composition to form a volatile rhodium compound. Finally, the method comprises substantially separating the volatile cerium compound and the nanoparticle to recover the nanoparticle.

The process of the present invention allows the recovery of nanoparticles from a decyl alkane material which allows the recycle or reuse of a decane material and/or nanoparticle. This method provides significant benefits and extends the useful life of both the siloxane material and the nanoparticle.

10‧‧‧Variable RF Amplifier/VHF RF Power Supply

11‧‧‧Dielectric discharge tube/dielectric tube/discharge tube/plasma generation chamber

12‧‧‧Glow discharge/plasma

13‧‧‧Electrode configuration / electrode / tip / porous electrode plate

14‧‧‧Electrode/VHF RF Power Supply Ring/Grounding Ring/Porous Electrode Plate

15‧‧‧ Large vacuum reactor

16‧‧‧Solid substrate

20‧‧‧ Plasma Reactor System / System

21‧‧‧Variable Frequency RF Amplifier/Variable Frequency RF Power Amplifier

22‧‧‧ Plasma generation chamber/outlet/chamber

23‧‧‧Area

24‧‧‧Electrode configuration / electrode / porous electrode plate

25‧‧‧Second electrode configuration / electrode / porous electrode plate

26‧‧‧Particle collection chamber/collection chamber

27‧‧‧ Capture fluid

28‧‧‧vacuum source

29‧‧‧Reaction gas inlet

30‧‧‧Export

31‧‧‧孔口/孔

32‧‧‧ Container

33‧‧‧Vacuum source/vacuum pump

50‧‧‧ Plasma Reactor System / System

101‧‧‧ chamber

103‧‧‧ entrance

105‧‧‧Export

107‧‧‧Reservoir

109‧‧‧heater

111‧‧‧jet components

113‧‧‧Nozzle/Cooling System

120‧‧‧Diffusion pump

Other advantages and aspects of the present invention are described in the following embodiments in consideration of the accompanying drawings in which: FIG. 1 illustrates low-voltage, high-frequency pulsed electrical power for producing nanoparticles. An embodiment of a slurry reactor; Figure 2 illustrates another embodiment of a low pressure high frequency pulsed plasma reactor for producing nanoparticle; Figure 3 illustrates a low pressure pulsed plasma reactor including nanoparticle generation and collection of nai An embodiment of a system of diffusion pumps for rice particles; and Figure 4 illustrates a schematic of one embodiment of a diffusion pump for collecting nanoparticles produced by means of a reactor.

The present invention provides a method of recovering nanoparticles from a decyl alkane material. The process of the invention allows recycling of the oxoxane material and/or nanoparticle. This extends the service life of both the siloxane material and the nano granules, and the recycled siloxane material and/or the nano granules can discard the siloxane material and the nano granules and reproduce the oxane materials and Rice granules are cheaper and less time consuming.

The method comprises providing a nanoparticle composition comprising a oxoxane material and a nanoparticle. The helium oxide materials of the nanoparticle composition are each described in more detail below. Nano particles.

The nanoparticle composition can be provided in any manner. For example, a nanoparticle composition can be purchased or prepared. When preparing the nanoparticle composition, the nanoparticles and the siloxane material may be purchased and combined to form a nanoparticle composition, or the nanoparticles and/or oxime may be prepared prior to forming the nanoparticle composition. Alkane material.

The siloxane material can be any siloxane material. The siloxane material means that the siloxane material comprises at least one siloxane chain, that is, a Si-O-Si bond. For example, the oxoxane material can comprise a solid decane, a liquid siloxane, a decane dispersion, a mixture of a decane and an organic and/or inorganic compound, or a combination thereof. More specifically, the oxoxane material may comprise a decane liquid, a decane fluid, a decane gel, a decane gel, a decane solid, a decane resin, a cured siloxane polymer, Curing oxyalkylene rubber, decane emulsion, decane sealant, polyoxyxene rubber, decane oil, decyl oxyhydroxide, decane tube material, liquid polyoxyethylene rubber, decane elasticity Body, decane band, decane tube material, filled siloxane polymer, fiber reinforced siloxane polymer, oxirane sheet, oxime mat, siloxane varnish, decane glove or combination. The decane materials can be crosslinked or uncrosslinked and can be cured or uncured.

The siloxane material may comprise any combination of siloxane units, that is, the siloxane material comprises R ₃ SiO _1/2 units (ie, M units), R ₂ SiO _2/2 units (ie, D units), RSiO. Any combination of _3/2 units (i.e., T units) and SiO _4/2 units (i.e., Q units), wherein R is typically a substituted or unsubstituted hydrocarbon group (as defined below). For example, when the oxoxane material comprises a rubber, elastomer or gel, the oxoxane material comprises or is formed from at least one polymer comprising repeating D units (ie, a linear or partially branched chain polymer). Alternatively, when the decane material is a resin, the siloxane material generally comprises a decane resin having T and/or Q units.

In the embodiment where the siloxane material is a resin, the siloxane material may include DT resin, MT resin, MDT resin, DTQ resin, MTQ resin, MDTQ resin, DQ resin, MQ resin, DTQ resin, MTQ resin or MDQ resin. Combinations of different resins may be present in the oxoxane material. Further, the siloxane material may comprise a resin in combination with a polymer.

When the siloxane material is cured or crosslinked, the ruthenium material can be formed by a variety of reaction mechanisms. For example, the oxoxane material can be composed of a ruthenium hydrogenation-curable decane composition, a radiation-curable siloxane composition, a peroxide-curable siloxane composition, or a condensation-curable oxirane combination. Object formation.

In various embodiments, the oxoxane material comprises a oxoxane fluid or polymer. The oxane fluid or polymer can be linear, branched, partially branched or cyclic. Additionally, the siloxane polymer can be crosslinked to form a decane material.

Specific examples of the phthalic oxide material include polydimethyl methoxy oxane (PDMS), phenylmethyl fluorene oxide, methyl hydroquinone, diphenyl siloxane, vinyl methyl oxane, fluorine. Alkyl oxiranes, methyl sesquioxanes, phenyl sesquioxanes, and copolymers or combinations thereof.

In embodiments where the oxoxane material comprises a siloxane polymer or fluid, the siloxane polymer comprises repeating R ₂ SiO _2/2 units, wherein R is an independently selected substituted or unsubstituted hydrocarbon group. For example, R can be aliphatic, aromatic, cyclic, alicyclic, and the like. Further, R may include ethylenic unsaturation. "Substituted" means that one or more hydrogen atoms of a hydrocarbon may be replaced by an atom other than hydrogen (eg, a halogen atom such as chlorine, fluorine, bromine, etc.), or a carbon atom in the R chain may be used Atom substitutions other than carbon, i.e., R may include one or more heteroatoms within the chain, such as oxygen, sulfur, nitrogen, and the like. R usually has 1 to 10 carbon atoms, or 1 to 6 carbon atoms. The substituted or unsubstituted hydrocarbon group having at least 3 carbon atoms may have a branched or unbranched structure. Examples of hydrocarbyl groups are represented by R and include, but are not limited to, alkyl groups such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl 1,1-dimethylethyl, pentyl, 1-methylbutyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropane , 2,2-dimethylpropyl, hexyl, heptyl, octyl, decyl and decyl; alkenyl, such as ethenyl; cycloalkyl, such as cyclopentyl, cyclohexyl and methylcyclohexyl; Aryl groups such as phenyl and naphthyl; alkaryl groups such as tolyl and xylyl; and aralkyl groups such as benzyl and phenethyl. Examples of halogen-substituted hydrocarbyl groups are represented by R and include, but are not limited to, 3,3,3-trifluoropropyl, 3-chloropropyl, chlorophenyl, dichlorophenyl, 2,2,2- Trifluoroethyl, 2,2,3,3-tetrafluoropropyl and 2,2,3,3,4,4,5,5-octafluoropentyl.

In addition to the groups represented by R, the siloxane polymer can include other substituents or functional groups at any terminal or pendant position. For example, the siloxane polymer may include a hydrazone-bonded hydroxyl group, a hydrogen atom, an amine group, a decylalkyl group, a (meth) acrylate group, an epoxy group, and the like. The groups or atoms may be present in a repeating D unit (described below) or a terminal M unit (which typically has the formula R ₃ SiO _1/3 unless one or more of R is by other substituents or functionalities such as One of the bases is replaced by). Most commonly, such groups, if present, are terminal in the decane polymer.

Since the siloxane polymer comprises repeating R ₂ SiO _2/2 units, the siloxane polymer has a linear portion. However, the siloxane polymer may optionally be branched, partially branched, and/or may comprise a resin portion having a three-dimensional networked structure. In such embodiments, the siloxane polymer further comprises RSiO _3/2 units and/or SiO _4/2 units. The branching of the siloxane polymer itself or the resin portion of the siloxane polymer, if any, can be attributed to the presence of T and/or Q units.

The siloxane polymer can be composed of a decane bond (Si-O-Si) in the main chain of the siloxane polymer. Alternatively, the decane polymer may comprise a decane linkage separated by one or more divalent groups such as a CH ₂ linkage group, wherein CH ₂ may be repeated up to, for example, 10 times. The presence or absence of such divalent groups is generally attributable to the reaction mechanism for the formation of the decane polymer, the formation of a decane polymer composed of a decane linkage by condensation and formation by hydrogenation of hydrazine including one or more A dioxane polymer of a divalent group.

The siloxane polymer may optionally have a functional group such as a fluorenyl bond, a hydrazone bond, a hydrazone, and the like. In various embodiments including such functional groups, the functional groups can be end groups, pendant groups, or both. Typically, the functional group is a terminal group. For example, the siloxane polymer can be terminated with dimethylvinyl, divinylmethyl terminated, dimethyl hydroxy terminated, dihydroxymethyl terminated, and the like. In certain embodiments, the decane polymer comprises a hydrolyzable selected from the group consisting of hydrolyzable The end group of a group, an alkenyl group or a combination thereof. In general, when the siloxane polymer includes the end group, the physical properties of the layer formed from the composition are improved.

In various embodiments in which the oxoxane material comprises a siloxane polymer, the siloxane polymer has the following general formula (A): (X) _3-a (R) _a -Si-(CH ₂ ) _b - ( O) _c -((SiR ₂ -O) _d -SiR ₂ ) _e -(CH ₂ ) _f -[((SiR ₂ -O) _g -SiR ₂ ) _h -(CH ₂ ) _i ] _j -((SiR ₂ -O) _k -SiR ₂ ) _l -(O) _m -(CH ₂ ) _n -Si-(X) _3-p (R) _p ; wherein X is an independently selected hydrolyzable group; R is defined above Wherein a and p are each independently selected from an integer from 0 to 3; b, f, i and n are each independently selected from an integer from 0 to 10; c and m are each independently 0 or 1; d, g And k are each independently selected from 0 or an integer from 1 to 200, the constraints being d, g, and k are not 0 at all; e, h and l are each an integer independently selected from 0 and 1, The constraint condition is that e, h, and l are not 0 at the same time; and j is an integer selected from 0 to 5; the constraint is that when the subscript d is 0, the subscript e is also 0; when the subscript d is greater than 0, the subscript e is 1; when the subscript g is 0, the subscripts h, i and j are also 0; when the subscript g is greater than 1, the subscript h is 1 and the subscript j is at least 1; when the subscript k is 0, the lower The index l is also 0; and when the subscript k is greater than 0, the subscript l is 1.

The hydrolyzable group represented by X in the general formula (A) may be selected from known hydrolyzable groups, such as a decyl alcohol group, a hydrazine-bonded hydrogen group, a hydrazone-bonded alkoxy group, a hydrazine-bonded halogen atom, a hydrazine nitrogen. Alkyl and the like.

In the above formula (A), the subscripts d, g and k represent repeating R ₂ SiO _2/2 units of the siloxane polymer.

In various embodiments, the subscripts c and m are 0 and the subscripts b, d, e, f, g, h, i, j, k, l, and n are each an integer of 1 or more. When the subscript j is 1, the obtained decane polymer includes three fragments each of which is separated by a divalent linking group, and the divalent linking groups are respectively subscripts b and f. , i and n are indicated. In such embodiments, the siloxane polymer is typically formed by hydrogenation of hydrazine and can be represented by the formula: (X) _3-a (R) _a -Si-(CH ₂ ) _b -((SiR ₂ -O) _d -SiR ₂ ) _e -(CH ₂ ) _f -[((SiR ₂ -O) _g -SiR ₂ ) _h - (CH ₂ ) _i ] _j -((SiR ₂ -O) _k -SiR ₂ ) _l - (CH ₂ ) _n -Si-(X) _3-p (R) _p .

Generally, when the subscripts d, g, and k are 1 or more, the subscript j is 1 (and as defined above, since the subscript d is greater than 0, the subscript e is 1, and since the subscript g is greater than 0, The standard h is 1. In these embodiments, the siloxane polymer has the general formula: (X) _3-a (R) _a -Si-(CH ₂ ) _b -(SiR ₂ -O) _d -SiR ₂ -(CH ₂ ) _f -(SiR ₂ -O) _g -SiR ₂ -(CH ₂ ) _i -(SiR ₂ -O) _k -SiR ₂ -(CH ₂ ) _n -Si-(X) _3-p (R) _p .

Most commonly, the subscripts d and k are each 1 and the subscript g is an integer greater than 1 such that the block represented by the subscript g provides a repeating R ₂ SiO _2/2 unit in the siloxane polymer. In these embodiments, the siloxane polymer has the general formula: (X) _3-a (R) _a -Si-(CH ₂ ) _b -SiR ₂ -O-SiR ₂ -(CH ₂ ) _f - (SiR ₂ -O) _g -SiR ₂ -(CH ₂ ) _i -SiR ₂ -O-SiR ₂ -(CH ₂ ) _n -Si-(X) _3-p (R) _p .

In other embodiments, the subscripts c and m are 1 and the subscripts b, f, i, and n are each zero. In such embodiments, the siloxane polymer is typically formed by condensation and can be represented by the formula: (X) _3-a (R) _a -Si-O-((SiR ₂ -O) _d -SiR ₂ ) _e -[((SiR ₂ -O) _g -SiR ₂ ) _h ] _j -((SiR ₂ -O) _k -SiR ₂ ) _l -O-Si-(X) _3-p (R) _p .

Since R is independently selected and can vary among different R ₂ SiO _2/2 units, the above formula can be rewritten to exclude any of the blocks represented by subscripts e, h, j, and l as long as it is not All of these subscripts are also 0. For example, when only the R ₂ SiO _2/2 unit is included in the block represented by the subscript d, the subscript h, the subscript j, and/or the subscript l, the above formula can be rewritten because such Each of the formulas will be repeated with respect to each other except for the potential difference in molecular weight in the examples where the oxane polymer comprises more than 200 repeating R ₂ SiO _2/2 units. As an example, the above-described general formula is rewritten below, in which the subscripts d, e, k, and l are 0, the subscript g is an integer greater than 1, and the subscripts h and j are 1: (X) _{3 -a} (R) _a -Si-O-(SiR ₂ -O) _g -SiR ₂ -O-Si-(X) _3-p (R) _p .

Furthermore, since R is independently selected, the formula described immediately above can be further condensed as follows: (X) _3-a (R) _a -Si-O-(SiR ₂ -O) _g -Si-(X) _3-p (R) _p .

The subscripts a and p can each independently be from 0 to 3 such that the oxirane polymers of these embodiments do not have to have any hydrazine-bonded hydrolyzable groups. Specific substances of the azoxyalkyl polymer in the formula immediately above are set forth below for the purpose of illustration only:

In each of these examples, the subscript g represents a repeating R ₂ SiO _2/2 unit, and g is selected based on the desired molecular weight and viscosity of the siloxane polymer.

A single substance of a siloxane polymer or a combination of different substances of a siloxane polymer which can be used together with each other can be used in the siloxane material. For example, two different types of decane polymers can be utilized in combination with each other, or a decane polymer can be utilized in combination with a decyl olefin resin, such as an MQ resin.

In a particular embodiment, the nanoparticle composition can be a nanoparticle composition of the same application number ___________ (H&H 071038.01249; DC11716), which is incorporated herein by reference in its entirety In this article.

As described above, the nanoparticle composition further comprises nanoparticle. Depending on the application or end use of the nanoparticle composition, the nanoparticles can be formed by any method and can comprise any type of material. In certain embodiments, the siloxane material of the nanoparticle composition is a liquid such that the nanoparticle composition is a suspension of nanoparticles in the oxoxane material. In general, the nanoparticles have at least one dimension that is less than 100 or less than 75 or less than 50 nanometers (as described in more detail below). Or, the nanoparticle has a small The average maximum size at 100 or less than 75 or less than 50 nanometers.

In certain embodiments, the nanoparticle of the nanoparticle composition is produced by means of a plasma process. As is readily understood in the art, the process of producing nanoparticle typically affects the physical properties of the nanoparticle. Specific plasma processes and corresponding plasma reactors or systems suitable for producing nanoparticles of nanoparticle compositions are described below.

In various embodiments, the nanoparticles of the nanoparticle composition are produced by means of an RF plasma based process. In such embodiments, shrinking RF plasma can be used to produce nanoparticle. More specifically, such processes utilize RF plasma operated in a shrink mode to produce nanoparticle from the precursor gas.

In such embodiments, the process of producing nanoparticle can be performed by introducing a precursor gas and optionally a buffer gas into the plasma chamber and generating an RF capacitor plasma in the chamber. RF plasma can be produced under conditions of pressure and RF power that promote the formation of plasma instability (i.e., plasma that is strongly heterogeneous in space and time) that causes the formation of a shrinking plasma in the chamber. Constricted plasma (also sometimes referred to as contracted plasma) results in the formation of high plasma density filaments, sometimes referred to as plasma channels. The plasma channel is characterized by a sharply elevated plasma density, ionization rate, and gas temperature compared to the surrounding plasma. It can be fixed or non-fixed. The periodic rotation of the filament in the discharge tube can be observed, for example, the filament can change its rotation direction, trajectory and rotation frequency randomly. The filaments may appear to be longitudinally uneven or striped. In other cases, the filaments may be longitudinally uniform.

Desirably, an inert buffer or carrier gas such as helium, argon, helium or neon may be included with the precursor gas. Doping these gases in a method based on shrinking plasma is especially desirable because such gases promote the formation of thermal instability to achieve thermal shrinkage. In the RF plasma, the dissociated gas species (i.e., the dissociated product resulting from the dissociation of the precursor molecules) are nucleated and grown into nanoparticles.

The formation of shrinking RF plasma promotes the formation of crystalline nanoparticles because shrinking plasma results in the formation of high current density current channels (ie, filaments) in which local ionization, plasma density, and gas temperature ratio tend to produce amorphous nanoparticles. They are generally much higher in diffusion plasma. For example, in some cases, a gas temperature of at least about 1000 K and a plasma density of up to about 10 ¹³ cm ^-3 can be achieved in the shrink plasma. The additive effect can cause the nanoparticle to be further heated to a temperature even above the gas temperature. These include recombination of plasma electrons and ions on the surface of the nanoparticles, hydrogen recombination on the surface of the particles, and condensation heat release associated with surface growth of the nanoparticles. In some cases, the nanoparticles can be heated to a temperature of a few hundred degrees Celsius above the gas temperature. The plasma can be continuous rather than pulsed plasma.

Accordingly, some embodiments of the process of the present invention use RF plasma shrinkage to provide a high gas temperature using a relatively low plasma frequency.

Conditions that promote the formation of shrinkage plasma can be achieved by using sufficiently high RF power and gas pressure in the production of RF plasma. Any RF power and gas pressure that results in the formation of a contracted RF plasma capable of promoting the formation of nanoparticles from the dissociated gas species prior to dissociation can be employed. The appropriate RF power and gas pressure levels may be slightly altered depending on the plasma reactor geometry. However, in an exemplary embodiment of the process provided herein, the RF power used to activate the RF plasma is at least about 100 watts and the total pressure in the plasma chamber in the presence of plasma (ie, total plasma) The pressure) is at least about 1 Torr. This includes embodiments in which the RF power is at least about 110 watts and further includes embodiments in which the RF power is at least about 120 watts. This also includes an embodiment wherein the total pressure in the plasma chamber in the presence of the plasma is at least about 5 Torr and further comprising a total pressure in the plasma chamber in the presence of the plasma of at least about 10 Torr (eg, about 10 to 15 Torr).

The conditions that promote the formation of non-shrinking RF plasma can be similar to those described above with respect to the generation of shrinkage plasma. However, nanoparticle is typically formed in non-shrink plasma at lower pressures, higher precursor gas flow rates, and lower buffer gas flow rates. For example, in some embodiments, the nanoparticles are produced in the RF plasma at a total pressure of less than about 5 Torr and desirably less than about 3 Torr. This includes embodiments in which the total pressure in the plasma reactor is about 1 to 3 Torr in the presence of plasma. Typical flow rate of the precursor gas in these embodiments The rate can be at least 5 sccm, including embodiments in which the flow rate of the precursor gas is at least about 10 sccm. Typical flow rates for buffer gases in such embodiments can range from about 1 to 50 sccm.

The frequency of the RF voltage used to activate the RF plasma can vary within the RF range. In some embodiments, a frequency of 13.56 MHz is employed, which is the primary frequency used in the RF plasma processing industry. However, the frequency can desirably be below the microwave frequency range, i.e., below about 1 GHz. This includes embodiments in which the frequency will desirably be below the very high frequency (VHF) range (e.g., below about 30 MHz). For example, the method of the present invention can generate radio frequency plasma using a radio frequency of 25 MHz or less.

Other aspects associated with this particular embodiment, wherein the nanoparticle is produced by means of the plasma process, are described in U.S. Patent No. 7,446,335 and U.S. Patent No. 8,016,944 each incorporated by reference in its entirety. Into this article.

In other embodiments, the nanoparticle of the decane composition is prepared in a low pressure plasma reactor, such as a low pressure high frequency pulsed plasma reactor.

In such embodiments, the pulsed plasma allows the operator to directly set the residence time of the particle nucleation and thereby control the particle size distribution and coalescence kinetics in the plasma. For example, the operating parameters of the pulse reactor can be adjusted to form crystalline nanoparticle or amorphous nanoparticle. The precursor containing the semiconductor enters the dielectric discharge tube in which the capacitively coupled plasma or inductively coupled plasma is operated. When the current body molecules dissociate in the plasma, the nanoparticles begin to nucleate. When the plasma is broken or in a low ion state during the pulse cycle, the charged nanoparticle can be transferred to a reactor chamber where the nanoparticle can be deposited on the substrate or subjected to further processing .

Power can be supplied by means of a variable frequency RF power amplifier triggered by an arbitrary function generator to establish high frequency pulsed plasma. In one embodiment, a radio frequency power source is capacitively coupled to the plasma in the gas using a ring electrode, a parallel plate, or an anode/cathode device. Alternatively, an RF coil device can be used around the discharge tube to couple the RF power source in an inductive coupling mode. Into the plasma. The precursor gas can be controlled by means of a mass flow controller or a calibrated rotary flow meter. The pressure differential from the discharge vessel to the reactor chamber can be controlled via a variable ground or biasing orifice. Depending on the pore size and pressure, the distribution of nanoparticles in the reactor chamber can vary, thus providing another process parameter that can be used to adjust the characteristics of the resulting nanoparticle.

In one embodiment, the plasma reactor can be operated at a frequency of 10 MHz to 500 MHz and a power of 5 watts to 100 watts in a discharge vessel at a pressure of 100 mTorr to 10 Torr.

Referring now to Figure 1, an illustrative embodiment of a low pressure high frequency pulsed plasma reactor is shown. In the illustrated embodiment, the precursor gas can be introduced into the evacuated dielectric discharge tube 11. The discharge tube 11 includes an electrode configuration 13 attached to the variable frequency RF amplifier 10. Another portion of the electrode 14 is grounded, DC biased, or operated in a push-pull manner relative to the electrode 13. The electrodes 13, 14 are used to couple a very high frequency (VHF) power source to the precursor gas to initiate and maintain the glow discharge or plasma 12. The precursor gas can then be dissociated and nucleated in the plasma to form nanoparticle.

In one embodiment, the electrodes 13, 14 are used in a plasma source within the dielectric tube 11 (which is a flow-through nozzle design) in which the VHF radio frequency biased upstream of the porous electrode plate 13 is separated from the downstream porous electrode plate 14, The apertures of the plates are aligned with one another. The apertures can be circular, rectangular or any other desired shape. Alternatively, the dielectric tube 11 can enclose an electrode 13 having a tip end coupled to the VHF RF power source 10, the tip having a variable distance between the tip end and the ground ring 14 inside the dielectric tube 11. In this case, the VHF RF power source 10 is operated in the frequency range of about 10 to 500 MHz. In another alternative embodiment, the tip 13 can be placed at a variable distance between the tip and the VHF RF power supply ring 14 operating in a push-pull mode (180° out of phase). In yet another alternative embodiment, the electrodes 13, 14 include an inductive coil coupled to the VHF radio frequency power source such that the radio frequency power source is transferred to the precursor gas by an electric field formed by the inductive coil. Part of the dielectric tube 11 can be evacuated to a vacuum of between 1 x 10 ^-7 and 500 Torr.

The nucleated nanoparticle can be passed to a larger vacuum reactor 15 where it can be collected on a solid substrate 16 (including a chuck) or collected into a suitable liquid matrix/solution. For example, nanoparticle can be collected in a siloxane material to form a nanoparticle combination. Things. Alternatively, the nanoparticles can be collected in a capture fluid and subsequently introduced into the curable siloxane composition to form a decane composition. The solid substrate 16 can be electrically grounded, biased, temperature controlled, rotated, placed relative to the electrodes that produce the nanoparticles, or placed on a reel system. If deposition onto the substrate is not selected, the particles are evacuated to a suitable pump for conversion to atmospheric pressure. The nanoparticle can then be sent to an atmospheric grading system, such as a differential mobility analyzer, and collected for further functionalization or other processing.

In the illustrated embodiment, the plasma is induced with high frequency plasma by means of a radio frequency power amplifier such as the AR Worldwide model KAA2040 or Electronics and Innovation 3200L. The amplifier can be driven (or pulsed) by any function generator from 0.15 to 150 MHz, such as the Tektronix AFG3252 function generator, which is capable of generating up to 200 watts of power. In various embodiments, any function may be capable of driving the power amplifier by pulse train, amplitude modulation, frequency modulation, or a different waveform. The power coupling between the amplifier and the precursor gas generally increases as the frequency of the RF power increases. Therefore, the ability to drive a power supply at higher frequencies may allow for more efficient coupling between power and discharge.

If necessary, the nanoparticle can be nucleated from at least one precursor gas by VHF RF low-pressure plasma discharge and by controlling the average free path of the nanoparticle in aerosol form (thus allowing particle-particle prior to collection) Interaction) Collecting nucleated nanoparticles to produce nanoparticles with different coalescence lengths. The nucleated nanoparticles can be collected on a solid substrate in a vacuum environment, the collection distance in a vacuum environment being greater than the mean free path of the particles controlled by pressure. In turn, the coalescence length of the nanoparticles can be controlled. Alternatively, the nucleated nanoparticles can be collected in a liquid matrix in a vacuum environment, the collection distance in a vacuum environment being greater than the mean free path of the particles controlled by pressure, thus controlling the coalescence length of the nanoparticles. The further the substrate is from the nucleation region (plasma discharge), the longer the coalescence at constant pressure. The synthetic nanoparticle can be pumped from the low pressure environment to the atmosphere in an aerosol form to at least partially control the coalescence length by the concentration of the aerosol.

In some embodiments, VHF RF low pressure plasma can be used to synthesize crystalline or amorphous The core nanoparticles produce nanoparticles that are discharged in a low pressure environment by pulsed discharge to control plasma residence time. For example, amorphous core nanoparticle can be synthesized via VHF radio frequency low voltage plasma discharge with a plasma residence time that is increased relative to the residence time of the precursor gas molecules. Alternatively, it can be operated at the same operating conditions as the discharge drive frequency, the drive amplitude, the discharge tube pressure, the chamber pressure, the plasma power density, the gas molecule residence time through the plasma, and the collection distance from the plasma source electrode. The crystal core nanoparticle is synthesized by the slurry residence time.

Other aspects associated with this particular embodiment in which nanoparticle is produced by means of this plasma process are described in the International Patent Publication No. WO 2010/027959 (PCT/US2009/055587), which is incorporated herein by reference. The manner of full reference is incorporated herein.

Referring to Figure 2, an alternate embodiment of a plasma reactor system is shown at 20. In this embodiment, the plasma reactor system 20 includes a plasma generation chamber 22 having a reactant gas inlet 29 and an outlet 30 having orifices or holes 31 therein. The particle collection chamber 26 is in communication with the plasma generation chamber 22. The particle collection chamber 26 contains a capture fluid 27 in the container 32. The container 32 can be adapted for agitation (by means of a tool not shown). For example, the container 32 can be disposed on a rotatable support (not shown) or can include a stirring mechanism. Preferably, the capture fluid is a liquid at the operating temperature of the system. The plasma reactor system 5 also includes a vacuum source 28 in communication with the particle collection chamber 26 and the plasma generation chamber 22.

The plasma generation chamber 22 includes an electrode configuration 24 that is attached to a variable frequency RF amplifier 21. The plasma generation chamber 22 also includes a second electrode configuration 25. The second electrode configuration 25 is operated in a push-pull manner via ground, DC bias or relative to the electrode configuration 24. Electrodes 24, 25 are used to couple a very high frequency (VHF) power source to the reactant gas mixture to initiate and maintain a glow glow of the plasma in a region identified as 23. The first reaction precursor gas is then dissociated in the plasma to provide charged atoms that are nucleated to form nanoparticle. However, other discharge tube configurations are contemplated and can be used to carry out the methods disclosed herein.

In the embodiment of Figure 2, nanoparticles are collected in the capture fluid in the particle collection chamber 26. Particles. To control the diameter of the formed nanoparticle, the distance between the orifice 31 in the outlet 22 of the plasma generating chamber 22 and the surface of the trapping fluid is in the range of between about 5 and about 50 orifice diameters. It has been discovered that positioning the surface of the capture fluid too close to the outlet of the plasma generation chamber can create undesirable interactions of the plasma with the capture fluid. Conversely, the surface of the capture fluid is positioned too far from the orifice to reduce particle collection efficiency. Since the collection distance is a function of the diameter of the orifice of the outlet and the pressure drop between the plasma generating chamber and the collection chamber, an acceptable collection distance of from about 1 to about 20, or about 5 to about the operating conditions described herein. About 10cm. In other words, the acceptable collection distance is from about 5 to about 50 orifice diameters.

The plasma generation chamber 22 also includes a power supply. The power supply is supplied by means of a variable frequency RF power amplifier 21 which is triggered by an arbitrary function generator to establish a high frequency pulsed plasma in region 23. Preferably, the RF power source is capacitively coupled into the plasma using a ring electrode, a parallel plate or an anode/cathode device in the gas. Alternatively, the RF power source can be coupled to the plasma in an inductive coupling mode using an RF coil device around the discharge tube.

The plasma generating chamber 11 may also include a dielectric discharge tube. Preferably, the reactant gas mixture enters a dielectric discharge tube that produces a plasma. When the first reaction precursor gas molecules dissociate in the plasma, the nanoparticles formed from the reactant gas mixture begin to nucleate.

Vacuum source 28 can include a vacuum pump. Alternatively, vacuum source 28 may comprise mechanical, turbo molecules or cryopumps.

In one embodiment, the electrodes 24, 25 for the plasma source within the plasma generating chamber 22 comprise a flow-through nozzle design in which the VHF radio frequency biased upstream of the porous electrode plate 24 is separated from the downstream porous electrode plate 25, The apertures of the plates are aligned with one another. The pores can be annular, rectangular or any other desired shape. Alternatively, the plasma generation chamber 22 can enclose an electrode 24 having a tip end coupled to the VHF RF power source, the tip having a variable distance between the tip end and the ground ring within the chamber 22.

In one embodiment, the VHF RF power source can be operated substantially in a manner similar to that described above with respect to the embodiment of FIG. Can be used with models such as AR Worldwide The RF power amplifier of KAA 2040 or Electronics and Innovation Model 3200L or EM Power RF Systems, Inc. Model BBS2E3KUT initiates the plasma in zone 23 with high frequency plasma. The amplifier can be driven (or pulsed) by any of the function generators as described above with respect to the embodiment of FIG.

In one embodiment, the power and frequency of the plasma system are preselected to produce the optimal operating space for the formation of nanoparticles. Preferably, both the tuned power source and the frequency produce a suitable ion and electron energy distribution in the discharge to help dissociate the molecules of the reaction precursor gas and nucleate the nanoparticles.

The plasma reactor system 20 illustrated in Figure 2 can be pulsed to enable an operator to directly manage the residence time of particle nucleation and thereby control the particle size distribution and coalescence kinetics in the plasma. The pulse function of system 20 allows for controlled tuning of the residence time of the particles in the plasma, which affects the size of the nanoparticles. By reducing the "on" time of the plasma, the nucleating particles have less coalescence time and thus reduce the average size of the nanoparticles (i.e., the nanoparticle distribution can be shifted to a smaller diameter particle size).

Advantageously, operating the plasma reactor system 20 and pulsed plasma in a higher frequency range provides the same conditions as conventional shrinkage/filament discharge techniques using plasma instability to produce high ion energy/density, but with use Operating conditions can be controlled to select and produce additional advantages of nanoparticles of various sizes that affect the characteristic physical properties of the nanoparticle, such as photoluminescence.

For pulse injection, the synthesis of nanoparticles can be carried out by a pulsed energy source such as pulsed very high frequency RF plasma, high frequency RF plasma or pulsed laser for pyrolysis. Preferably, the VHF radio frequency is pulsed at a frequency in the range of about 1 to about 50 kHz.

Another method of transferring nanoparticle to a capture fluid is the input of a pulsed reactant gas mixture upon activation of the plasma. For example, one may activate a plasma in which a first reaction precursor gas is present in the presence of at least one other gas that sustains the discharge, such as an inert gas, to synthesize the nanoparticles. When the first reaction precursor gas is made by the mass flow controller Stop the synthesis of nanoparticles when the flow stops. The synthesis of the nanoparticles is continued when the first reaction precursor gas begins to flow again. This produces a pulsed stream of nanoparticles. If the flux of the nanoparticle impacting the capture fluid is greater than the absorption of the nanoparticle absorbed into the capture fluid, this technique can be used to increase the concentration of the nanoparticle in the capture fluid.

In another embodiment, the nucleated nanoparticles are transferred from the plasma generation chamber 22 to the particle collection chamber 26 containing the capture fluid by means of orifices or holes 31 that create a pressure differential. It is contemplated that the pressure differential between the plasma generation chamber 22 and the particle collection chamber 26 can be controlled via a variety of methods. In one configuration, the inner diameter of the discharge tube of the plasma generation chamber 22 is much smaller than the inner diameter of the particle collection chamber 26, thus creating a pressure drop. In another configuration, a grounded physical aperture or aperture can be placed between the discharge tube and the collection chamber 26, which forces the plasma based on the Debye length of the plasma and the size of the chamber 22. Part of it stays in the hole. Another configuration involves the use of different electrostatic holes in which a positive concentric charge is generated which forces the negatively charged plasma through the orifice 31.

The capture fluid is expected to be useful as a material handling and storage medium. In one embodiment, the capture fluid is selected to allow the nanoparticles to absorb and disperse in the fluid as it is collected, thereby forming a dispersion or suspension of nanoparticles in the capture fluid. If the nanoparticle is miscible with the fluid, it will be absorbed into the fluid. For example, the capture fluid can comprise a siloxane material such that the nanoparticles can be collected in a siloxane material to form a nanoparticle composition. Alternatively, the nanoparticles can be collected in a capture fluid and subsequently introduced into a siloxane material to form a nanoparticle composition.

The capture fluid is selected to have the properties required for the capture and storage of the nanoparticles. In a particular embodiment, the vapor pressure of the capture fluid is lower than the operating pressure in the plasma reactor. Preferably, the operating pressure in the reactor and collection chamber 26 is in the range of from about 1 to about 5 milliTorr. Other operating pressures are also covered. The capture fluid may comprise a helium alkane fluid such as polydimethylsiloxane, phenylmethyl-dimethylcyclooxane, tetramethyltetraphenyltrioxane, and/or pentaphenyltrimethyl Trioxane. These helioxane fluids may constitute a nanoparticle composition A oxoxane material, in which case the nanoparticle composition can be prepared in the collection or capture of nanoparticles in a oxane fluid. Typically, however, the capture fluid comprises a oxane fluid to form a nanoparticle composition once the nanoparticles are captured or collected in the capture fluid. In such embodiments, the nanoparticulate composition is typically a suspension of nanoparticle in a oxoxane material which is a liquid.

The capture fluid can be agitated during direct capture of the nanoparticles, such as by agitation, rotation, inversion, and other suitable methods of providing agitation. If a higher absorption rate of nanoparticles absorbed into the capture liquid is desired, then a more aggressive form of agitation, such as ultrasonic treatment, is considered.

As first described above, in the embodiment of FIG. 2, when the first reaction precursor gas is dissociated in the plasma generation chamber 22, nanoparticle is formed and entrained in the gas phase. The distance between the nanoparticle synthesis site and the surface of the capture fluid must be short enough that no undesirable functionalization occurs when the nanoparticle is entrained. If the nanoparticles interact in the gas phase, agglomerates of many individual small nanoparticles will be formed and captured in the capture fluid. If too much interaction occurs in the gas phase, the nanoparticles can agglomerate together and form nanoparticles having a larger average diameter. The collection distance is defined as the distance from the exit of the plasma generation chamber to the surface of the capture fluid.

Other aspects related to this particular embodiment in which nanoparticle is produced by means of this plasma process are described in the International Patent Publication No. WO 2011/109299 (PCT/US2011/026491), which is incorporated herein by reference. The manner of full reference is incorporated herein.

Referring to Figure 3, an alternate embodiment of a plasma reactor system is shown at 50. In this embodiment, it is prepared in a system having a reactor for generating a nanoparticle aerosol (e.g., nanoparticle in a gas) and a diffusion pump in fluid communication with the reactor to collect aerosol nanoparticles. Nanoparticles of a decane composition. For example, a nanoparticle aerosol produced in a reactor (eg, a low pressure plasma reactor) can be introduced into a diffusion pump in fluid communication with the reactor, from a diffusion pump oil, liquid or fluid ( Such as a helium oxide fluid) Nanoparticles of various size distributions and characteristics are prepared by trapping aerosol nanoparticles in the condensate and collecting the captured nanoparticles in a reservoir.

Exemplary reactors are described in WO 2010/027959 and WO 2011/109229, each of which is incorporated herein by reference in its entirety. The reactors can be, but are not limited to, low pressure high frequency pulsed plasma reactors. By way of example, Figure 3 illustrates a plasma reactor of the embodiment of Figure 2, but including a diffusion pump in fluid communication with the reactor. For this purpose, with respect to the embodiment of Figure 3, the description of this particular plasma reactor is not repeated herein.

In the embodiment of FIG. 3, the plasma reactor system 50 includes a diffusion pump 120. Therefore, the nanoparticles can be collected by the diffusion pump 120. The particle collection chamber 26 can be in fluid communication with the plasma generation chamber 22. The diffusion pump 120 can be in fluid communication with the particle collection chamber 26 and the plasma generation chamber 22. In other forms of the invention, system 50 may not include particle collection chamber 26. For example, the outlet 30 can be coupled to the inlet 103 of the diffusion pump 120, or the diffusion pump 120 can be in substantially direct fluid communication with the plasma generation chamber 22.

4 is a schematic cross-sectional view of an exemplary diffusion pump 120 suitable for system 50 of the embodiment of FIG. The diffusion pump 120 can include a chamber 101 having an inlet 103 and an outlet 105. The inlet 103 can have a diameter of from about 2 to about 55 inches, and the outlet can have a diameter of from about 0.5 to about 8 inches. The inlet 103 of the chamber 101 is in fluid communication with the outlet 30 of the reactor 20. The diffusion pump 120 can have a pumping speed of, for example, from about 65 to about 65,000 liters per second or greater than about 65,000 liters per second.

The diffusion pump 120 includes a reservoir 107 in fluid communication with the chamber 101. The reservoir 107 is loaded or contains a diffusion pump fluid. The reservoir can have a volume of from about 30 cc to about 15 liters. The volume of the diffusion pump fluid in the diffusion pump can range from about 30 cc to about 15 liters.

The diffusion pump 120 can further include a heater 109 for vaporizing the diffusion pump fluid in the reservoir 107 into a vapor. The heater 109 heats the diffusion pump fluid and vaporizes the diffusion pump fluid to form a vapor (eg, liquid to gas phase conversion). For example, the diffusion pump fluid can be heated to from about 100 to about 400 °C or from about 180 to about 250 °C.

The jetting assembly 111 can be in fluid communication with the reservoir 107 that includes a nozzle 113 to discharge vaporized diffusion pump fluid into the chamber 101. The vaporized diffusion pump fluid flows and rises through the jetting assembly 111 and is emitted from the nozzle 113. The flow of the vaporized diffusion pump fluid is illustrated by arrows in Figure 4. The vaporized diffusion pump fluid condenses and flows back to the reservoir 107. For example, the nozzle 113 can discharge vaporized diffusion pump fluid relative to the wall of the chamber 101. The wall of the chamber 101 can be cooled by a cooling system 113, such as a water cooling system. The cooled wall of chamber 101 allows the vaporized diffusion pump fluid to condense. The condensed diffusion pump fluid can then flow along the walls of the chamber 101 and flow down the walls and back to the reservoir 107. The diffusion pump fluid can be continuously circulated via the diffusion pump 120. The flow of the diffusion pump fluid causes gas entering the inlet 103 to diffuse from the inlet 103 of the chamber 101 to the outlet 105. Vacuum source 33 may be in fluid communication with outlet 105 of chamber 101 to assist in the removal of gas from outlet 105.

When the gas flows through the chamber 101, the nanoparticle in the gas can be absorbed by the diffusion pump fluid, thereby collecting the nanoparticle from the gas. For example, the surface of the nanoparticle can be wetted by a vaporized and/or condensed diffusion pump fluid. In addition, the agitation of the circulating diffusion pump fluid can additionally improve the absorption rate of the nanoparticles compared to the static fluid. The pressure within chamber 101 can be less than about 1 mTorr.

The diffusion pump fluid with nanoparticle can then be removed from the diffusion pump 120. For example, the diffusion pump fluid with nanoparticle can be continuously removed and replaced by a diffusion pump fluid that is substantially free of nanoparticle.

Advantageously, the diffusion pump 120 can be used not only to collect nanoparticles but also to evacuate the reactor 20 (and the collection chamber 26). For example, the operating pressure in reactor 20 can be a low pressure, such as less than atmospheric pressure, less than 760 Torr, or between about 1 and about 760 Torr. Collection chamber 26 can be, for example, in the range of from about 1 to about 5 millitorr. Other operating pressures are also covered.

The diffusion pump fluid can be selected to have the characteristics required for nanoparticle capture and storage. The diffusion pump fluid can be the same as the capture fluid described above with respect to the embodiment of FIG. 2. Similarly, the diffusion pump fluid can comprise a oxoxane material, such as any of the oxane fluids described above, such that when the nanoparticles are captured in a diffusion pump fluid, a nanoparticle composition is formed. Alternatively, the nanoparticles can be separated or isolated from the diffusion pump fluid and combined with the siloxane material to form a nanoparticle composition. For example, the diffusion pump fluid can be centrifuged and/or decanted to concentrate or separate the nanoparticles therein. Other diffusion pump fluids and oils may include hydrocarbons, phenyl ethers, fluorinated polyphenylene ethers, and ionic fluids. The fluid may have 0.001 to 1, 0.005 to 0.5 or 0.01 to 0.1 Pa at 23 ± 3 °C. s viscosity. Additionally, the fluid can have a vapor pressure of less than about 1 x 10 ^-4 Torr. Typically, the diffusion pump fluid comprises a helium oxide diffusion pump fluid such that once the nanoparticles are captured or collected in the helium diffusion pump fluid (once condensed) a nanoparticle composition is formed. In such embodiments, the nanoparticulate composition is typically a suspension of nanoparticle in a oxoxane material which is a liquid.

System 50 can also include a vacuum pump or vacuum source 33 in fluid communication with outlet 105 of diffusion pump 120. Vacuum source 33 can be selected to properly operate diffusion pump 120. In one form of the invention, vacuum source 33 includes a vacuum pump (e.g., an auxiliary pump). Vacuum source 33 can include mechanical, turbo molecules, or cryopumps. However, other vacuum sources are also covered.

A method of producing nanoparticle by system 50 of FIG. 3 can include forming a nanoparticle aerosol in reactor 20. The nanoparticle aerosol can comprise nanoparticle in a gas, and the method further comprises introducing a nanoparticle aerosol from the reactor 5 into the diffusion pump 120. The method may also include heating the diffusion pump fluid in the reservoir 107 to form a vapor, transferring the vapor via the injection assembly 111, emitting vapor through the nozzle 113 into the chamber 101 of the diffusion pump 120, condensing the vapor to form a condensate, and The condensate is returned to the reservoir 107. Additionally, the method can further include capturing the aerosolized nanoparticles in the condensate and collecting the captured nanoparticles in the reservoir 107. The method can further include removing the gas from the diffusion pump by a vacuum pump.

Other aspects associated with this particular embodiment, wherein the nanoparticle is produced by means of this plasma process, are described in the Chinese Patent Application Serial No. 61/655,635, which is incorporated herein in its entirety by reference.

As described in the various embodiments above, plasma systems typically rely on precursor gases, regardless of the particular plasma system and process used to produce the nanoparticles of the decane composition. The precursor gas may alternatively be referred to as a reactant gas mixture or a gas mixture. As described in more detail below with reference to nanoparticles, the precursor gas is typically selected based on the desired composition of the nanoparticles. For example, when the nanoparticle contains the nanoparticle, the precursor gas may contain cerium, and when the nanoparticle contains cerium, the precursor gas may contain cerium. Further, the precursor gas may be selected from the group consisting of decane, dioxane, halogen-substituted decane, halogen-substituted dioxane, C ₁ -C ₄ alkyldecane, C ₁ -C ₄ alkyldioxane, and mixtures thereof. In one form of the invention, the precursor gas may comprise decane which comprises from about 0.1% to about 2% of the total gas mixture. However, the gas mixture may also contain other percentages of decane and/or other or alternative precursor gases (as described below with respect to the nanoparticles formed therefrom).

The precursor gas can be mixed with other gases such as an inert gas to form a gas mixture. Examples of the inert gas which may be included in the gas mixture include a mixture of argon, helium, neon or inert gas. When present in the gas mixture, the inert gas can comprise from about 1% to about 99% of the total volume of the gas mixture. The precursor gas can have from about 0.1% to about 50% of the total volume of the gas mixture. However, precursor gases are also expected to account for other volume percentages, such as from about 1% to about 50% of the total volume of the gas mixture.

In one form of the invention, the reactant gas mixture also contains a second precursor gas which may itself comprise from about 0.1 to about 49.9% by volume of the reactant gas mixture. The second precursor gas may comprise BCl ₃ , B ₂ H ₆ , PH ₃ , GeH ₄ or GeCl ₄ . The second precursor gas may also contain other gases containing carbon, helium, boron, phosphorus or nitrogen. The combination of the first precursor gas and the second precursor gas may comprise from about 0.1% to about 50% of the total volume of the reactant gas mixture.

In another form of the invention, the reactant gas mixture further comprises hydrogen. Hydrogen may be present in an amount from about 1% to about 10% by total volume of the reactant gas mixture. However, it is also contemplated that the reactant gas mixture may comprise other percentages of hydrogen.

Nanoparticles for the nanoparticle composition can be prepared by any of the methods described above. Nanoparticles of various compositions can be produced depending on the precursor gases and molecules used in the plasma process. For example, the nanoparticle may be a semiconducting nanoparticle comprising at least one element selected from the group consisting of Group IV, Group IV-IV, Group II-IV, and Group III-V. Alternatively, the nanoparticle may comprise at least one member selected from the group consisting of Group IIA, Group IIIA, Group IVA, Group VA, Group IB, Group IIB, Group IVB, Group VB, Group VIB, and VIIB. Metal nanoparticles of the family and elements of Group VIIIB metals. These family names of the periodic table are usually derived from CAS or the old IUPAC nomenclature, although the Group IV elements are referred to as Group 14 elements according to the modern IUPAC system (as is readily understood in the art). Alternatively, the nanoparticles may be metal alloy nanoparticles, metal oxide nanoparticles, metal nitride nanoparticles, ceramic nanoparticles or the like.

The processes disclosed herein are particularly useful for producing nanocrystals from a precursor molecule containing a Group IV semiconductor (including ruthenium, osmium, and tin) and comprising such elements. Oxane and decane are examples of precursor molecules that can be used to produce nanoparticles comprising ruthenium and osmium, respectively. Organometallic precursor molecules can also be used. These molecules include Group IV metals and organic groups. Organometallic Group IV precursors include, but are not limited to, organic germanium, organic germanium, and organotin compounds. Some examples of Group IV precursors include, but are not limited to, alkyl hydrazines, alkyl decanes, alkyl stannanes, chlorodecanes, chloranil, chlorostannane, aromatic decanes, aromatic hydrazines, and aromatic stannanes. Other examples of ruthenium precursors include, but are not limited to, dioxane (Si ₂ H ₆ ), hafnium tetrachloride (SiCl ₄ ), trichlorodecane (HSiCl ₃ ), and dichlorodecane (H ₂ SiCl ₂ ). Still other suitable precursor molecules for forming crystalline cerium nanoparticles include alkyl and aromatic decanes such as dimethyl decane (H ₃ C--SiH ₂ -CH ₃ ), tetraethyl decane (CH ₃ CH ₂ ) ₄ Si) and diphenyl decane (Ph-SiH ₂ -Ph). Specific examples of the ruthenium precursor molecule which can be used to form the crystalline Ge nanoparticle in addition to decane include, but are not limited to, ruthenium tetrachloride (GeCl ₄ ), tetraethyl decane ((CH ₃ CH ₂ ) ₄ Ge And diphenyl decane (Ph-GeH ₂ -Ph).

In certain embodiments, the nanoparticle comprises at least one of ruthenium and osmium. In addition, The nanoparticle may comprise a niobium alloy and/or a niobium alloy. The alloys that can be formed include, but are not limited to, tantalum carbide, niobium, tantalum boron, hafnium phosphorus, and tantalum nitride. The niobium alloy may be formed by mixing at least one first precursor gas with a second precursor gas or using a precursor gas containing a different element. However, other methods of forming alloyed nanoparticle are also contemplated.

In another form of the invention, the nanoparticles can undergo another doping step. For example, the nanoparticles can undergo gas phase doping in the plasma, wherein the second precursor gas is dissociated and incorporated into the nanoparticles during nucleation of the nanoparticle. The nanoparticle can also be downstream of the production of the nanoparticle, but undergoes doping in the gas phase before the nanoparticle is captured in the liquid. In addition, doped nanoparticles can also be produced in the diffusion pump fluid, wherein the dopant is preloaded into the diffusion pump fluid and interacts with the nanoparticle after capturing the nanoparticle. The doped nanoparticles can be formed by contact with an organic hydrazine gas or liquid, including but not limited to trimethyl decane, dioxane, and trioxane. Gas phase dopants can include, but are not limited to, BCl ₃ , B ₂ H ₆ , PH ₃ , GeH _{4 ,} or GeCl ₄ .

Due to quantum confinement effects, nanoparticles exhibit a variety of unique electronic, magnetic, catalytic, physical, optoelectronic, and optical properties. For example, many semiconductor nanoparticles exhibit a photoluminescence effect that is significantly greater than the photoluminescence effect of macroscopic materials having the same composition.

The nanoparticles can have a largest dimension or an average maximum dimension of less than 50, less than 20, less than 10, or less than 5 nm. Further, the largest or average maximum size of the nanoparticles may be between 1 and 50, between 2 and 50, between 2 and 20, between 2 and 10, or between about 2.2 and about 4.7 nm. Nanoparticles can be measured by a variety of methods, such as by transmission electron microscopy (TEM). For example, as understood in the art, the particle size distribution is typically calculated by TEM image analysis of hundreds of different nanoparticles. In various embodiments, the nanoparticles can comprise quantum dots, typically germanium quantum dots. Quantum dots have excitons that are constrained in all three spatial dimensions and may contain individual crystals, ie, each quantum dot is a single crystal.

In various embodiments, the nanoparticles can be photoluminescent upon exposure to UV light. Depending on the average diameter of the nanoparticles, it can be photoluminescent at any wavelength in the visible spectrum and can appear visually as any other color in red, orange, green, blue, violet or visible spectrum. For example, nanoparticles having an average diameter of less than about 5 nm can produce visible light luminescence, and nanoparticles having an average diameter of less than about 10 nm can produce near infrared (IR) luminescence. In one form of the present invention, the photoluminescent silicon nano-particles having at least 1 × 10 ⁶ light of photoluminescence intensity at an excitation wavelength of about 365nm. Fluorolog3 Spectrofluorometer with 450W Xe excitation source, excitation monochromator, sample holder, sideband filter (400nm), emission monochromator and xenon detector photomultiplier tube (available from Edison) , NJ's Horiba) measures the photoluminescence intensity. To measure the photoluminescence intensity, the excitation and emission slit widths were set to 2 nm and the integration time was set to 0.1 s. In this or other embodiments, the HR400 spectrophotometer (available from Ocean Optics, Dunedin, Florida) by means of a 1000 micron fiber coupled to a cumulative sphere and spectrophotometer (with >10% incident photon absorption) As measured above, the photoluminescent nanoparticle can have a quantum efficiency of at least 4% at an excitation wavelength of about 395 nm. Quantum efficiency was calculated by placing the sample into a cumulative sphere and exciting the sample by means of a 395 nm LED driven by an Ocean Optics LED driver. The absolute irradiance from the cumulative sphere is measured by a known light source calibration system. The quantum efficiency is then calculated by the ratio of the total photons emitted by the nanoparticles to the total photons absorbed by the nanoparticles. Moreover, in this or other embodiments, the nanoparticles may have a full width at half maximum of 20 to 250 at an excitation wavelength of 270-500 nm.

Furthermore, both photoluminescence intensity and luminescence quantum efficiency may continue to increase over time as the nanoparticles (as the case may be in the capture fluid, diffusion pump fluid or helium oxide material) are exposed to air. In another form of the invention, the maximum emission wavelength of the nanoparticles is shifted to shorter wavelengths over time when exposed to oxygen. The luminescence quantum efficiency of the nanoparticle composition can be increased by about 200% to about 2500% when exposed to oxygen. However, other increases in luminescence quantum efficiency are also covered. The photoluminescence intensity can be increased by 400% to 4500% depending on the time of exposure to oxygen and the concentration of nanoparticles in the oxane material (or capture fluid (if different from the oxane material)). However, other increases in photoluminescence intensity are also covered. The wavelength emitted from the direct capture composition also undergoes a blue shift in the emission spectrum. In one form of the invention, the maximum emission wavelength is reduced by about 1 nm based on the core size of the nanoparticle and displaced by about 100 nm, depending on the time of exposure to oxygen. However, other maximum emission wavelength shifts are also covered.

Independent of the particular nanopellet material nanoparticle used in the nanoparticulate composition, the method further comprises depolymerizing the rhodium oxide material of the nanoparticle composition to form a volatile rhodium compound. The depolymerized siloxane material can comprise any known method of depolymerizing a siloxane material and can be a continuous, semi-continuous or batch process.

In one embodiment, the decane material is depolymerized in the presence of a dialkyl carbonate. In this embodiment, the decane material may or may not be depolymerized in the presence of a catalyst other than the dialkyl carbonate. Specific examples of catalysts suitable for depolymerization include inorganic salts, metal oxides, metal hydroxides, inorganic bases, and organic Lewis bases (as appropriate, in combination with alcohols). The catalyst can increase the rate of depolymerization of the siloxane material. Various combinations of catalysts may be used in the depolymerization as appropriate. For example, two different types of inorganic salts can be used in combination with each other, and/or inorganic salts can be used in combination with metal oxides, and the like. The volatile hydrazine compound produced by this depolymerization process is generally an alkoxy decane as described below.

Dialkyl carbonates are known in the art and generally refer to carbonates (i.e., organic carbonates). The dialkyl carbonate is usually an ester of carbonic acid. For this purpose, in certain embodiments, the dialkyl carbonate used to depolymerize the oxoxane material typically has the general formula: (R ¹ O) ₂ C=O, wherein R ¹ is independently selected C ₁ -C ₁₂ alkyl. In certain embodiments, R ^{1 is} independently selected from the group consisting of methyl, ethyl, and propyl. Specific examples of dialkyl carbonates suitable for the depolymerization of a oxoxane material include dimethyl carbonate, diethyl carbonate and dipropyl carbonate, although the alkyl groups are not necessarily the same in the dialkyl carbonate.

The dialkyl carbonate can be used in varying amounts, although usually in an amount sufficient to depolymerize the rhodium alkane material. In one embodiment, each of the molybdenum materials is at least Dialkyl carbonate is used in an amount of 0.1, or at least 0.2, or at least 0.5, or at least 1, or at least 2, or at least 5, or at most 10 moles of dialkyl carbonate.

As described above, the deoxygenated alkane can be depolymerized in the presence of a catalyst. Specific examples of inorganic salts suitable for the catalyst include alkali metal salts such as KF, NaF, NaCl, LiCl, KI, KCl and CsCl. Specific examples of metal oxides suitable for the catalyst include those comprising an alkali metal or an alkaline earth metal such as CaO, Na ₂ O, K ₂ O and MgO. Specific examples of metal hydroxides suitable for the catalyst also include those catalysts comprising an alkali metal or an alkaline earth metal such as KOH, NaOH, CsOH, LiOH and Ca(OH) ₂ .

Alternatively or additionally, the catalyst may comprise an organic Lewis base. The organic Lewis base can be selected from known organic Lewis bases. Organic Lewis bases typically have a lone pair of electrons that can be supplied to a Lewis acid to form a Lewis adduct. The organic Lewis base can be a liquid or a solid at atmospheric pressure. Alternatively, the organic Lewis base can be a homogeneous catalyst or a heterogeneous catalyst. A homogeneous catalyst is one that is generally co-dissolved in a solvent such that the organic Lewis base is in the same phase as the reactant. The heterogeneous catalyst is one of the catalysts in a different phase (e.g., solid to gas) to the reactants. The different phases may also be liquid-liquids in which the liquids are immiscible with each other. Typically, the organic Lewis base is selected such that it is soluble at atmospheric pressure to be miscible with the dialkyl carbonate.

The organic Lewis base can comprise, for example, nitrogen, phosphorus, sulfur, oxygen, selenium, and/or cesium. For example, when the organic Lewis base contains nitrogen, the organic Lewis base can include a primary amine, a secondary amine, a tertiary amine, a heterocyclic amine, a bicyclic amine, or a combination thereof. Alternatively, when the organic Lewis base contains phosphorus, the organic Lewis base can include a primary phosphine, a secondary phosphine, a tertiary phosphine, a phosphazene, a cyclophosphazene or a combination thereof.

In a particular embodiment, the organic Lewis base comprises 1,4-diazabicyclo[2.2.2]octane (DABCO), At least one of pyridine, N,N-dimethylbenzylamine and morpholine.

The organic Lewis base can be used in varying amounts, although usually in an amount sufficient to depolymerize the rhodium alkane material. In one embodiment, from 1:1,000 to 5:1; or from 1:100 to about 1:1 The weight ratio of the organic Lewis base to the oxoxane material is an organic Lewis base.

When the depolymerized oxoxane material comprises an alcohol, the alcohol is typically an organic compound having a single hydroxy functional group, although the alcohol may have two or more hydroxy functional groups. Typically, the hydroxy functional group is at the end in the alcohol, although the hydroxy functional group may alternatively be located on the side of the chain from the organic compound. The organic compound may be a C ₁ -C ₁₂ organic compound. Specific examples of the alcohol include methanol, ethanol, isopropanol, butanol and the like.

If used, alcohol can be used in various amounts. In some embodiments, from 1:50 to 5:1, or 1:30 to 4:1, or 1:20 to 3:1, or at least 2:10, 3:10, 4:10, 5: The alcohol is used in the volume ratio of 10:6, 7:10, 8:10, 9:10, 1:1, 1.5:1, 2:1 or 2.5:1 alcohol to dialkyl carbonate.

If necessary, the oxoxane material can be depolymerized in the presence of an acid catalyst or in the absence of an acid catalyst.

The depolymerized siloxane material typically comprises heating a mixture comprising a nanoparticle composition, a dialkyl carbonate, a catalyst, and optionally an alcohol. The mixture can be heated at a pressure above or below atmospheric pressure. In certain embodiments, the mixture is heated to a temperature of less than 275, or less than 225, or less than 175 °C. For example, the mixture can be heated to a temperature of from 75 to 250 ° C in various embodiments. However, since the catalyst and the alcohol are optionally present in the depolymerization, those skilled in the art can optimize the parameters of the process (e.g., temperature, pressure, and relative amount of dialkyl carbonate) to exclude the catalyst and/or Or the need for alcohol.

The depolymerized oxymethane material may optionally be carried out in an inert atmosphere such as an atmosphere comprising nitrogen (N ₂ ) and/or argon (Ar).

As described below, the period of depolymerization of the decane material is generally sufficient for substantial depolymerization of the siloxane material. This period can be 5 to 72 or 6 to 64 hours.

As first introduced above, in this embodiment, the volatile oxime compound produced by depolymerizing the siloxane material is typically an alkoxy decane and/or an alkoxy decane. Alkoxy The decane can be a mixture of different alkoxy decanes or a mixture comprising a plurality of identical alkoxy decanes. The alkoxydecane typically comprises from 0 to 3 substituted or unsubstituted hydrocarbyl groups and from 1 to 4 alkoxy groups, with the proviso that the alkoxydecane comprises a second deuterium atom. However, the alkoxydecane may be monomeric or oligomeric, although the latter is typically an alkoxy oxirane.

The volatile hydrazine compound (i.e., alkoxy decane) generally has the general formula: (R ² ) _w (R ³ ) _x Si(OR ⁴ ) _y (OR ⁵ ) _z , wherein R ^{2 -} R ^{5 are} independently selected from The above R, that is, R ^{2 -} R ^{5 are} independently selected from a substituted or unsubstituted hydrocarbon group; y + z 1; and w+x+y+z=4. Specific examples of R ^{2 to} R ⁵ include an alkyl group, an aryl group, an aralkyl group, and an alkylaryl group.

In general, the type of alkyl carbonate used affects the resulting alkoxydecane. For example, R ^{1 of the} alkyl carbonate is generally the same as R ⁴ and/or R ^{5 of the} alkoxy decane.

Specific examples of the alkoxydecane which can be formed by means of depolymerization include Me ₂ Si(OMe) ₂ , PhMeSi(OMe) ₂ , Me ₂ Si(OEt) ₂ , (MeO) ₂ SiMe(CH ₂ CH ₂ CF ₃ ) MeSi(OMe) ₃ , PhSi(OMe) ₃ , Ph ₂ Si(OMe) ₂ and Me ₂ (OMe)Si-O-SiMe ₂ (OMe).

In a particular embodiment, the alkoxy is obtained in a yield of at least about 40, or at least 50, or at least 75, or at least 90, or at least 95, or at least 98% by weight relative to the decane content of the siloxane material. Base decane.

Additional information relating to this particular depolymerization technique can be found in U.S. Patent Application Serial No. 61/768,709, which is incorporated herein in its entirety by reference.

In an alternate embodiment, the decane material is depolymerized in the presence of a depolymerization catalyst other than the dialkyl carbonate described above. In these embodiments, the volatile rhodium compound typically comprises a cyclodecane compound.

In this alternative embodiment, the depolymerization catalyst can be selected from any depolymerization catalyst suitable for depolymerizing a decane material. In certain embodiments, the depolymerization catalyst comprises an organic or inorganic base. In other embodiments, the depolymerization catalyst comprises an organic or inorganic acid.

Specific examples of the solid acid which can be used as the depolymerization catalyst include aluminosilicate, acid Aluminate, zeolite, mixed metal oxide, heteropoly acid, sulfated metal oxide, carbon-based solid acid, ion exchange resin, sulfonated polymer, high molecular weight carboxylic acid, acidic metal salt, and combinations thereof .

Alternatively, the depolymerization catalyst can comprise clay, mixed metal oxides, sulfonated metal oxides, or a combination thereof. Alternatively, the depolymerization catalyst may comprise kaolin, bentonite, illite, chlorite, palygorskite or a combination thereof. The clay can be pickled, that is, the clay can contain pickled clay. Other examples of depolymerization catalysts include montmorillonite, saponite, nontronite (iron montmorillonite), beidellite, bentonite, laponite, and combinations thereof.

In various embodiments, the depolymerization of the oxoxane material is carried out in the presence of an organic polymer other than the depolymerization catalyst described above. The organic polymer can be a waste product that is otherwise suitable for recycling. The organic polymer can be a thermoplastic organic polymer such as a polyolefin.

In a particular embodiment, the organic polymer comprises at least one of: a linear polyolefin or copolymer polyolefin, a branched polyolefin or copolymer polyolefin, a grafted polyolefin or copolymer polyolefin, a borane A polyolefin of a branch, a polyolefin having a side hydroxyl group, a polyolefin grafted with another polymer, a blend of a polyolefin with another polymer, and a polyolefin filled with an inorganic material.

In a particular embodiment, the organic polymer comprises at least one of polyethylene (PE), polypropylene (PP), polymethylpentene (PMP), polybutene-1 (PB-1), poly Isobutylene, poly(ethylene-co-propylene), poly(propylene-co-1,4-hexadiene), poly(isobutylene-co-isoprene), poly(ethylene-co-propylene-total-1, 4-hexadiene, PE-g-PVA, PP-g-PMMA, PP-g-PVA, PE-g-PCL, PP-g-PCL, EP-g-PMMA, butyl-g-PMMA, PMMA , PVA, PS, PVC, PVAC, and a polyolefin filled with at least one of mica, calcium carbonate, cerium oxide, glass, magnesia, alumina, and clay. The polyethylene may be, for example, low density polyethylene (LDPE). Medium density polyethylene (MDPE) and / or high density polyethylene (HDPE).

In a particular embodiment, the organic polymer is a thermoplastic comprising at least one of the following Organic polymer: polyoxymethylene, polyoxymethylene copolymer with oxygen extended ethyl group and other structural units as the case exists, polymethyl methacrylate (PMMA), PMMA copolymer, polystyrene, polystyrene copolymer , celluloid, celluloid acetate, cyclic olefin copolymer, ethylene vinyl acetate (EVA), ethylene vinyl alcohol (EVOH), fluoroplastic, PTFE, acrylonitrile-butadiene -styrene (ABS), polyacrylate, polyamine, polyamido-imide, polyimine, polyetherimide, polyfluorene, polyether oxime, polyketone, polyetheretherketone (PEEK ), polycarbonate, polyester, polycaprolactone, polybutylene terephthalate, polyethylene terephthalate, polylactic acid, polyphenylene ether, polyphenylene sulfide, thermoplastic polyurethane Ester, polyvinyl acetate (PVA), polyvinyl chloride (PVC), polydichloroethylene (PVDC) and styrene-acrylonitrile (SAN) copolymers.

When the depolymerization of the decane material of the nanoparticle composition is carried out in the presence of an organic polymer, it is expected that the nanoparticle may be directly incorporated into the organic polymerization during and/or after the depolymerization of the siloxane material. In. The incorporation of nanoparticle into the organic polymer can be carried out before, during or after any separation of the volatile rhodium compound from the nanoparticle/organic polymer mixture.

In general, the nanoparticle composition, the depolymerization catalyst, and optionally the organic polymer are combined to form a mixture. The mixture may comprise a depolymerization catalyst in an amount of 0.01 to 25, or 0.01 to 20, or 0.01 to 15, or 0.01 to 10% by weight, based on the total weight of the mixture. In such embodiments, the mixture may comprise an organic polymer, if present, in an amount from 0.1 to 99% by weight based on the total weight of the mixture. In certain embodiments, the mixture may comprise an organic polymer, if present, in an amount of at least 90 or at least 95% by weight, based on the total weight of the mixture. In other embodiments, the mixture comprises an organic polymer, if present, in an amount from 1 to 25% by weight based on the total weight of the mixture.

The mixture can optionally be sheared to form a homogeneous or semi-homogenous mixture. For example, the nanoparticle composition, optionally the organic polymer and the depolymerization catalyst can be combined and mixed for high shear mechanical devices, extruders, twin screw extruders, etc. (as appropriate) A mixture is formed in the degassing port).

Although the mixture may be free of solvents, the mixture may also include organic solvents. However, usually, the mixture contains the organic solvent in an amount of less than 20, or less than 10, or less than 1, or less than 0.5, or less than 0.1, or less than 0.05% by weight based on the total weight of the mixture.

The oxirane material is typically depolymerized in this embodiment by heating the mixture described above. Heating may be performed for a period of time sufficient to depolymerize the siloxane material to form a volatile hydrazine compound. In certain embodiments, the mixture is heated at least 0.1, or at least 1, or at least 5, or at least 10, or at least 30, or at least 60 minutes. It can last for a much longer period of time than 60 minutes, for example 24 hours for heating.

The temperature of the heated mixture is typically less than 350 °C. When the depolymerization is carried out in the presence of an organic polymer, the temperature is usually less than the decomposition temperature of the organic polymer, for example, at least 5 or at least 10 ° C below the decomposition temperature of the organic polymer. For this purpose, the temperature of the heated mixture depends on the organic polymer used in the mixture. The temperature is usually from 60 to 340 °C. This temperature range is usually used even when the mixture does not include an organic polymer.

As described above, the volatile rhodium compound produced in this particular embodiment comprises a cyclodecane. Cyclodecane is known in the art and comprises repeating D decyloxy units. For example, when the volatile ruthenium compound comprises a cyclodecane, the cyclodecane can have the formula: (R ⁶ R ⁷ SiO ₂ ) _{n '} , wherein R ⁶ and R ^{7 are} independently selected from R, which is As defined above. The subscript n' represents the number of decyloxy units in the cyclodecane. The cyclodecane produced by means of the depolymerized oxoxane material may comprise a mixture wherein the cyclodecane may be varied in terms of the number of substituents and/or decyloxy units. In general, n' is an integer from 3 to 25, or from 3 to 20, or from 3 to 12, or from 3 to 7. When n' is less than 3, the cyclodecane is not substantially cyclic in nature.

Volatile ruthenium compounds other than cyclodecane can be produced by means of the depolymerized siloxane material (excluding and including cyclodecane). For example, volatile bismuth compounds can be additionally packaged Containing acyclic alkoxysilane oligomers and/or monomers. Further, the volatile hydrazine compound may additionally comprise a linear siloxane alkane oligomer or monomer.

Additional information relating to this particular depolymerization technique can be found in U.S. Patent Application Serial No. 61/768,710, which is incorporated herein in its entirety by reference.

Independent of the technique for depolymerizing a naphthenic material of a nanoparticulate composition, the method further comprises the step of substantially separating the nanoparticle from the volatile rhodium compound. When the rhodium alkane material is depolymerized while the nanoparticulate composition is present in the mixture, the method can comprise the step of substantially separating the nanoparticles from the mixture. This may alternatively be referred to as substantially separating the nanoparticles. Separating or separating the nanoparticle substantially allows for incorporation or use in other compositions or applications, thereby increasing the useful life of the nanoparticle.

"Substantially" as used herein with reference to substantially separating a nanoparticle from a volatile oxime compound means the initial removal (reduction) of the nanoparticle composition by substantially separating the nanoparticle with the volatile cerium compound. At least 10, or at least 20, or at least 30, or at least 40, or at least 50, or at least 60, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90% by weight. For example, a nanoparticle composition having a mass of 100 kg is assumed to depolymerize the siloxane material and substantially separate the nanoparticle with volatile hydrazine compounds and other by-products, including oxime monomers, oligomerization. After the article or polymer, the resulting composition has a mass of less than 100 kg, for example in an amount of only 10 kg, which corresponds to a 90% mass reduction. This can be readily measured by measuring the initial mass of the nanoparticle composition and the quality of the nanoparticle after substantially separating the nanoparticle from the volatile anthraquinone compound and any other by-products. This reduction also depends on the amount of nanoparticle in the nanoparticle composition, which can vary. For example, if the nanoparticulate composition comprises nanoparticles in an amount of 50% by weight based on the total weight of the nanoparticulate composition, the mass reduction will generally not exceed 50%.

The volatile cerium compound and the nanoparticle can be substantially separated from known methods. For example, the volatile cerium compound and the nanoparticle can be separated by means of distillation and/or degassing. Distillation The temperature and conditions generally depend on the volatile rhodium compound produced by the depolymerization of the rhodium alkane material and its boiling point.

Once the nanoparticles and volatile hydrazine compounds are substantially separated, the nanoparticles and/or volatile hydrazine compounds can be reused or recycled for other end uses and applications. For example, nanoparticles can be included in other compositions and used in many end uses depending on physical properties. The volatile hydrazine compound can be polymerized to form a decane.

It should be understood that the scope of the appended claims is not limited to the particulars described in the embodiments. A compound, composition or method (which may vary between specific embodiments within the scope of the appended claims). For any Markush group on which the various features or aspects of the various embodiments are described, it can be obtained from each member of the respective Marcuse group independent of all other Markusi members. Different, special and/or unexpected results. Each member of the Markush group may be relied upon individually and/or in combination to provide sufficient support for a particular embodiment within the scope of the appended claims.

In addition, any range and sub-ranges that are relied upon in the various embodiments of the present invention are intended to be within the scope of the appended claims. The fractional value, even if the equivalent is not explicitly written in this article. The scope and sub-ranges of the present invention are readily described and enabled by the skilled artisan, and the various embodiments of the invention can be practiced, and the scope and sub-ranges can be further described as related half, one third, and four. One, one fifth, etc. As an example, the "0.1 to 0.9" range can be further described as the lower third (ie 0.1 to 0.3), the middle third (ie 0.4 to 0.6) and The upper third (ie, 0.7 to 0.9), which is individually and collectively within the scope of the appended claims, and which may be individually and/or collectively dependent and within the scope of the appended claims Particular embodiments provide sufficient support. In addition, with respect to languages that define or modify a range, such as "at least", "greater than", "less than", "not exceeding", and the like, it is understood that the language includes sub-ranges and/or upper or lower limits. As another example, the scope of "at least 10" Qualitatively includes at least a range of 10 to 35 sub-ranges, a sub-range of at least 10 to 25, a sub-range of 25 to 35, etc., and each sub-range can be individually and/or collectively dependent and specific implementation within the scope of the appended claims The example provides sufficient support. Finally, it is possible to rely on individual numbers within the scope of the disclosure and to provide sufficient support for the specific embodiments within the scope of the appended claims. For example, the "1 to 9" range includes various individual integers, such as 3, and individual numbers including decimal points (or fractions), such as 4.1, which may depend on such numbers and are within the scope of the appended claims. Particular embodiments provide sufficient support.

The following examples are intended to illustrate the invention and are not intended to limit the scope of the invention in any way.

Instance Example 1:

The nanoparticle composition is prepared in situ by producing nanoparticle by means of a plasma process and directly capturing or collecting the nanoparticles in the siloxane material. Specifically, in the case of additional Ar and H ₂ in the precursor gas, nanoparticle was prepared by means of a plasma reactor system containing ₁₆ % by volume of SiH ₄ (2 vol% in Ar) precursor gas. The precursor gas is delivered to the reactor by means of a mass flow controller.

The nanoparticle is produced and captured or collected in a siloxane material to produce a nanoparticle composition. The oxoxane material comprises a polydimethyloxane fluid. The nanoparticle composition was removed from the plasma reactor system and aged in a humid oven to increase the photoluminescence intensity of the nanoparticle of the nanoparticle composition.

5 g of the nanoparticle composition and 0.25 g of the depolymerization catalyst were placed in a round bottom flask and sonicated for 5 minutes. The depolymerization catalyst comprises acidified clay (montmorillonite). The flask was attached to a rotary evaporator and spun at 85 ° C to 90 ° C for 2 hours under atmospheric pressure. Vacuum was applied and the temperature was increased to 145 ° C to distill the contents of the flask for about 1 hour. The temperature was increased to about 180 ° C over one hour, and the contents of the flask were again distilled at this temperature for about 15 minutes. Distillation results in a volatile oxime formed by the depolymerization of a oxoxane material, ie a polydimethyl methoxy alkane fluid Substantial separation of the compound from the nanoparticles. The contents of the flask were cooled and toluene was placed in the flask. The contents of the flask were subjected to a sonic bath and filtered through a fine glass filter while flushing with additional toluene. The toluene particles were separated by removing the toluene by rotary evaporation. The isolated nanoparticle has a mass reduction of about 90% compared to the initial nanoparticle composition, which can be attributed to the depolymerization of the siloxane material and the substantial separation of the nanoparticle from the volatile cerium compound. When irradiated by UV radiation, the separated nanoparticles exhibit bright red photoluminescence.

Example 2:

A nanoparticle composition was prepared in the same manner as the nanoparticle composition of Example 1.

A 5 g nanoparticle composition, 8.5 g of dimethyl carbonate, 20 g of methanol, 17 g of mesitylene, and 0.25 g of NaCl were placed in a 100 mL Parr reactor vessel, and then the reactor vessel was sealed. The vessel was set at 600rpm and at a fixed N ₂ purge for about 10 minutes, after which the container resealed. The vessel was heated to about 180 ° C for 16 hours with stirring to depolymerize the rhodium oxide material of the nanoparticle composition to form a volatile rhodium compound. Once the container is cooled and the pressure is reduced to near normal pressure, the vent valve is opened on the container and a vacuum is applied. The vessel was slowly heated to 80 ° C and a distillate containing volatile rhodium compounds was collected in a flask under a dry ice cold trap. After distillation, the contents of the vessel were measured and, by measurement, about 50% by weight of the liquid phase, i.e., the decane material, was depolymerized by distillation. In other words, the nanoparticles are substantially separated from the volatile ruthenium compound formed from the depolymerized siloxane material, i.e., the polydimethyl siloxane fluid.

The present invention has been described in an illustrative manner, and it is understood that the terms that have been used are intended to have a Obviously many modifications and variations of the present invention are possible in the light of the teaching. The invention may be practiced otherwise than as specifically described.

10‧‧‧Variable RF Amplifier/VHF RF Power Supply

11‧‧‧Dielectric discharge tube/dielectric tube/discharge tube/plasma generation chamber

12‧‧‧Glow discharge/plasma

13‧‧‧Electrode configuration / electrode / tip / porous electrode plate

14‧‧‧Electrode/VHF RF Power Supply Ring/Grounding Ring/Porous Electrode Plate

15‧‧‧ Large vacuum reactor

16‧‧‧Solid substrate

Claims (15)

A method for recovering nanoparticle from a decyl alkane material, the method comprising: providing a nanoparticle composition comprising a siloxane material and a nanoparticle; and depolymerizing the siloxane material of the nanoparticle composition to form Volatile hydrazine compound; and substantially separating the volatile hydrazine compounds from the nanoparticles to recover the nanoparticles. The method of claim 1, wherein the oxoxane material is selected from the group consisting of a decane fluid, a decane gel, a decane resin, and a decane elastomer. The method of claim 1, wherein the decane material is a decane fluid. The method of claim 1, wherein the nanoparticles of the nanoparticle composition are produced by a plasma process. The method of claim 1, wherein the nanoparticle composition is produced by forming a nanoparticle aerosol in a low pressure reactor, wherein the nanoparticle aerosol comprises nanoparticle present in a gas And collecting the nanoparticle of the nanoparticle aerosol in a oxoxane fluid to produce the nanoparticle composition. The method of claim 5, wherein the nanoparticle composition is produced by a process comprising the steps of: in a plasma reactor having a reactant gas inlet and an outlet having an orifice therein, the application has a ratio of about 10 to a preselected VHF radio frequency to reactant gas mixture having a continuous frequency in the range of about 500 MHz and a coupling power in the range of from about 5 to about 1000 W to produce a plasma for a time sufficient to form the nanoparticle aerosol, wherein the reactant gas The mixture comprises from about 0.1 to about 50% by volume of the first precursor gas and at least one inert gas; and the nanoparticles of the nanoparticle aerosol are collected in a helium alkane fluid The nanoparticle composition is produced. The method of claim 5, wherein the nanoparticle composition is produced by a method comprising the steps of: forming the nanoparticle aerosol in the reactor; introducing the nanoparticle aerosol from the reactor to the reactor a diffusion pump in which a helium oxide diffusion pump fluid is heated to form a vapor and is delivered via a jetting assembly; the vapor is emitted into a chamber of the diffusion pump via a nozzle and the vapor is condensed to form a condensate; Returning the condensate stream to the reservoir; capturing the nanoparticles of the aerosol in the condensate; and collecting the captured nanoparticles in the reservoir to produce the nanoparticle combination. The method of any one of claims 1 to 7, wherein depolymerizing the siloxane material comprises heating the oxoxane material in the presence of acidified clay. The method of any one of claims 1 to 7, wherein the depolymerizing the siloxane material comprises heating the oxoxane material in the presence of a dialkyl carbonate. The method of any one of claims 1 to 7, wherein substantially separating the volatile cerium compounds from the nano sized particles comprises distilling the volatile cerium compounds and the nano sized particles. The method of any one of claims 1 to 7, wherein the nanoparticles of the nanoparticle composition are photoluminescent. The method of claim 11, wherein the nanoparticles have an average diameter of less than 5 nm. The method according to item 11 of the request, wherein the nano particle composition has at least 1 × 10 ⁶ of the optical luminescence intensity at an excitation wavelength of about 365nm. The method of claim 11, wherein the nanoparticle composition has a quantum efficiency of at least 4% at an excitation wavelength of about 365 nm. The method of claim 11, wherein the nanoparticle composition has a full width at half maximum of 20 to 250 at an excitation wavelength of 270-500 nm.