TWI397548B - Composite particle including nano wires and method for making the same - Google Patents

Description

Composite particle containing nanowire and preparation method thereof

The invention relates to a composite particle and a preparation method thereof, in particular to a nano composite particle and a preparation method thereof.

The nanocomposite particles are composed of two or more solid phase powders having different properties. A composite particle having a diameter of nanometer formed of nano particles and a matrix material, and having excellent physical properties. The structure of the nanocomposite particles is usually a core-shell structure, see the document "Preparation and Sintering Behaviour of Nanostructured Alumina/Titania Composite Powders Modified with Nano-dopants" (Yong Yang, You Wang, Materials Science and Engineering A, Vol. 490, P457-464 (2008)). In this document, Yong Yang et al. disclose a nano-composite particle formed of nano-alumina particles and a titanium oxide matrix and a preparation method thereof. The nano composite particles are a core-shell structure, and the preparation method is a sintering method. However, the sintering method is generally only suitable for preparing composite particles whose matrix is a ceramic material, and it is not suitable to prepare composite particles based on a polymer or other materials. Therefore, the application of the nano composite particles is limited.

In order to solve this problem, a zinc oxide-polymer core-shell luminescent particle and a preparation method thereof are disclosed in CN 101245126 A, which is published on Feb. 28, 2008 by Xiong Huanming and Ren Qingguang. The core of the zinc oxide-polymer core-shell luminescent particles is a zinc oxide quantum dot having a particle diameter of about 10 nm in each direction, and the outer layer is composed of an inner layer of polymethacrylic acid and an outer layer of polyethylene glycol monomethyl group. Ether group to make. The preparation method of the nano composite particles is a sol-gel method, wherein the specific steps are: dissolving a zinc salt of an organic carboxylic acid into anhydrous ethanol, and then adding an alkali solution to promote hydrolysis of the zinc salt to form a surface modification in an anhydrous environment. The organic double-bonded zinc oxide nanoparticle; the initiator and the polymer monomer are added to the reaction system, and the polymerization reaction is initiated at a temperature of 70-80 ° C to form a copolymerized polymer shell on the surface of the zinc oxide nanoparticle. .

Nanocomposite particles are usually surface-modified in applications to have different surface activities for use in different fields. However, since the zinc oxide-polymer core-shell luminescent particles of the above core-shell structure contain only one zinc oxide quantum dot, when the number of zinc oxide quantum dots required is large, for example, the zinc oxide-polymer core The surface modification of the shell luminescent particles for use as a fluorescent label in medical treatment requires surface modification of the complex zinc oxide-polymer core-shell luminescent particles. Therefore, more modifiers are needed for the zinc oxide-polymer core shell. The luminescent particles are modified.

In view of the above, it is necessary to provide a nano composite particle which can save the amount of surface modifier in the application and has a simple preparation method and a preparation method thereof.

A composite particle comprising a nanowire comprising a polymer matrix and a plurality of nanowires uniformly dispersed in the polymer matrix, the nanowire-containing composite particles having a diameter of less than 1000 micrometers.

A method for preparing a composite particle containing a nanowire, comprising the steps of: providing a plurality of nanowires; providing a liquid polymer material or a polymer monomer; dispersing the plurality of nanowires to the liquid polymer material or In the polymer monomer; solidifying to form a composite material; and pulverizing the composite material to form a nano composite particle.

Compared with the prior art, the nano composite particle provided by the invention and the preparation method thereof have the following advantages: First, the nano composite particle provided by the invention contains at least one nanowire, and in practical applications, a plurality of nanowires are required. Therefore, it is necessary to modify the surface of the nano-composite particles containing nanowires. When the properties are small, only a few nano composite particles may be surface-modified, and the amount of surface modifier required for the nano-composite particles of the core-shell structure is less; second, the nano-composite particles provided by the present invention The preparation method first disperses the nanowire in a liquid polymer or a polymer monomer and solidifies it, and then directly pulverizes by a pulverization method. Compared with the sol-gel method or the sintering method, the method is simple and easy to realize the industry. Chemical.

10‧‧‧Nano composite particles

104‧‧‧Nan line

102‧‧‧ polymer matrix

FIG. 1 is a schematic structural view of a nano composite particle according to an embodiment of the present invention.

2 is a flow chart of a method for preparing nano composite particles according to an embodiment of the present invention.

The nano composite particles provided by the present invention and a preparation method thereof will be further described below in conjunction with the accompanying drawings and specific embodiments.

Referring to FIG. 1 , an embodiment of the present invention provides a nano composite particle 10 comprising a polymer matrix 102 and at least one nanowire 104 disposed in the polymer matrix 102 .

The material of the polymer matrix 102 is one or more of resin, rubber and plastic. Specifically, the material of the polymer matrix 102 according to different applications is one or more of polyethylene, polyethylene, polypropylene, polyvinyl chloride, polytetrafluoroethylene, natural rubber, polyoxymethylene, and polyacetal. In this embodiment, the material of the polymer matrix 102 is selected from translucent, non-toxic polyethylene.

The nanowires 104 comprise different types, including metal nanowires, the metal materials thereof include nickel, platinum or gold; the semiconductor nanowires, the semiconductor materials thereof include gallium arsenide, gallium phosphide, gallium nitride, cadmium sulfide , tin oxide, titanium dioxide or zinc oxide; insulator nanowires, the insulator material of which includes cerium oxide or titanium dioxide. The diameter of the nanowire 104 is less than 10 microns and the length is not limited. Preferably, the material of the nanowire 104 is a semiconductor nanowire. In the present embodiment, the nanowire 104 is a zinc oxide nanowire. The diameter of the zinc oxide nanowire is less than 50 microns and the length is not limited. Nanocomposite The diameter of the sub-10 is less than 1000 microns, and preferably the diameter of the nanocomposite particles 10 is 300-700 microns. In this embodiment, the nano composite particles 10 have a diameter of 500 μm.

Additionally, a plurality of nanowires 104 may be included in the nanocomposite particles 10. When the nano composite particles 10 contain a plurality of nanowires 104, the nanowires 104 are uniformly dispersed in the nanocomposite particles 10. In this embodiment, the nano composite particles include a plurality of zinc oxide nanowires dispersed in a polyethylene matrix.

Alternatively, the nanocomposite particle 10 further includes an additive or a mixture of a plurality of additives. The additive includes a curing agent, a modifier, a filler or a diluent, and the like. The curing agent is used to promote curing of the polymer matrix material. Commonly used curing agents include one or a mixture of a fatty amine, an alicyclic amine, an aromatic amine, a polyamine, an acid anhydride, a resin, and a tertiary amine. The modifier is used to improve the flexibility, shear resistance, bending resistance, impact resistance or insulation of the polymer matrix material. Commonly used modifiers include one or a mixture of polysulfide rubber, polyamide resin, polyvinyl butyral or nitrile rubber. The filler is used to improve the heat dissipation condition of the polymer matrix material when it is cured, and the use of the filler can also reduce the amount of the polymer material and reduce the cost. Commonly used fillers include one or a mixture of asbestos fibers, glass fibers, quartz powder, porcelain powder, alumina and tannin powder. The diluent is used to lower the viscosity of the resin and improve the permeability of the resin. The diluent includes diglycidyl ether, polyglycidyl ether, propylene oxide butyl ether, propylene oxide phenyl ether, dipropylene oxide ethyl ether, tripropylene oxide propyl ether and allyl phenol. One or a mixture of several.

The nanocomposite particles 10 have different applications depending on the material of the nanowire 104. In this embodiment, a nano-composite particle provided with polyethylene as a matrix material and at least one zinc oxide nanowire disposed in the polyethylene can be used as a fluorescent marker in medical treatment. When applied, the surface of the nano composite particle is first modified to fix a biochemical identification mark on the surface of the nano composite particle, so that the nano composite particle can adhere to the cancer having the biochemical identification mark. On the cell. The zinc oxide nanowire is a semiconductor luminescent material that emits light of a specific wavelength, and the polyethylene is translucent due to Therefore, the light emitted by the zinc oxide nanowire can penetrate the polyethylene, and the position and the luminescence intensity of the zinc oxide nanowire can be seen through the optical identification device, thereby determining the presence or absence of a certain cancer cell, and Location and quantity.

The nano composite particle provided by the invention contains at least one nanowire. In practical applications, when a plurality of nanowires are required, it is necessary to modify only a few nano composite particles when surface modification of the nano composite particle is required. That is, the amount of surface modifier required for the nanocomposite particles compared to the core-shell structure is small.

Referring to FIG. 2, an embodiment of the present invention further provides a method for preparing the nano composite particle 10, comprising the following steps:

Step 1: Provide multiple nanowires.

The nanowires comprise different types, including metal nanowires, the metal materials thereof include nickel, platinum, gold, etc.; the semiconductor nanowires, the semiconductor materials thereof include gallium arsenide, gallium phosphide, gallium nitride, cadmium sulfide , tin oxide, titanium dioxide, zinc oxide, etc.; insulator nanowire, the insulator material includes cerium oxide or titanium dioxide. Preferably, the nanowire is a semiconductor nanowire having a diameter of less than 50 micrometers and an unlimited length. The preparation method of the nanowire includes a chemical vapor deposition method, a template-limited auxiliary growth method, a metal organic vapor phase epitaxial growth method, and a colloidal chemical self-assembly method. In this embodiment, the nanowire is a zinc oxide nanowire, and the diameter of the zinc oxide nanowire is less than 100 nm, and the length is not limited. In this embodiment, the method for preparing the zinc oxide nanowire is a template-limited auxiliary growth method, which specifically includes the following steps: providing a porous alumina template; and depositing a silver film on the porous alumina template a cathode; one side of the silver plated film is fixed on a conductive substrate, and the other side of the silver film is exposed to the zinc chloride electrolyte; and at a constant potential state, zinc oxide is deposited into the nanopore in the template to remove The template obtained a zinc oxide nanowire.

Alternatively, the plurality of nanowires further comprises prior treatment with an organic solvent. Organic dissolution The agent is one or a mixture of ethanol, methanol, acetone, dichloroethane and chloroform. After the nanowire is treated with an organic solvent, the surface thereof is infiltrated with an organic solvent. According to the principle of similar compatibility, the treatment of the nanowires with an organic solvent contributes to their dispersion in the polymer material. In this embodiment, the zinc oxide nanowire is infiltrated by immersing the zinc oxide nanowire in ethanol for a period of time.

Step 2: Providing a liquid polymeric material or polymer monomer.

The polymer is one or more of thermosetting or thermoplastic resin, rubber and plastic. Specifically, the material of the polymer is polyethylene, polyethylene, polypropylene, polyvinyl chloride, polytetrafluoroethylene, natural rubber. One or more of polyoxymethylene or polyacetaldehyde. Alternatively, the polymer or polymer monomer may further comprise an additive or a mixture of a plurality of additives, and the liquid polymer material or polymer monomer mixed with the additive is stirred to make The polymer material or polymer monomer is uniformly mixed with the additive to obtain a liquid matrix material. The additive includes a curing agent, a modifier, a filler or a diluent, and the like. The time during which the liquid polymer material or polymer monomer to be mixed with the additive is stirred is determined by the type and amount of the polymer material, the polymer monomer material, and the additive. The more viscous the polymer, the more the type and amount of additives, the longer the mixing time. Alternatively, if the polymer provided is a polymeric material that is solid at room temperature, it is heated to melt to form a liquid polymeric material.

In this embodiment, a liquid polyethylene is provided without adding other additives. Since the polyethylene is waxy at normal temperature, it is heated to 112 ° C - 135 ° C and melted to obtain a liquid polyethylene.

Step 3: Adding the plurality of nanowires to the liquid polymer material or polymer monomer and dispersing.

The specific step of adding the plurality of nanowires to the liquid polymer material or polymer monomer and dispersing is: adding the plurality of nanowires to the liquid polymer material or polymer sheet In the body; mechanically agitating the polymer material or a mixture of polymer monomers and nanowires Mix and use ultrasonic treatment at the same time.

Mechanical agitation or sonication allows the nanowires to be uniformly dispersed in a liquid polymeric material or polymer monomer to form a liquid mixture. The agitation time is determined by the type and amount of polymer, polymer monomer and nanowire. The more the number of nanowires, the more viscous the polymer, the longer the mixing time is required. The ultrasonic treatment may be carried out by stirring or dispersing a mixture of the nanowires with a polymer material or a polymer monomer using an ultrasonic mixer or an ultrasonic disperser.

It will be appreciated that the method of dispersing the plurality of nanowires into the polymeric material may be other methods, such as dispersing the plurality of nanowires into the polymeric material using a magnetic stirrer.

In this embodiment, the plurality of zinc oxide nanowires are dispersed in the polyethylene, and the mixture of the zinc oxide nanowire and the polyethylene is mechanically stirred, and the zinc oxide nanowire is uniformly dispersed in the polyethylene by ultrasonic stirring. in.

Step 4: Curing to form a composite material.

For the liquid polymer material or the mixture of the polymer monomer and the nanowire, the composite material may be solidified by different methods depending on the polymer or the polymer monomer material to form a composite material.

The mixture of the thermosetting polymer material and the nanowire is cured by a stepwise heating method. The method of curing the thermosetting material by heating is specifically: heating a mixture of the nanowire and the liquid polymer by a heating device to form a composite material. Thermosetting materials require a gradual increase in temperature. Heating too fast can cause the thermoset polymer material to blast and affect the properties of the material. The temperature and time at which the thermoset material cures is determined by the type and amount of the polymer, additives, and nanowires. The higher the melting point of the polymer, the greater the amount of additives and nanowires, the longer the curing time. The heating device may be one of a heating device such as a heating plate, a hot press, a flat vulcanizer, an autoclave or an oven.

The mixture of the thermoplastic polymer material and the nanowire is cured by cooling. The method of lowering the temperature of the thermoplastic material is to cool the mixture of the liquid nanowire and the polymer by natural cooling at room temperature or by a cooling device to form a composite material. The cooling device may be one of a cooling device such as a circulating water cooler, a hydraulic oil cooler, or a water-oil cooler.

For the mixture of the polymer monomer and the nanowire, the polymerization reaction is initiated by adding an initiator to polymerize the polymer monomer to form a solidified polymer.

It is understood that the method of forming the mixture of the cured nanowires with the polymer material or the polymer monomer is not limited to the above method, and the composite material of the ruthenium rubber as the polymer material may also be cured by a photocuring technique, for example, by ultraviolet light curing.

In this embodiment, the mixture of the zinc oxide nanowire and the polyethylene material is a thermoplastic material, so that a mixture of the zinc oxide nanowire and the polyethylene is cooled by a circulating water cooler to form a composite material.

Step 5: pulverizing the above composite material to form nano composite particles.

The method of pulverizing the above composite material to form a nano composite particle includes a ball milling method, a granulator pulverization method, a crusher pulverization method, or a jet mill pulverization method. Preferably, the composite material is pulverized by a ball mill, and the method for pulverizing the composite material by the ball mill comprises the following steps: the grinding body having a diameter of 8 mm, a diameter of 5.5 mm, and a diameter of 3.9 mm The ratio of the ingredients in the 3:2:1-1:2:3 ratio to the material obtained in the fourth step is loaded into the barrel of the ball mill at a ratio of 1:1-40:1; the ball mill is started, and the barrel is ground. Under the action of inertia, centrifugal force and friction, the composite collides with the composite material in the cylinder, the ball mill rotates at 200-580 rpm, and the ball mill takes 1-50 hours to pulverize the composite to form nano composite particles.

In the ball milling process, the longer the ball milling time, the higher the ball milling speed, the larger the ball to material ratio and the grinding ball ratio The medium-sized ball has a small mass and the number of small balls can make the diameter of the nano-composite particles obtained by ball milling smaller. In the ball milling process, the shorter the ball milling time, the lower the ball milling speed, the smaller the ball-to-batch ratio and the larger the mass of the ball in the grinding ball ratio, and the smaller the number of small balls, the larger the diameter of the nano-composite particles obtained by ball milling. In this embodiment, the ball ratio of the large ball, the middle ball and the small ball is 1:2:3, the ball to material ratio is 3:1, the ball mill rotation speed is 350 rpm, and the ball milling time is 5 hours.

Alternatively, the nano composite particles obtained by the ball mill pulverization may be further placed in a jet mill to be further pulverized. The method for further pulverizing the nano composite particles obtained by the ball mill by using a jet mill comprises the steps of: adding the nano composite particles obtained by pulverizing the ball mill to the pulverization chamber of the jet mill; and spraying the compressed air through the nozzle The pulverization chamber is entered; the nano composite particles are further pulverized by repeated collision, friction, shearing under the action of the air formed by the compressed air. The pulverized nano composite particles move to the classification zone with the upward airflow under the action of the fan suction force, and the nano composite particles satisfying the particle size requirements are collected into the cyclone and the dust collector through the grading wheel, and the coarse particles that do not meet the particle size requirements are lowered to The crushing zone continues to smash.

The prepared nanocomposite particles have a diameter of less than 1000 microns, and preferably the nanocomposite particles have a diameter of from 300 to 700 microns. In this embodiment, the zinc oxide nanowire/polyethylene composite material is pulverized by ball milling to form nano composite particles, and the prepared nano composite particles have a diameter of 500 μm.

The nano composite particle provided by the invention and the preparation method thereof have the following advantages: First, the nano composite particle provided by the invention contains at least one nanowire, and in practical applications, when a plurality of nanowires are required, the When the nanowire is surface-modified with nano-composite particles, only a few nano-composite particles can be surface-modified, and the amount of surface modifier required for the nano-composite particles of the core-shell structure is less; Secondly, the preparation method of the nano composite particle provided by the invention first disperses the nanowire in a liquid polymer or a polymer monomer and solidifies it, and then directly pulverizes by using a pulverization method, compared to the sol-gel. The method or the sintering method is simple in method and easy to realize industrialization.

In summary, the present invention has indeed met the requirements of the invention patent, and has filed a patent application according to law. However, the above description is only a preferred embodiment of the present invention, and it is not possible to limit the scope of the patent application of the present invention. Equivalent modifications or variations made by those skilled in the art in light of the spirit of the invention are intended to be included within the scope of the following claims.

10‧‧‧Nano composite particles

104‧‧‧Nan line

102‧‧‧ polymer matrix

Claims (19)

A composite particle comprising a nanowire, comprising a polymer matrix, wherein the nanowire-containing composite particle further comprises a plurality of nanowires uniformly dispersed in the polymer matrix, wherein the nanowire-containing layer The composite particles have a diameter of less than 1000 microns. The composite particle containing a nanowire according to claim 1, wherein the nanowire-containing composite particle has a diameter of 300 to 700 μm. The composite particle containing a nanowire according to claim 1, wherein the material of the nanowire is nickel, platinum, gold, cerium oxide, gallium arsenide, gallium phosphide, gallium nitride, cadmium sulfide, One or more of tin oxide, titanium dioxide or zinc oxide. The composite particle containing a nanowire according to claim 1, wherein the nanowire has a diameter of less than 50 μm. The composite particle containing a nanowire according to claim 1, wherein the material of the polymer matrix is one or more of a resin, a rubber or a plastic. The nanowire-containing composite particle according to claim 1, wherein the nanowire-containing composite particle comprises an additive or a mixture of a plurality of additives. The composite particle containing a nanowire according to claim 6, wherein the additive comprises a fatty amine, an alicyclic amine, an aromatic amine, a polyamine, an acid anhydride, a resin, a polysulfide rubber, a polyamide resin, Polyvinyl alcohol tert-butyraldehyde, nitrile rubber, asbestos fiber, glass fiber, quartz powder, porcelain powder, alumina, tannin powder, diglycidyl ether, polyglycidyl ether, propylene oxide butyl ether, propylene oxide benzene Ethyl ether, dipropylene oxide ethyl ether, tripropylene oxide propyl ether, allyl phenol. A method for preparing a composite particle containing a nanowire, comprising the steps of providing a plurality of nanowires; providing a liquid polymer material or a polymer monomer; Adding the plurality of nanowires to the liquid polymer material or polymer monomer and dispersing; solidifying to form a composite material; and pulverizing the composite material to form composite particles containing nanowires. The method for preparing a nanowire-containing composite particle according to claim 8, wherein the specific step of adding the plurality of nanowires to the liquid polymer material or polymer monomer and dispersing is: adding The plurality of nanowires are in the liquid polymer material or polymer monomer; the polymer material or the mixture of the polymer monomer and the nanowire is mechanically stirred while using ultrasonic treatment. The method for preparing a nanowire-containing composite particle according to claim 8, wherein the step of adding the nanowire to the liquid polymer material or the polymer monomer further comprises infiltrating with an organic solvent. The steps of the nano line. The method for producing a nanowire-containing composite particle according to claim 10, wherein the organic solvent is one or a mixture of ethanol, methanol, acetone, dichloroethane and chloroform. The method for producing a nanowire-containing composite particle according to claim 8, wherein the method of curing to form a composite material is a method of initiating a polymerization reaction by adding an initiator. The method for producing a nanowire-containing composite particle according to claim 8, wherein the method of curing to form a composite material is a method of ultraviolet light curing. The method for preparing a nanowire-containing composite particle according to claim 8, wherein the method of curing to form a composite material is a method of cooling or gradually increasing the temperature. The method for preparing a composite particle containing a nanowire according to claim 8, wherein the method of forming the composite material containing the nanowire by the pulverized composite material comprises a ball milling method, a granulator pulverization method, a crusher Pulverization method or jet mill pulverization method. The method for producing a composite particle containing a nanowire according to claim 15, wherein the pulverization The method of forming the composite material containing the composite material of the nanowire is a ball milling method. The method for producing a composite particle containing a nanowire according to claim 16, wherein the method of forming the composite material containing the nanowire by the pulverized composite material further comprises: composite particle containing a nanowire obtained by pulverizing the ball mill It was further pulverized by being placed in a jet mill. The method for preparing a composite particle containing a nanowire according to claim 15, wherein the ball, the middle ball and the small ball have a ratio of 1:2:3 and a ball to ball ratio of 3 during the ball milling process. :1, the ball mill speed is 350 rpm, and the ball milling time is 5 hours. The method for preparing a composite particle containing a nanowire according to claim 17, wherein the method of further pulverizing the composite particle containing the nanowire obtained by pulverizing the ball mill into a jet mill comprises the following steps: The composite particles containing the nanowire obtained by pulverization by a ball mill are added into the pulverizing chamber of the jet mill; the compressed air is injected into the pulverizing chamber through the nozzle; the composite particles containing the nanowire are repeatedly collided under the action of the air formed by the compressed air. , rubbing, shearing and further pulverizing.