CN115028994A - Far infrared radiation material with adjustable resistivity and preparation method thereof - Google Patents
Far infrared radiation material with adjustable resistivity and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of polymer composite materials, and discloses a far infrared radiation material with adjustable resistivity and a preparation method thereof, wherein the preparation method comprises the following steps: (1) preparing composite modified ceramic powder by adopting a high-temperature solid-phase reaction method; (2) modifying the composite ceramic powder by using a silane coupling agent, and stirring and reacting the chemically modified composite ceramic powder and the carbon nanotube chloride to obtain a composite ceramic powder grafted carbon nanotube; (3) 70-90 parts of polymer resin, 5-20 parts of composite ceramic powder grafted carbon nano tube, 1-2 parts of antioxidant and 1-2 parts of lubricant are mixed, and the mixed raw materials are extruded, granulated and dried to finally obtain the far infrared radiation composite material with adjustable resistivity. Based on the grafting amount of the carbon nano tube and the addition amount of the composite ceramic powder grafted carbon nano tube, the controllability of the volume resistivity of the carbon nano tube is realized, the far infrared emissivity is improved, and the absorption capacity of a human body is enhanced.
Description
Technical Field
The invention belongs to the technical field of polymer composite materials, and relates to a sustainable far infrared emission composite material and a preparation method thereof.
Background
The wavelength range of infrared ray is very wide, people refer to electromagnetic waves with different wavelength ranges as near infrared ray, middle infrared ray and far infrared ray, the wavelength range of the far infrared ray is 6000-15000 nanometers, and as the vibration frequency of the far infrared ray is close to the vibration frequency of cell molecules in a human body, after the 'vital light wave' permeates into the human body, atoms and molecules of human cells can be caused to resonate, through resonance absorption, the molecules generate heat through friction and heat to form a thermal reaction, the subcutaneous deep layer temperature is increased, the capillaries are expanded, the blood circulation is accelerated, the blood vessel deposits and harmful substances in the body are favorably removed, the obstacle hindering the metabolism is removed, the tissues are reactivated, the enzyme is promoted to generate, and the purposes of activating the tissue cells, preventing aging and strengthening the immune system are achieved.
The eye mask has the characteristics of promoting blood circulation by utilizing far infrared rays, and the eye mask made of the far infrared materials and the high polymer materials can promote blood circulation and metabolism around eyes, so that self-recovery and regulation capability of the eyes are enhanced. In the plastic material for manufacturing the eye rim on the market at present, although far infrared light can be radiated by itself, the wavelength of the far infrared light is not consistent with that of the far infrared light absorbed by a human body, so that the far infrared light has no protection effect basically. Meanwhile, the far infrared emissivity can be improved by increasing the temperature of the infrared sensor. Therefore, it is urgently needed to develop a far infrared composite material with adjustable resistivity, which has excellent far infrared emission performance, the emitted wavelength is consistent with the wavelength of far infrared light absorbed by a human body, and the self temperature can be adjusted by regulating and controlling the resistivity, so that the far infrared emissivity is improved.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide a sustainable emission far infrared composite material and a preparation method thereof, the composite material can be prepared by composite modified ceramic powder and surface grafting modification, and after being mixed with polymer resin, the composite material has excellent infrared emission performance, and the emitted wavelength is consistent with the wavelength of far infrared light absorbed by a human body, and simultaneously has excellent mechanical properties.
The invention provides a sustainable emission far infrared composite material, which is prepared by obtaining composite modified ceramic powder through multi-component compounding, rare earth doping modification and radiation grafting modification, and then carrying out multi-component blending with polymer resin.
The specific technical scheme of the invention is as follows:
a preparation method of a far infrared radiation material with adjustable resistivity comprises the following steps:
(1) mixing 50-70 parts of tourmaline, 20-30 parts of medical stone, 5-10 parts of silicon dioxide, 3-5 parts of yttrium oxide and 2-5 parts of cerium carbonate in parts by weight, and preparing composite ceramic powder by adopting a high-temperature solid-phase reaction method;
(2) modifying the composite ceramic powder by using a silane coupling agent to obtain chemically modified composite ceramic powder; adding chemically modified composite ceramic powder and acyl chloride carbon nanotube into dry solvent, ultrasonic dispersing, and adding into the mixture at 70-90 deg.C o C, stirring and reacting for 8-12h under the condition of C, cooling, filtering, washing and drying to obtain the composite ceramic powder grafted carbon nano tube;
(3) according to the weight parts, 70-90 parts of polymer resin, 5-20 parts of composite ceramic powder grafted carbon nano tube, 1-2 parts of antioxidant and 1-2 parts of lubricant are mixed, and the mixed raw materials are extruded, granulated and dried to finally obtain the far infrared radiation composite material with adjustable resistivity.
Preferably, the preparation of the chemically modified composite ceramic powder of step (2): dispersing composite ceramic powder in water to form uniform dispersion, adjusting pH to 4-5, adding silane coupling agent into ethanol, stirring to dissolve, adding into the dispersion, and adding into the mixture at 25-70 deg.C o And C, reacting for 6-24 hours under the condition of C, cooling, washing and drying to obtain the chemically modified composite ceramic powder.
Preferably, the preparation of the acyl chloride carbon nanotube in the step (2): mixing the carboxylated carbon nanotube with thionyl chloride solvent, ultrasonically dispersing, and then carrying out ultrasonic dispersion on the mixture at 60-90 DEG C o Under C condition is reversedCooling, filtering, washing and drying after 12-24h to obtain the carbon nanotube chloride.
Preferably, the mass ratio of the composite ceramic powder to water in the step (2) is 0.5-1: 100, respectively; the mass ratio of the silane coupling agent to the composite ceramic powder is 5-10: 100, respectively; the mass ratio of the ethanol to the silane coupling agent is 100: 10-20.
Preferably, the mass ratio of the carboxylated carbon nanotubes to the thionyl chloride is 0.5-1: 100.
preferably, the mass ratio of the chemically modified composite ceramic powder to the carbon acyl chloride nanotubes is 1: 0.3-0.5; the mass ratio of the total mass of the chemically modified composite ceramic powder and the acyl chloride carbon nano tube to the solvent is 0.5-1: 100.
preferably, the solvent in step (2) is N, N-dimethylformamide or N, N-dimethylacetamide; the carboxylated carbon nanotube is one or more than two of carboxylated single-wall carbon nanotube, carboxylated double-wall carbon nanotube and carboxylated multi-wall carbon nanotube.
Preferably, the silane coupling agent in the step (2) is one or two of gamma-aminopropyltriethoxysilane and gamma-glycidoxypropyltrimethoxysilane.
Preferably, the polymer resin in the step (3) is one or two of nylon 12 and nylon 6.
Preferably, the antioxidant is one or more of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, dilauryl thiodipropionate and tris (2, 4-di-tert-butylphenyl) phosphite.
Preferably, the lubricant is one or two of ethylene bis stearamide and white oil.
Preferably, the mixing conditions in the step (3) are that the raw materials are uniformly mixed in a high-speed mixer, the mixing speed is 35-50 r/min, and the mixing time is 35-50 min; the extrusion conditions are that the temperature range of the extruder is 220-260 ℃, the extrusion speed is controlled at 80-120r/min, and the main feeding speed is controlled at 8-10r/min in a double-screw extruder.
Preferably, the drying conditions for preparing the chemically modified composite ceramic powder in the step (2) are 10Pa under pressure and 10Pa under temperatureIs-55 o Freeze-drying for 24-48h under the condition of C; the drying condition for preparing the acyl chloride carbon nano tube is vacuum drying for 24 hours, and washing by adopting a low-boiling point solvent; the drying condition for preparing the composite ceramic powder grafted carbon nano tube is freeze drying for 24-48 h.
Preferably, the composite ceramic powder in the step (2) is dispersed in water and subjected to ultrasonic treatment for 0.5 to 2 hours to form a uniform dispersion liquid.
Preferably, the preparation of the composite modified ceramic powder in the step (1): fully grinding the raw materials to uniformly mix the raw materials, and then calcining the raw materials at the temperature of 1200-1400 ℃, wherein the gas atmosphere is H with the volume content of 10-20 percent 2 With 80-90% of N 2 Mixing the gas, calcining for 4-8h, and cooling after calcining, and grinding into powder.
Compared with the prior art, the invention has the following beneficial effects:
the invention prepares the composite modified ceramic powder by multi-component compounding and chemical grafting, and then carries out multi-component blending with polymer resin to prepare the sustainable radiation far infrared composite material, the maximum far infrared emissivity is 0.92 in the wavelength range of 8-14 mu m, the composite material has higher far infrared emissivity, the emitted wavelength is matched with the wavelength of far infrared light absorbed by human body, the spectral density ratio is 72.6% in the wavelength range of 9-10 mu m, according to the matched absorption theory, the far infrared emitted by the sustainable radiation far infrared composite material can be easily absorbed by the skin around the eyes, and the blood circulation and metabolism around the eyes are promoted.
Compared with the method that the carbon nano tubes are blended and added into a composite material system, the sustainable radiation far infrared composite material taking the composite ceramic powder grafted carbon nano tubes as the filler has lower volume resistivity and higher far infrared emissivity.
Based on the grafting amount of the carbon nano tubes in the composite ceramic powder grafted carbon nano tubes and the addition amount of the composite ceramic powder grafted carbon nano tubes in the sustainable radiation far infrared composite material, the controllability of the volume resistivity of the composite ceramic powder grafted carbon nano tubes is realized, and the volume resistivity of the composite ceramic powder grafted carbon nano tubes is 8.46 multiplied by 10 6 -6.25×10 9 The omega/sq can be adjusted, the self temperature can be adjusted in practical application by an electric heating mode,the far infrared emissivity is improved, so that the self-recovery and adjustment capability of eyes are enhanced.
Drawings
Fig. 1 shows far infrared emissivity of composite material samples obtained by adding 17.5%, 9.6% and 13.8% of composite ceramic powder grafted carbon nanotubes to examples 1, 3 and 4, respectively, at different temperatures.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto, and may be carried out with reference to conventional techniques for process parameters not particularly noted.
Example 1
(1) Composite ceramic powder
The composite modified ceramic powder is synthesized by adopting a high-temperature solid-phase reaction method, which comprises the following steps: 70g of tourmaline, 30g of medical stone, 10g of silicon dioxide, 5g of yttrium oxide and 5g of cerium carbonate. All the raw materials are weighed and then placed in an agate mortar, 10g of ethanol is added, and the mixture is fully ground for more than 60min to be uniformly mixed. Then the mixture was placed in a crucible and calcined in a tube furnace at 1400 ℃. The gas atmosphere is H with the volume content of 20 percent 2 And 80% of N 2 The mixed gas and the calcining time are 8 h. And after the calcination is finished and the temperature is cooled to room temperature, grinding the calcined product into powder to obtain the final sample.
(2) Composite ceramic powder grafted carbon nanotube
Firstly, 10g of composite ceramic powder is dispersed in 1000g of deionized water and subjected to ultrasonic treatment for 2 hours to form a uniform dispersion liquid, the pH value is adjusted to 5 by hydrochloric acid, then 1g of gamma-aminopropyltriethoxysilane is added into 10g of ethanol to be stirred and dissolved, and then the mixture is added into the dispersion liquid at 70 DEG o And C, reacting for 6 hours. And cooling to room temperature, centrifugally washing for 5 times by deionized water, and removing the unreacted coupling agent. At a pressure of 10Pa and a temperature of-55 o And C, carrying out freeze drying for 48 hours under the condition of C to obtain the chemically modified composite ceramic powder.
Adding 10g of carboxylated single-walled carbon nanotubes and 2000g of thionyl chloride solvent into a reaction kettle, carrying out ultrasonic treatment at room temperature for 3 hours, and then carrying out ultrasonic treatment at 90 DEG o Reacting for 24 hours under the condition of C, cooling to room temperature, filtering, washing with acetone for 5 timesAnd drying for 24 hours in vacuum at room temperature to obtain the carbon nanotube of acyl chloride.
Adding 10g of chemically modified composite ceramic powder and 5g of acyl chloride carbon nano tube into dried 3000g of N, N-dimethylformamide, carrying out ultrasonic treatment at room temperature for 3h, and then carrying out ultrasonic treatment at 90g o And C, stirring and reacting for 12 hours under the condition of C, cooling to room temperature after the reaction is finished, filtering, washing for 5 times by using deionized water, and freeze-drying for 48 hours to obtain the composite ceramic powder grafted carbon nanotube.
(3) Sustainable far infrared emission composite material
90g of nylon 6, 20g of composite ceramic powder grafted carbon nano tube, 2g of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester and 2g of ethylene bis stearamide. Mixing uniformly in a high-speed mixer at a mixing speed of 50r/min for 50 min. The mixed raw materials are added into a cylinder of a double-screw extruder. The temperature range of the extruder is 260 ℃, the extrusion speed is controlled at 120r/min, and the main feeding speed is controlled at 10 r/min. And (3) granulating and drying by adopting a conventional granulating process to finally obtain the sustainable emission far infrared composite material (the addition amount of the composite ceramic powder grafted carbon nano tube is 17.5%).
Example 2
(1) Composite ceramic powder
The composite modified ceramic powder is synthesized by adopting a high-temperature solid-phase reaction method, which comprises the following steps: 50g of tourmaline, 20g of medical stone, 5g of silicon dioxide, 3g of yttrium oxide and 2g of cerium carbonate. All the raw materials are weighed and then placed in an agate mortar, 5g of ethanol is added, and the mixture is fully ground for more than 30min to be uniformly mixed. Then the mixture was placed in a crucible and calcined in a tube furnace at a calcination temperature of 1200 ℃. The gas atmosphere is H with the volume content of 10 percent 2 And 90% of N 2 The mixed gas and the calcining time are 4 h. And after the calcination is finished and the temperature is cooled to room temperature, grinding the calcined product into powder to obtain the final sample.
(2) Composite ceramic powder grafted carbon nanotube
Firstly, 10g of composite ceramic powder is dispersed in 2000g of deionized water and subjected to ultrasonic treatment for 0.5h to form a uniform dispersion liquid, the pH value is adjusted to 4 by using hydrochloric acid, and then 0.5g of gamma-aminopropyltriethoxysilane is added into 2.5g of ethanol and stirred to be dissolved and added into the dispersion liquidIn 25 o And reacting for 24 hours under the condition of C. And cooling to room temperature, centrifugally washing for 3 times by deionized water, and removing the unreacted coupling agent. At a pressure of 10Pa and a temperature of-55 o And C, freeze-drying for 24 hours under the condition of C to obtain the chemically modified composite ceramic powder.
Adding 10g of carboxylated double-walled carbon nanotubes and 1000g of thionyl chloride solvent into a reaction kettle, carrying out ultrasonic treatment at room temperature for 1 hour, and then carrying out ultrasonic treatment for 60 hours o And C, reacting for 12 hours under the condition of C, cooling to room temperature, filtering, washing with acetone for 3 times, and vacuum-drying at room temperature for 24 hours to obtain the carbon nanotubes.
Adding 10g of chemically modified composite ceramic powder and 3g of carbon oxychloride nanotube into 1300g of dry N, N-dimethylacetamide, performing ultrasonic treatment at room temperature for 1h, and performing ultrasonic treatment at 70g o And C, stirring and reacting for 8 hours under the condition of C, cooling to room temperature after the reaction is finished, filtering, washing for 3 times by using deionized water, and freeze-drying for 24 hours to obtain the composite ceramic powder grafted carbon nanotube.
(3) Sustainable far infrared emission composite material
70g of nylon 12, 5g of composite ceramic powder grafted carbon nano tube, 1g of dilauryl thiodipropionate and 1g of white oil. Mixing in a high-speed mixer. The mixing speed was 35r/min and the mixing time was 35 min. The mixed raw materials are added into a cylinder of a double-screw extruder. The temperature range of the extruder is 220 ℃, the extrusion speed is controlled at 80r/min, and the main feeding speed is controlled at 8 r/min. And granulating and drying by adopting a conventional granulating process to finally obtain the sustainable emission far infrared composite material.
Example 3
(1) Composite ceramic powder
The composite modified ceramic powder is synthesized by adopting a high-temperature solid-phase reaction method, which comprises the following steps: 70g of tourmaline, 30g of medical stone, 10g of silicon dioxide, 5g of yttrium oxide and 5g of cerium carbonate. All the raw materials are weighed and then placed in an agate mortar, 10g of ethanol is added, and the mixture is fully ground for more than 60min to be uniformly mixed. The mixture was then calcined in a crucible in a tube furnace at 1400 ℃. The gas atmosphere is H with the volume content of 20 percent 2 And 80% of N 2 The mixed gas and the calcining time are 8 h. And after the calcination is finished and the temperature is cooled to room temperature, grinding the calcined product into powder to obtain the final sample.
(2) Composite ceramic powder grafted carbon nanotube
Firstly, 10g of composite ceramic powder is dispersed in 1000g of deionized water and subjected to ultrasonic treatment for 2 hours to form uniform dispersion liquid, the pH value is adjusted to 5 by hydrochloric acid, then 1g of gamma-aminopropyltriethoxysilane is added into 10g of ethanol to be stirred and dissolved and then added into the dispersion liquid, and the mixture is stirred and dissolved at 70 DEG C o And reacting for 6 hours under the condition of C. And cooling to room temperature, centrifugally washing for 5 times by deionized water, and removing the unreacted coupling agent. At a pressure of 10Pa and a temperature of-55 o And C, carrying out freeze drying for 48 hours under the condition of C to obtain the chemically modified composite ceramic powder.
Adding 10g of carboxylated single-walled carbon nanotubes and 2000g of thionyl chloride solvent into a reaction kettle, carrying out ultrasonic treatment at room temperature for 3 hours, and then carrying out ultrasonic treatment at 90 DEG o And C, reacting for 24 hours under the condition of C, cooling to room temperature, filtering, washing with acetone for 5 times, and vacuum-drying for 24 hours at room temperature to obtain the carbon nanotubes.
Adding 10g of chemically modified composite ceramic powder and 5g of acyl chloride carbon nano tube into dried 3000g of N, N-dimethylformamide, carrying out ultrasonic treatment at room temperature for 3h, and then carrying out ultrasonic treatment at 90g o And C, stirring and reacting for 12 hours under the condition of C, cooling to room temperature after the reaction is finished, filtering, washing for 5 times by using deionized water, and freeze-drying for 48 hours to obtain the composite ceramic powder grafted carbon nanotube.
(3) Sustainable far infrared emission composite material
90g of nylon 6, 10g of composite ceramic powder grafted carbon nano tube, 2g of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester and 2g of ethylene bis stearamide. Mixing in a high-speed mixer. The mixing speed is 50r/min, and the mixing time is 50 min. The mixed raw materials are added into a cylinder of a double-screw extruder. The temperature range of the extruder is 260 ℃, the extrusion speed is controlled at 120r/min, and the main feeding speed is controlled at 10 r/min. And (3) granulating and drying by adopting a conventional granulating process to finally obtain the sustainable emission far infrared composite material (the addition amount of the composite ceramic powder grafted carbon nano tube is 9.6%).
Example 4
(1) Composite ceramic powder
The composite modified ceramic powder is synthesized by adopting a high-temperature solid-phase reaction method, which comprises the following steps: electric appliance70g of stone, 30g of medical stone, 10g of silicon dioxide, 5g of yttrium oxide and 5g of cerium carbonate. All the raw materials are weighed and then placed in an agate mortar, 8g of ethanol is added, and the mixture is fully ground for more than 60min to be uniformly mixed. Then the mixture was placed in a crucible and calcined in a tube furnace at 1400 ℃. The gas atmosphere is H with the volume content of 20 percent 2 And 80% of N 2 The calcination time of the mixed gas is 8 h. And after the calcination is finished and the temperature is cooled to room temperature, grinding the calcined product into powder to obtain the final sample.
(2) Composite ceramic powder grafted carbon nanotube
Firstly, 10g of composite ceramic powder is dispersed in 1000g of deionized water and subjected to ultrasonic treatment for 2 hours to form a uniform dispersion liquid, the pH value is adjusted to 5 by hydrochloric acid, then 1g of gamma-aminopropyltriethoxysilane is added into 10g of ethanol to be stirred and dissolved, and then the mixture is added into the dispersion liquid at 70 DEG o And reacting for 6 hours under the condition of C. And cooling to room temperature, centrifugally washing for 5 times by deionized water, and removing unreacted coupling agent. At a pressure of 10Pa and a temperature of-55 o And C, carrying out freeze drying for 48 hours under the condition of C to obtain the chemically modified composite ceramic powder.
Adding 10g of carboxylated single-walled carbon nanotubes and 2000g of thionyl chloride solvent into a reaction kettle, carrying out ultrasonic treatment at room temperature for 3 hours, and then carrying out ultrasonic treatment at 90 DEG o And C, reacting for 24 hours under the condition of C, cooling to room temperature, filtering, washing for 5 times by using acetone, and drying for 24 hours in vacuum at room temperature to obtain the carbon oxychloride nanotube.
Adding 10g of chemically modified composite ceramic powder and 5g of acyl chloride carbon nano tube into dried 3000g of N, N-dimethylformamide, carrying out ultrasonic treatment at room temperature for 3h, and then carrying out ultrasonic treatment at 90g o And C, stirring and reacting for 12 hours under the condition of C, cooling to room temperature after the reaction is finished, filtering, washing for 5 times by using deionized water, and freeze-drying for 48 hours to obtain the composite ceramic powder grafted carbon nanotube.
(3) Sustainable far infrared emission composite material
The weight percentage of the nylon 6 is 90g, the composite ceramic powder is grafted with 15g of carbon nano-tube, 2g of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester and 2g of ethylene bis stearamide. Mixing in high-speed mixer. The mixing speed is 50r/min, and the mixing time is 50 min. The mixed raw materials are added into a cylinder of a double-screw extruder. The temperature range of the extruder is 260 ℃, the extrusion speed is controlled at 120r/min, and the main feeding speed is controlled at 10 r/min. And (3) granulating and drying by adopting a conventional granulating process to finally obtain the sustainable emission far infrared composite material (the addition amount of the composite ceramic powder grafted carbon nano tube is 13.8%).
Example 5
(1) Composite ceramic powder
The composite modified ceramic powder is synthesized by adopting a high-temperature solid-phase reaction method, which comprises the following steps: 60g of tourmaline, 25g of medical stone, 7.5g of silicon dioxide, 4g of yttrium oxide and 3.5g of cerium carbonate. All the raw materials are weighed and placed in an agate mortar, 6g of ethanol is added, and the mixture is fully ground for more than 45min to be uniformly mixed. Then the mixture was calcined in a crucible in a tube furnace at 1300 ℃. The gas atmosphere is H with the volume content of 10 percent 2 And 90% of N 2 The mixed gas and the calcining time are 6 h. And after the calcination is finished and the temperature is cooled to room temperature, grinding the calcined product into powder to obtain the final sample.
(2) Composite ceramic powder grafted carbon nanotube
Firstly, 10g of composite ceramic powder is dispersed in 1000g of deionized water and subjected to ultrasonic treatment for 2 hours to form a uniform dispersion liquid, the pH value is adjusted to 5 by hydrochloric acid, then 1g of gamma-aminopropyltriethoxysilane is added into 10g of ethanol to be stirred and dissolved, and then the mixture is added into the dispersion liquid at 70 DEG o And reacting for 6 hours under the condition of C. And cooling to room temperature, centrifugally washing for 5 times by deionized water, and removing the unreacted coupling agent. At a pressure of 10Pa and a temperature of-55 o And C, carrying out freeze drying for 48 hours under the condition of C to obtain the chemically modified composite ceramic powder.
Adding 10g of carboxylated multi-walled carbon nanotubes and 2000g of thionyl chloride solvent into a reaction kettle, performing ultrasonic treatment for 3 hours at room temperature, and then performing ultrasonic treatment at 90 DEG o And C, reacting for 24 hours under the condition of C, cooling to room temperature, filtering, washing with acetone for 5 times, and vacuum-drying for 24 hours at room temperature to obtain the carbon nanotubes.
Adding 10g of chemically modified composite ceramic powder and 5g of acyl chloride carbon nano tube into dried 3000g of N, N-dimethylformamide, carrying out ultrasonic treatment at room temperature for 3h, and then carrying out ultrasonic treatment at 90g o Stirring under C condition for reaction for 12 hr, cooling to room temperature, filtering, washing with deionized water for 5 times, and freeze dryingAnd drying for 48 hours to obtain the composite ceramic powder grafted carbon nano tube.
(3) Sustainable far infrared emission composite material
80g of nylon 12, 15g of composite ceramic powder grafted carbon nano tube, 1.5g of tris (2, 4-di-tert-butylphenyl) phosphite and 1.5g of white oil. Mixing in high-speed mixer. The mixing speed is 40r/min, and the mixing time is 40 min. The mixed raw materials are added into a cylinder of a double-screw extruder. The temperature range of the extruder is 240 ℃, the extrusion speed is controlled at 100r/min, and the main feeding speed is controlled at 9 r/min. And (4) granulating and drying by adopting a conventional granulating process to finally obtain the sustainable emission far infrared composite material.
Comparative example 1
The nylon 6 comprises 90g of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester 2g and ethylene bisstearamide 2 g. Mixing in high-speed mixer. The mixing speed is 50r/min, and the mixing time is 50 min. The mixed raw materials are added into a cylinder of a double-screw extruder. The temperature range of the extruder is 260 ℃, the extrusion speed is controlled at 120r/min, and the main feeding speed is controlled at 10 r/min. And (4) granulating and drying by adopting a conventional granulating process to finally obtain the comparative composite material 1.
Comparative example 2
(1) Composite ceramic powder
The composite modified ceramic powder is synthesized by adopting a high-temperature solid-phase reaction method, which comprises the following steps: 70g of tourmaline, 30g of medical stone, 10g of silicon dioxide, 5g of yttrium oxide and 5g of cerium carbonate. All the raw materials are weighed and then placed in an agate mortar, 10g of ethanol is added, and the mixture is fully ground for more than 60min to be uniformly mixed. Then the mixture was placed in a crucible and calcined in a tube furnace at 1400 ℃. The gas atmosphere is H with the volume content of 20 percent 2 And 80% of N 2 The mixed gas and the calcining time are 8 h. And after the calcination is finished and the temperature is cooled to room temperature, grinding the calcined product into powder to obtain the final sample.
(2) Composite ceramic powder/carbon nano tube
And uniformly mixing 10g of composite ceramic powder and 5g of carbon nano tube to obtain the composite ceramic powder grafted carbon nano tube.
(3) Sustainable far infrared emission composite material
90g of nylon 12, 20g of composite ceramic powder/carbon nano tube, 2g of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester and 2g of ethylene bis stearamide. Mixing uniformly in a high-speed mixer at a mixing speed of 50r/min for 50 min. The mixed raw materials are added into a cylinder of a double-screw extruder. The temperature range of the extruder is 260 ℃, the extrusion speed is controlled at 120r/min, and the main feeding speed is controlled at 10 r/min. And (3) granulating and drying by adopting a conventional granulating process to finally obtain a comparative composite material 2 (the addition amount of the composite ceramic powder/the carbon nano tube is 17.5%).
Comparative example 3
(1) Tourmaline graft carbon nano-tube
Firstly, 10g of tourmaline is dispersed in 1000g of deionized water and subjected to ultrasonic treatment for 2 hours to form a uniform dispersion, the pH value is adjusted to 5 by using hydrochloric acid, then 1g of gamma-aminopropyltriethoxysilane is added into 10g of ethanol and dissolved by stirring, and the mixture is added into the dispersion at 70 DEG o And reacting for 6 hours under the condition of C. And cooling to room temperature, centrifugally washing for 5 times by deionized water, and removing the unreacted coupling agent. At a pressure of 10Pa and a temperature of-55 o And C, carrying out freeze drying for 48h to obtain the chemically modified tourmaline.
Adding 10g of carboxylated single-walled carbon nanotubes and 2000g of thionyl chloride solvent into a reaction kettle, carrying out ultrasonic treatment at room temperature for 3 hours, and then carrying out ultrasonic treatment at 90 DEG o And C, reacting for 24 hours under the condition of C, cooling to room temperature, filtering, washing for 5 times by using acetone, and drying for 24 hours in vacuum at room temperature to obtain the carbon oxychloride nanotube.
Adding 10g of chemically modified tourmaline and 5g of carbon oxychloride nanotube into dried 3000g of N, N-dimethylformamide, performing ultrasonic treatment at room temperature for 3h, and performing ultrasonic treatment at 90 deg.C o And C, stirring and reacting for 12h, cooling to room temperature after the reaction is finished, filtering, washing for 5 times by using deionized water, and freeze-drying for 48h to obtain the tourmaline grafted carbon nanotube.
(2) Sustainable far infrared emission composite material
90g of nylon 12, 20g of tourmaline grafted carbon nano tube, 2g of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester and 2g of ethylene bis stearamide. Mixing uniformly in a high-speed mixer at a mixing speed of 50r/min for 50 min. The mixed raw materials are added into a cylinder of a double-screw extruder. The temperature range of the extruder is 260 ℃, the extrusion speed is controlled at 120r/min, and the main feeding speed is controlled at 10 r/min. And (3) granulating and drying by adopting a conventional granulating process to finally obtain the comparative composite material 3 (the addition amount of the tourmaline grafted carbon nano tube is 17.5%).
And (3) performance testing:
the tensile strength test is carried out according to the GB/T1040-2018 standard; the notch impact strength test is carried out according to the GB/T1843-2008 standard; the far infrared emissivity test is executed according to the GB/T30127-2013 standard, and the far infrared emissivity is the ratio of the far infrared emission intensity of the test sample to the far infrared emission intensity of a standard black board; the spectral density ratio is calculated according to the test result of far infrared emissivity, namely the ratio of the area of a far infrared emissivity curve in a region of 9-10 mu m to the area of a far infrared emissivity curve in a region of 8-14 mu m; the volume resistivity test was performed in accordance with GB/T2439-. The test results are shown in the following table 1, comparative example 1 without adding composite ceramic powder to graft carbon nano-tube, the volume resistivity of the composite material is as high as 10 12 Omega/sq. Examples 3, 4 and 1 with increasing addition of the composite ceramic powder grafted carbon nanotubes, the volume resistivity of the composite material gradually decreases to 10 6 Omega/sq. Therefore, the volume resistivity of the composite material can be reduced step by controlling the addition amount of the composite ceramic powder grafted carbon nano tube, and the far infrared emissivity can be improved at the same time. Comparative example 2 uses composite ceramic powder/carbon nano tube as filler, and the dosage is the same as that of example 1, but the volume resistivity is obviously higher than that of example 1, and the far infrared emissivity is lower. The comparison example 3 adopts the tourmaline grafted carbon nano tube, and the composite material has lower performances, especially spectral density ratio.
TABLE 1 Properties of sustainable far infrared emission composite Material
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such modifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a far infrared radiation material with adjustable resistivity is characterized by comprising the following steps:
(1) mixing 50-70 parts of tourmaline, 20-30 parts of medical stone, 5-10 parts of silicon dioxide, 3-5 parts of yttrium oxide and 2-5 parts of cerium carbonate in parts by weight, and preparing composite ceramic powder by adopting a high-temperature solid-phase reaction method;
(2) modifying the composite ceramic powder by using a silane coupling agent to obtain chemically modified composite ceramic powder; adding the chemically modified composite ceramic powder and the carbon oxychloride nanotube into a dry solvent, performing ultrasonic dispersion, and performing ultrasonic dispersion on the mixture at 70-90 DEG C o C, stirring and reacting for 8-12h under the condition of C, cooling, filtering, washing and drying to obtain the composite ceramic powder grafted carbon nano tube;
(3) according to the weight parts, 70-90 parts of polymer resin, 5-20 parts of composite ceramic powder grafted carbon nano tube, 1-2 parts of antioxidant and 1-2 parts of lubricant are mixed, and the mixed raw materials are extruded, granulated and dried to finally obtain the far infrared radiation composite material with adjustable resistivity.
2. The method for preparing the chemically modified composite ceramic powder according to claim 1, wherein the step (2) of preparing the chemically modified composite ceramic powder comprises: dispersing composite ceramic powder in water to form uniform dispersion, adjusting pH to 4-5, adding silane coupling agent into ethanol, stirring to dissolve, adding into the dispersion, and adding into the mixture at 25-70 deg.C o And C, reacting for 6-24 hours under the condition of C, cooling, washing and drying to obtain the chemically modified composite ceramic powder.
3. The method according to claim 2, wherein the preparation of the carbon nanotubes acylchloride according to step (2): mixing the carboxylated carbon nanotube with thionyl chloride solvent, ultrasonically dispersing, and then carrying out ultrasonic dispersion on the mixture at 60-90 DEG C o Reacting for 12-24h under the condition of C, cooling, filtering,washing and drying to obtain the carbon nanotube.
4. The production method according to claim 3,
the mass ratio of the composite ceramic powder to water in the step (2) is 0.5-1: 100, respectively; the mass ratio of the silane coupling agent to the composite ceramic powder is 5-10: 100, respectively; the mass ratio of the ethanol to the silane coupling agent is 100: 10-20 parts of;
the mass ratio of the carboxylated carbon nanotube to the thionyl chloride is 0.5-1: 100;
the mass ratio of the chemically modified composite ceramic powder to the acyl chloride carbon nano tube is 1: 0.3-0.5; the mass ratio of the total mass of the chemically modified composite ceramic powder and the acyl chloride carbon nano tube to the solvent is 0.5-1: 100.
5. the method according to claim 4, wherein the solvent in the step (2) is N, N-dimethylformamide or N, N-dimethylacetamide; the carboxylated carbon nano tube is one or more than two of a carboxylated single-wall carbon nano tube, a carboxylated double-wall carbon nano tube and a carboxylated multi-wall carbon nano tube.
6. The production method according to any one of claims 1 to 5,
the silane coupling agent in the step (2) is one or two of gamma-aminopropyltriethoxysilane and gamma-glycidoxypropyltrimethoxysilane;
the polymer resin in the step (3) is one or two of nylon 12 and nylon 6;
the antioxidant is one or more than two of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, dilauryl thiodipropionate and tris (2, 4-di-tert-butylphenyl) phosphite;
the lubricant is one or two of ethylene bis stearamide and white oil.
7. The preparation method according to any one of claims 1 to 5, wherein the mixing conditions in the step (3) are uniform mixing in a high-speed mixer, the mixing speed is 35 to 50r/min, and the mixing time is 35 to 50 min; the extrusion conditions are that the temperature range of the extruder is 220-260 ℃, the extrusion speed is controlled at 80-120r/min, and the main feeding speed is controlled at 8-10r/min in a double-screw extruder.
8. The method according to any one of claims 1 to 5, wherein the chemically modified composite ceramic powder prepared in the step (2) is dried under a pressure of 10Pa and a temperature of-55 Pa o Freeze-drying for 24-48h under the condition of C; the drying condition for preparing the acyl chloride carbon nano tube is vacuum drying for 24 hours; the drying condition for preparing the composite ceramic powder grafted carbon nano tube is freeze drying for 24-48 h.
9. The preparation method according to any one of claims 1 to 5, wherein the preparation of the composite modified ceramic powder in the step (1): fully grinding the raw materials to uniformly mix the raw materials, and then calcining the raw materials at the temperature of 1200-1400 ℃, wherein the gas atmosphere is H with the volume content of 10-20 percent 2 With 80-90% of N 2 Mixing the gas, calcining for 4-8h, and grinding into powder after the calcination is finished and the gas is cooled.
10. A far infrared radiation composite material with adjustable resistivity, which is prepared by the method of any one of claims 1 to 9.
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