CN110776672A - Multifunctional nano composite material - Google Patents
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Abstract
The invention provides a multifunctional nano composite material which is mainly prepared from the following nano raw materials: 1-10 parts of modified kaolin, 1-10 parts of nano zinc oxide, 1-10 parts of chitosan, 1-10 parts of starch, 1-10 parts of calcium carbonate, 1-10 parts of modified montmorillonite and 1-10 parts of anatase. The multifunctional nano composite material integrates and optimizes the characteristics of various nano materials, thereby generating various functions and being suitable for being used as functional addition of various materials. The multifunctional nano composite material has good fluidity and compatibility, can be excellently fused with various traditional materials such as plastics and the like, and exerts the functional characteristics to the greatest extent. Meanwhile, the medicine has no radioactivity, no toxicity, no irritation and safe use.
Description
Technical Field
The invention relates to the field of nano material preparation, in particular to a multifunctional nano composite material.
Background
Nanotechnology, which began in the end of the 80 th 20 th century, is an emerging comprehensive technology that studies the characteristics of atoms, molecular structures, and their interaction principles on the nanoscale, and manipulates molecules, atoms, and even electrons directly on the nanoscale as needed to produce various specific products or create nanoscale processes. Nanomaterials bring scientific research from the macro to the micro domain, initiating a revolution in production, life science and technology, and human cognition.
The nano material has wide technical prospect, but the industrial application is still in the initial development stage. At present, enterprises and scientific research institutions mainly focus on single materials, and research and application of composite materials are few, so that the prepared nano materials are single in performance and only can be used for specific purposes. For example, the nano material film disclosed in patent CN 107629346 a only has flame retardant property, and can only be used for specially making flame retardant functional film, and the application is limited.
Disclosure of Invention
In view of the above, the invention provides a multifunctional nano composite material, which has the functions of resisting and inhibiting bacteria, deodorizing and purifying, strong oxidation reduction, radiation protection, dredging channels and collaterals and the like, and can be used as an additive for manufacturing different functional materials to realize product functionalization.
The technical scheme of the invention is as follows:
the invention provides a multifunctional nano composite material which is mainly prepared from the following nano raw materials: 1-10 parts of modified kaolin, 1-10 parts of nano zinc oxide, 1-10 parts of chitosan, 1-10 parts of starch, 1-10 parts of calcium carbonate, 1-10 parts of modified montmorillonite and 1-10 parts of anatase.
Preferably, at least one dimension of the nano composite material is within the range of 0.1-100 nm.
Preferably, the modified kaolin is obtained by ball milling modification of kaolin and hydrogen-containing silicone oil.
Preferably, the modified montmorillonite is obtained by ball-milling modification of sodium-based montmorillonite and hexadecyl trimethyl ammonium bromide.
Preferably, the ball milling medium is steel balls, the rotating speed is 800-1200 r/min, and the ball milling time is 1-2 hours.
The invention also provides a preparation method of the multifunctional nano composite material, which comprises the following steps:
(1) mixing chitosan, nano zinc oxide and starch at 60-70 ℃ by taking water as a medium to obtain a chitosan/nano zinc oxide/starch compound;
(2) stirring and mixing the modified kaolin, the calcium carbonate, the modified montmorillonite and the anatase with the compound obtained in the step (1), and grinding and sieving to obtain a sieved material;
(3) and (3) treating the sieved material with alcohol, washing and drying to obtain the multifunctional nano composite material.
Preferably, in the blending process in the step (1), the mass percentage of water is 20-45%, and the pH value is 6-7.
Preferably, a dispersing agent is also added during the grinding in the step (2).
Further preferably, the sieved particle size in step (2) is less than 800 mesh.
Compared with the prior art, the invention has the advantages that:
the multifunctional nano composite material integrates and optimizes the characteristics of various nano materials, thereby generating various functions and being suitable for being used as functional addition of various materials.
1. The antibacterial and bacteriostatic functions are as follows: the multifunctional nano material can generate free radicals with strong oxidizing property to denature microbial protein, thereby inhibiting and killing microbes and achieving good antibacterial effect. Can effectively inhibit the proliferation and growth of pathogenic bacteria such as salmonella, candida albicans, escherichia coli, staphylococcus aureus and the like. Meanwhile, the commonly used bactericides can inactivate cells, but after bacteria are killed, pyrogenic and toxic components such as endotoxin can be released. Endotoxin is a lethal substance and can cause diseases such as typhoid fever and cholera. However, the nanometer functional material of the invention not only can kill bacteria in the environment, but also can degrade toxic compounds released by the bacteria at the same time, and can be used in the fresh-keeping packaging industry, such as fresh-keeping films, fresh-keeping bags and other soft packages.
2. The deodorization function is as follows: has strong oxidation and deodorization effects on various odor substances, thereby rapidly eliminating odor, killing decay-causing microorganisms, eliminating odor sources and being effective for a long time.
3. Purification function: has strong oxidative decomposition effect on harmful substances such as formaldehyde, benzene, ammonia, radioactive radon and the like, and is decomposed into water and carbon dioxide.
4. The radiation protection function has the functions of absorbing and scattering α gamma rays, and simultaneously has high refractivity and high optical activity, the ultraviolet resistance and the mechanism thereof are related to the particle size, and because the particle size is small and the activity is high, the radiation protection function can reflect and scatter ultraviolet rays and absorb ultraviolet rays, thereby having stronger blocking capability on the ultraviolet rays and being capable of transmitting visible light.
5. Strong redox function: can generate free radicals with high catalytic activity, can generate strong photooxidation and reduction capability, and can catalyze and photolyze various organic pollutants and partial inorganic matters attached to the surface of an object.
6. Energy-saving and environment-friendly functions: the nano composite material can generate a micro-vibration signal, so that fuel oil macromolecular groups generate resonance to be cracked into high-activity small molecular groups, and the fuel oil macromolecular groups are fully mixed with air, thereby achieving the effects of complete combustion, fuel oil saving, horsepower enhancement and tail gas pollution reduction.
7. The function of dredging the channels and collaterals: the nano composite material has micro-amplitude high-frequency vibration, carries out photon energy conduction through resonance effect and strong osmotic force thereof, supplies energy required by cell activation, promotes blood circulation and improves the basal metabolic rate. Can be used in the material addition of the functional protective clothing.
The multifunctional nano composite material has good dispersion and compatibility, thereby providing a foundation for the multi-field transformation application of the multifunctional nano composite material. By utilizing the inhibition and decomposition effects of the antibacterial and organic pollutant-inhibiting agent on bacteria and other organic pollutants, textiles, daily necessities, household products, packaging products and the like with antibacterial functions can be developed. By utilizing the high-frequency vibration property of the nano material, energy-saving and environment-friendly products for reducing the pollution of automobile exhaust and medical products beneficial to human health can be developed. By utilizing the decomposition characteristics of the organic pollutant and harmful gas, the pollution treatment technology and solution for atmosphere pollution, water pollution and domestic garbage treatment for environmental protection can be developed. The multifunctional nano composite material can be excellently fused with various traditional materials such as plastics, metals, rubber and the like, and the functional characteristics of the multifunctional nano composite material are exerted to the greatest extent. Meanwhile, the composite material also has high chemical stability and thermal stability, no radioactivity, no toxicity, no irritation and safe use.
Drawings
FIG. 1 is a colony comparison chart of a common film and an antibacterial film A (an upper common film and a lower antibacterial film A);
FIG. 2 shows the concentration of bacteria at 10
-5Then, comparing the two bacterial colonies (the left side is a common film, and the right side is an antibacterial film A);
FIG. 3 is a colony comparison chart of the common film and the antibacterial film B (upper common film, lower antibacterial film B).
Detailed Description
The invention provides a multifunctional nano composite material which is mainly prepared from the following nano raw materials: 1-10 parts of modified kaolin, 1-10 parts of nano zinc oxide, 1-10 parts of chitosan, 1-10 parts of starch, 1-10 parts of calcium carbonate, 1-10 parts of modified montmorillonite and 1-10 parts of anatase. The proportion of one or more nano-scale raw materials can be adjusted according to requirements, so that the composite material has different characteristics and can be applied to different material purposes.
The nano composite material has at least one dimension of 0.1-100 nm, more preferably 1-80 nm, and further 10-40 nm. The nano composite material can increase the dispersibility and the compatibility of the composite material in the particle size range, and improve the application effect of the nano composite material.
The nano-scale raw material comprises modified kaolin, and the addition amount of the modified kaolin is preferably 3-8 parts by weight, and more preferably 5-7 parts by weight. Kaolin is a non-metallic mineral, a clay and claystone based on clay minerals of the kaolinite group. The chemical formula of the crystal is 2SiO
2·Al
2O
3·2H
2O, kaolin mineral belongs to 1:1 type layered silicate, the crystal mainly comprises silicon-oxygen tetrahedrons and Shaoxing-oxygen octahedrons, wherein the silicon-oxygen tetrahedrons are connected along two-dimensional directions in a mode of sharing a vertex angle to form a grid layer in hexagonal arrangement, and tip oxygen which is not shared by the silicon-oxygen tetrahedrons faces to one side; the 1:1 type unit layer is composed of the oxygen peaks of the common silicon oxygen tetrahedral layer and the oxygen attracting octahedral layer. The modified kaolin is obtained by ball-milling and modifying kaolin and hydrogen-containing silicone oil, wherein the mass ratio of the kaolin to the hydrogen-containing silicone oil is 10:1 to 3, and more preferably 10:1.2 to 1.8. The ball milling medium is preferably steel balls, the rotating speed is preferably 800-1200 r/min, more preferably 1000r/min, and the ball milling time is preferably 1-2 hours. After ball milling, the particle size of the kaolin is reduced, the specific surface area is increased, the hydrophobicity is enhanced, and the fusion capability of the kaolin and other raw materials is improved.
The nano-scale raw material comprises nano zinc oxide, and the addition amount of the nano zinc oxide is preferably 3-9 parts by weight, and more preferably 4-7 parts by weight. The nano zinc oxide has excellent antibacterial performance, and the antibacterial principle is from two points: one is a photocatalysis mechanism, namely, the nano zinc oxide can release electrons with negative electricity in water and air under the irradiation of sunlight, particularly ultraviolet light, and simultaneously leave holes with positive electricity to excite the air to generate active oxygen, and the active oxygen can generate oxidation reaction with various microorganisms, thereby achieving the sterilization effect. The other is a metal ion dissolution mechanism, namely, the dissociated zinc ions are combined with protease when contacting the bacterial body, so that the activity of the zinc ions is lost, and the bactericidal effect is achieved. The nano zinc oxide has the specific surface interface effect of the nano particles because the particle size reaches the nano level, and the antibacterial effect is embodied in that the number of surface atoms of the nano particles is greatly more than that of the traditional particles, and the surface atoms have high energy because of lack of adjacent coordination atoms, so that the affinity of the zinc oxide and bacteria can be enhanced, and the antibacterial efficiency is improved. The nano-zinc oxide is used in the nano-material, so that the defects and limitations of silver-series and titanium dioxide-series antibacterial agents such as easy discoloration and ultraviolet irradiation are overcome, and an excellent antibacterial effect is achieved. The source of the nano zinc oxide is not specially limited, and the nano zinc oxide can be obtained by adopting a commercial product.
The nano-scale raw material comprises chitosan, and the addition amount of the chitosan is preferably 2-7 parts by weight, and more preferably 4-6 parts by weight. Chitosan (chitosan), also known as chitosan, is obtained by deacetylation of chitin (chitin) widely existing in nature, and is chemically named polyglucosamine (1-4) -2-amino-B-D glucose. Because chitosan molecules have free amino groups, the chitosan molecules are easy to form salts in an acidic solution and have cationic property. The amino group characteristics of chitosan are more remarkable as the number of amino groups in the molecule of the chitosan increases, which is the basis of the unique properties of the chitosan, thereby laying the foundation of a plurality of biological characteristics and processing characteristics of the chitosan. The chitosan and its derivatives have good antibacterial activity, and can inhibit growth and reproduction of fungi, bacteria and viruses.
The nanoscale raw material comprises starch, and the addition amount of the starch is preferably 2-7 parts by weight, and more preferably 4-6 parts by weight. Starch is the polymerization of glucose molecules, which is the most common storage form of carbohydrates in cells. The starch is nano starch, and has the appearance characteristics that: the product is white, odorless, tasteless, and hygroscopic.
The nano-scale raw material comprises calcium carbonate, and the addition amount of the calcium carbonate is preferably 2-8 parts by weight, and more preferably 4-6 parts by weight. Calcium carbonate is an inorganic compound, the main components of which are: calcite, of the formula CaCO3, is neutral, substantially insoluble in water, and soluble in hydrochloric acid. The nano calcium carbonate is used in plastic, has high affinity with resin, and can raise or regulate the rigidity, toughness, bending strength, etc. of the material effectively. The rheological property of a plastic processing system can be improved, the plasticizing temperature is reduced, and the size stability, heat resistance and surface smoothness of a product are improved; can be easily kneaded and uniformly dispersed in rubber systems such as NR, BR and BR. And the rubber can be made soft, and the extrusion processing performance and the model fluidity can be improved, so that the rubber product has the characteristics of smooth surface, high elongation, high tensile strength, small permanent deformation, good bending resistance, high tearing strength and the like.
The nano-scale raw material of the invention comprises modified montmorillonite, and the addition amount is preferably3 to 8 parts by weight, more preferably 4 to 6 parts by weight. Montmorillonite, a natural mineral of silicate, is the main mineral component of bentonite ore. Containing Al
2O
316.54％，MgO 4.65％，SiO
250.95 percent. Monoclinic system, multi-site microcrystals, aggregates in the form of soil, spheres, etc. The modified montmorillonite is obtained by ball milling modification of sodium-based montmorillonite and hexadecyl trimethyl ammonium bromide. The mass ratio of the montmorillonite to the hexadecyl trimethyl ammonium bromide is 10:1 to 3, and more preferably 10:1.2 to 1.8. The ball milling medium is preferably steel balls, the rotating speed is preferably 800-1200 r/min, more preferably 1000r/min, and the ball milling time is preferably 1-2 hours. The modified montmorillonite has strong adsorption capacity and good dispersion performance, can be widely applied to the high polymer material industry as an additive of a nano polymer high polymer material, and improves the impact resistance, the fatigue resistance, the dimensional stability, the gas barrier performance and the like, thereby playing a role in enhancing the comprehensive physical properties of the polymer and improving the material processing performance.
The nano-scale raw material comprises anatase, and the addition amount of the anatase is preferably 3-8 parts by weight, and more preferably 4-6 parts by weight. Anatase is titanium dioxide (TiO)
2) One of the three minerals of (1). The product appearance was a white loose powder. The nano-scale titanium dioxide has high chemical stability, thermal stability, super-hydrophilicity and non-migration property, and can be used for long-term sterilization under the action of ultraviolet rays in light. The physical shielding type ultraviolet protective agent can absorb ultraviolet rays, reflect and scatter the ultraviolet rays and transmit visible light, has excellent performance and has great development prospect. Can be activated and generated under the action of ultraviolet rays in sunlight or lamp light to generate free radicals with high catalytic activity, can generate strong photooxidation and reduction capability, and can catalyze and photolyze a plurality of organic matters and partial inorganic matters attached to the surface of an object.
The invention also comprises a preparation method of the multifunctional nano composite material, which comprises the following steps:
(1) mixing chitosan, nano zinc oxide and starch at 60-70 ℃ by taking water as a medium to obtain a chitosan/nano zinc oxide/starch compound;
(2) stirring and mixing the modified kaolin, the calcium carbonate, the modified montmorillonite and the anatase with the compound obtained in the step (1), and grinding and sieving to obtain a sieved material;
(3) and (3) treating the sieved material with alcohol, washing and drying to obtain the multifunctional nano composite material.
In the invention, in the blending process in the step (1), the mass percent of water is preferably 20-45%, and more preferably 30-35%. The blending temperature is preferably 64-67 ℃, and the pH value is preferably 6-7.
In the invention, a dispersant is also added during the grinding in the step (2). The dispersant of the present invention is not particularly limited in kind, and may be any dispersant conventionally used in the art.
The method of the grinding and sieving is not particularly limited in the present invention, and the conventional grinding and sieving in the art is adopted. Wherein, the screened grain diameter in the step (2) is less than 800 meshes, and more preferably 1000-1200 meshes.
The sieved material was treated with alcohol. The volume concentration of the alcohol is preferably 70-85%, and more preferably 75%. The invention washes and dries the material after alcohol treatment to obtain the multifunctional nano composite material. The manner of washing and drying in the present invention is not particularly limited, and a conventional method in the art may be used.
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
20g of kaolin and 1.2g of hydrogen-containing silicone oil are introduced into the pot of a planetary ball mill. 50 steel balls with different sizes are prepared in the tank body, the rotating speed of the main disc is controlled at 896r/min, and ball milling is carried out for 2 hours to obtain the modified kaolin.
20g of montmorillonite and 1.2g of cetyltrimethylammonium bromide were placed in the pot of a planetary ball mill. 50 steel balls with different sizes are prepared in the tank body, the rotating speed of the main disc is controlled at 896r/min, and ball milling is carried out for 2 hours to obtain the modified montmorillonite.
10g of nano chitosan, 10g of nano zinc oxide, 10g of nano starch and 20ml of water are mixed at 65 ℃, and the pH value of the mixed material is 7, so that the chitosan/nano zinc oxide/starch compound is obtained. Stirring and mixing 10g of modified kaolin, 10g of calcium carbonate, 10g of modified montmorillonite, 10g of anatase and 2g of dispersing agent with the chitosan/nano zinc oxide/starch compound, grinding and sieving with a 1000-mesh sieve, treating the sieved material with 75% alcohol, washing and drying with deionized water to obtain the multifunctional nano composite material.
Example 2
20g of kaolin and 1.5g of hydrogen-containing silicone oil are introduced into the pot of a planetary ball mill. 50 steel balls with different sizes are prepared in the tank body, the rotating speed of the main disc is controlled at 1126r/min, and the modified kaolin is obtained after ball milling for 1.5 hours.
20g of montmorillonite and 1.7g of cetyltrimethylammonium bromide were placed in the pot of a planetary ball mill. 50 steel balls with different sizes are prepared in the tank body, the rotating speed of the main disc is controlled at 11266r/min, and ball milling is carried out for 1.5 hours to obtain the modified montmorillonite.
10g of nano chitosan, 20g of nano zinc oxide, 10g of nano starch and 20ml of water are mixed at 70 ℃, and the pH value of the mixed material is 6.5, so that the chitosan/nano zinc oxide/starch compound is obtained. Stirring and mixing 10g of modified kaolin, 15g of calcium carbonate, 10g of modified montmorillonite, 10g of anatase and 2g of dispersing agent with the chitosan/nano zinc oxide/starch compound, grinding and sieving with a 1200-mesh sieve, treating sieved materials with 75% alcohol, washing and drying with deionized water to obtain the multifunctional nano composite material with excellent sterilization function.
Example 3
20g of kaolin and 1.8g of hydrogen-containing silicone oil are introduced into the pot of a planetary ball mill. 50 steel balls with different sizes are prepared in the tank body, the rotating speed of the main disc is controlled at 976r/min, and the modified kaolin is obtained after ball milling for 2 hours.
20g of montmorillonite and 1.8g of cetyltrimethylammonium bromide were placed in the pot of a planetary ball mill. 50 steel balls with different sizes are prepared in the tank body, the rotating speed of the main disc is controlled at 976r/min, and the modified montmorillonite is obtained after ball milling for 2 hours.
And (3) blending 20g of nano chitosan, 10g of nano zinc oxide, 10g of nano starch and 20ml of water at 65 ℃, wherein the pH value of the blended material is 7, so as to obtain the chitosan/nano zinc oxide/starch compound. Stirring and mixing 20g of modified kaolin, 10g of calcium carbonate, 10g of modified montmorillonite, 12g of anatase and 2g of dispersing agent with the chitosan/nano zinc oxide/starch compound, grinding and sieving with a 1000-mesh sieve, treating the sieved material with 80% alcohol, washing and drying with deionized water to obtain the multifunctional nano composite material.
Example 4
Radionuclide limit detection
The radionuclide limits of the nanocomposite material of the invention were determined according to the method in GB6566-2010 "building material radionuclide limits", and the results are shown in Table 1.
TABLE 1 radionuclide limits of nanocomposites of the invention
The result shows that the nano composite material has no radioactivity and accords with the standard of A-class products.
Example 5
Acute oral toxicity test
Experimental animals: kunming mouse
Preparing a test substance: weighing 7.500g of the nano composite material, using corn oil to fix the volume to 60ml, and uniformly mixing for later use.
The test method comprises the following steps: the maximum dose given to the test animals was 7500mg/kg body weight by the dose-limiting method. 20 animals, male and female, were administered orally by gavage at maximum use concentration and maximum gavage volume of 20ml/kg, 3 times with 4 hour intervals. Animals were fasted overnight before the experiment without restriction of water.
Observation indexes are as follows: animals were observed immediately after dosing for signs of intoxication and mortality, at least once daily thereafter for 14 days. During the test, the weekly body weight, the number of animal deaths and the death time of the animals were recorded, and the dead animals and the sacrificed animals at the end of the observation were subjected to autopsy to visually observe whether or not there was abnormality in the tissues or organs.
TABLE 2 clinical symptoms and mortality of the test animals
TABLE 3 weight status of the animals tested
And (4) evaluating the results: the tested animals do not have any toxic symptoms and death conditions within the observation period of 14 days after gastric lavage, and the weight of each sex animal is in a growing trend. After the observation period, the animals were sacrificed for necropsy, and no abnormality was found in the organ or tissue.
And (4) conclusion: according to the grading standard of the acute oral toxicity test in GB15193.3-2014, the nanocomposite disclosed by the invention is used for treating acute oral LD of Kunming mice
50>7500mg/kg body weight, is nontoxic in practice.
Example 6
Multiple skin irritation test
Experimental animals: new Zealand Rabbit
The test method comprises the following steps: the hair on two sides of the spine of 3 rabbits is removed 24 hours before the test, the epidermis is not damaged, and the hair removal range is about 3cm multiplied by 3 cm. In the test, 0.5g of the nanocomposite material is taken per rabbit, the nanocomposite material is directly smeared on the unhaired skin of one side of each rabbit, gauze is covered and fixed by a non-irritating bandage, the residual nanocomposite material is removed by warm water after the application for 4 hours, and the nanocomposite material is smeared once a day and is smeared continuously for 14 days. The other skin was left untreated as a blank control. The results were observed 24h after each application.
Observation indexes are as follows: the skin at the site of application was observed daily for erythema and edema formation, and scored and recorded according to skin irritation response scoring criteria. The average score per animal per day was calculated. The stimulation intensity was graded according to skin stimulation intensity grading criteria.
Table 4 table for recording the results of multiple skin irritation tests
And (4) evaluating the results: in the observation period, 3 rabbits showed no erythema and no symptoms in water, and the score of each animal was evaluated to be 0 every day. According to the skin irritation intensity grading standard of disinfection technical specification (2002 edition of Ministry of health), the skin irritation intensity of the nano composite material is non-irritant.
The detection of non-radioactivity, oral non-toxicity and skin contact in the embodiments 4 to 6 provides sufficient guarantee for the safety application of the nanocomposite material of the present invention, and the nanocomposite material can be used as a packaging material or a component of food, clothes, daily necessities, and the like.
Example 7
The invention relates to an antibacterial film prepared from a nano composite material
The antibacterial film is prepared by adopting an antibacterial master batch method, wherein the antibacterial master batch method is a highly concentrated body formed by dispersing an antibacterial agent in carrier resin, namely an antibacterial master batch, and then the antibacterial master batch is processed together with plastic or is blended and dispersed again together with the plastic to form the antibacterial film.
An antibacterial film A: adding 10% of the film of the nanocomposite material of the invention,
and (3) an antibacterial film B: a film with 10% silver molybdate antimicrobial added.
The two films are directly trial-manufactured on a production line by Hubei Hui Shi plastic industry Co., Ltd by adopting an antibacterial masterbatch method, 100kg of each film is prepared, and the type of the film is SCPP.
TABLE 5 antimicrobial film Performance test report
As seen from Table 5, all the properties of the prepared film are in accordance with the industrial standard, and compared with the common film, the antibacterial film has small changes in four indexes of thickness, haze, surface wetting tension and glossiness, which shows that the addition of the nano composite material of the invention has no influence on the appearance of the film; in addition, in the three indexes of tensile strength, elongation at break and friction coefficient, the difference between the film containing the nano composite material and a common film is not large, and the performance change is not obvious, which indicates that the addition of the nano composite material has little influence on the physical properties of the film. The three criteria of the silver-containing antibacterial agent-containing film are greatly changed as compared with the conventional film, but are within the standard range.
Detection of antibacterial properties of antibacterial film
Antibacterial performance testing method
1) Sample pretreatment: cutting a film with a certain area, scrubbing the surface with 75% ethanol solution, washing the surface with distilled water for three times, continuously washing for several times to ensure that no ethanol residue exists on the surface, and placing the film in an ultra-clean bench to sterilize with an ultraviolet lamp. The weighed paper was cut to the same size as the film and sterilized in a phi 90 dish with wet filter paper laid on the bottom.
2) Preparing strains: shake culturing the bacterial suspension on a shaker at 37 deg.C for 24 hr, detecting bacterial concentration, and diluting 100 μ l bacterial suspension to 10%
5～10
6cuf/ml。
3) The diluted bacterial suspension (100. mu.l) was applied to the surface of the membrane, and the membrane was covered with a weighing paper and incubated in an incubator at 37 ℃ for 24 hours. (surface area of sample 6cm
2The preparation is applied by 100 μ l of bacteria, not 6cm
2Time conversion according to the proportion)
4) After the culture is finished, the surface of the film is scrubbed by using a sterile cotton ball, the weighing paper is crushed by using forceps, 1ml of supernatant is absorbed and placed in a culture dish, and the supernatant is poured into a flat plate after three ten-fold dilution. The cells were incubated at 37 ℃ for 24 hours. Three replicates were made for this step.
5) Counting viable bacteria: and selecting a plate among 30-300 colonies as a colony total number determination standard. After counting the number of colonies on each plate, the average number of colonies on each plate of the same dilution was determined.
6) And (3) calculating the 24-hour sterilization rate:
FIG. 1 is a colony comparison diagram of a conventional film and an antibacterial film A. The bacterial concentration of the plate is reduced by 10 times from left to right, respectively 10
-4，10
-5，10
-6The colony number is observed to be in a descending trend, and almost no colony exists in the three plates at the lower row, which shows that the sample added with the antibacterial agent has excellent antibacterial effect.
For clearer comparison of colony counts, the two plates used in FIG. 2 were set to the bacteria concentration 10 in FIG. 1
-5The left side of the two comparison plates is a common film, the right side of the two comparison plates is an antibacterial film A, pictures show that the right plate has no bacteria, and the sterilization rate is 100 percent.
FIG. 3 is a comparative graph of colonies of the conventional film and the antibacterial film B. The bacterial concentration of the plate is reduced by 10 times from left to right, respectively 10
-4，10
-5，10
-6The number of colonies is observed to be in a descending trend, and the colonies appear in the three down plates, and the comparison shows that the antibacterial performance of the antibacterial film A is better than that of the antibacterial film B.
From the colony count of the blank to a concentration of 10
-6The number of the bacterial colonies is more than 300, and the sterilization rate of the antibacterial film B sample is calculated to be 90 percent. The sterilization rate of the sample of the antibacterial film A reaches 100 percent, and the antibacterial film A has better sterilization performance.
The embodiment can show that the multifunctional nano composite material has good fluidity and compatibility, can be excellently fused with various traditional plastic materials, and exerts the functional characteristics to the greatest extent.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. The multifunctional nano composite material is characterized by being mainly prepared from the following nano raw materials: 1-10 parts of modified kaolin, 1-10 parts of nano zinc oxide, 1-10 parts of chitosan, 1-10 parts of starch, 1-10 parts of calcium carbonate, 1-10 parts of modified montmorillonite and 1-10 parts of anatase.
2. The multifunctional nanocomposite material of claim 1 wherein the nanocomposite material has at least one dimension in the range of 0.1 to 100 nm.
3. The multifunctional nanocomposite as claimed in claim 1, wherein the modified kaolin is obtained by ball milling modification of kaolin with hydrogen-containing silicone oil.
4. The multifunctional nanocomposite material of claim 1, wherein the modified montmorillonite is obtained by ball-milling modification of sodium montmorillonite and hexadecyl trimethyl ammonium bromide.
5. The multifunctional nanocomposite material of claim 3 or 4, wherein the ball milling medium is steel balls, the rotation speed is 800-1200 r/min, and the ball milling time is 1-2 hours.
6. A method for preparing the multifunctional nanocomposite material of any one of claims 1 to 5, comprising the steps of:
(1) mixing chitosan, nano zinc oxide and starch at 60-70 ℃ by taking water as a medium to obtain a chitosan/nano zinc oxide/starch compound;
(2) stirring and mixing the modified kaolin, the calcium carbonate, the modified montmorillonite and the anatase with the compound obtained in the step (1), and grinding and sieving to obtain a sieved material;
(3) and (3) treating the sieved material with alcohol, washing and drying to obtain the multifunctional nano composite material.
7. The preparation method of the multifunctional nano composite material according to claim 6, wherein in the blending process in the step (1), the mass percent of water is 20-45%, and the pH value is 6-7.
8. The method of claim 6, wherein a dispersant is further added during the grinding in the step (2).
9. The method for preparing multifunctional nanocomposites according to claim 6 or 8, wherein the sieved particle size of step (2) is less than 800 mesh.
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