CN115651338A - Preparation method of acrylic acid-based nano composite material - Google Patents
Preparation method of acrylic acid-based nano composite material Download PDFInfo
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Abstract
The invention discloses a preparation method of an acrylic acid-based nano composite material, which comprises the following steps of carrying out modification treatment on nano zirconia ceramic particles; grinding and modifying the boron nitride nanosheets; preparing a lanthanum salt ethanol solution; mixing the modified boron nitride nanosheet with a lanthanum salt ethanol solution for reaction to obtain a lanthanum salt modified boron nitride nanometer solution; mixing the modified zirconia ceramic particles and the lanthanum salt modified boron nitride nano solution under an ice bath condition to obtain a nano composite reinforcement solution, and performing centrifugal separation and drying treatment to obtain a multi-dimensional nano reinforcement for later use; adding the multi-dimensional nano reinforcement into acrylic photosensitive resin for mixing treatment to obtain composite slurry, and carrying out photocuring 3D printing on the composite slurry; the composite material prepared by the method has good comprehensive performance.
Description
Technical Field
The invention belongs to the field of acrylic resin processing, and particularly relates to a preparation method of an acrylic-based nano composite material.
Background
The photocuring 3D printing technology is characterized in that a computer is used for controlling ultraviolet light beams to selectively cure photosensitive resin layer by layer, controlling the displacement of a platform in the z-axis direction, and curing the next layer of photosensitive resin on the upper layer of cured layer, so that the 3D printed part is manufactured. The acrylic resin is a generic term for polymers of acrylic acid, methacrylic acid and derivatives thereof. Acrylic polymers, i.e., thermosetting acrylic resins, formed by crosslinking acrylic monomers (e.g., methyl acrylate, ethyl acrylate, methyl methacrylate, etc.) as the basic components have high wear resistance.
The low-odor acrylic resin has low viscosity and excellent fluidity, is applied to the field of 3D printing photocuring forming, can quickly infiltrate the model, reduces the resin release force and improves the printing model precision. However, in the prior production application, when the pure acrylic resin is prepared, a thermoplastic molding forming process is adopted, and the product prepared by the process has the problems of interface defects, low mechanical strength and the like.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made in view of the above and/or other problems occurring in the preparation of acrylic resins in the prior art.
Therefore, the invention aims to overcome the defects in the prior art and provide a preparation method of the acrylic-based nanocomposite material, and the acrylic-based nanocomposite material prepared by the method has smooth surface and higher physical and chemical properties.
In order to solve the technical problems, the invention provides the following technical scheme: a method for preparing an acrylic-based nanocomposite, comprising the steps of,
carrying out modification treatment on the nano zirconia ceramic particles;
grinding and modifying the boron nitride nanosheets;
preparing a lanthanum salt ethanol solution;
mixing the modified boron nitride nanosheet with a lanthanum salt ethanol solution for reaction to obtain a lanthanum salt modified boron nitride nanometer solution;
mixing the modified zirconia ceramic particles and the lanthanum salt modified boron nitride nano solution under an ice bath condition to obtain a nano composite reinforcement solution, and performing centrifugal separation and drying treatment to obtain a multi-dimensional nano reinforcement for later use;
adding the multi-dimensional nano reinforcement into acrylic photosensitive resin for mixing to obtain composite slurry, and carrying out photocuring 3D printing on the composite slurry.
As a further improvement of the invention, the step of performing modification treatment on the nano zirconia ceramic particles comprises,
carrying out carboxylation coating treatment on the nano zirconia ceramic particles, wherein a modification solution required in the coating treatment comprises an ethanol saturated solution of adipic acid, the mass volume ratio of the ethanol saturated solution of the adipic acid is 2.3g/100mL, and the solution after the coating treatment is a first mixed suspension;
and carrying out centrifugal separation on the first mixed suspension and drying to obtain the modified zirconia powder.
As a further improvement of the method, the solution used for grinding and hydroxylating the boron nitride nanosheets comprises a sodium hydroxide solution, and the solution after hydroxylating and modifying is a second mixed suspension;
and carrying out centrifugal separation on the second mixed suspension and drying to obtain the modified boron nitride powder.
As a further improvement of the invention, the solution used for preparing the lanthanum salt ethanol solution comprises LaCl 3 、NH 4 Cl, DEA, EDTA ammonia solution and ethanol, laCl 3 、NH 4 The concentration weight percentage of Cl, DEA, EDTA ammonia water solution and ethanol is 0.1-2.0%, 0.05-1.0%, 0.02-0.4%, 5-20% and 76.6-94.83%.
As a further improvement of the invention, the mass ratio of the lanthanum salt ethanol solution to the first mixed suspension is 1 to 1.5:3.
as a further improvement of the invention, the mass ratio of the first mixed suspension to the second mixed suspension is 1 to 4:2.
as a further improvement of the invention, when the first mixed suspension and the second mixed suspension are dried, the working parameters of the vacuum drying oven comprise that the temperature is 70 to 85 ℃, and the working time is 16 to 24h.
In order to further improve the uniform dispersibility of the powder added into the photosensitive resin, the multidimensional nano-reinforcement is pretreated before the photosensitive resin is added, the multidimensional nano-reinforcement is pre-dispersed in deionized water, and the pre-dispersion concentrations of the zirconium oxide powder and the boron nitride powder are respectively 0.025-0.1% and 0.1-0.5% by weight.
As a further improvement of the invention, the mode of grinding the boron nitride nanosheet is wet ball milling, the ball milling rotation speed is 200-250r/min, and the ball milling ratio is 10:1, stopping the machine for 10 min after ball milling is carried out for 30 to 50 min, wherein the ball milling time is 16 to 24h, repeatedly centrifuging, washing and filtering a ball milling product by using dilute hydrochloric acid, wherein the rotation speed of a centrifugal machine is 1800 to 2000rpm, the centrifugation time is 0.5 to 1h during centrifuging, calibrating the washing product by using a pH test paper, and repeatedly filtering the washing product by using deionized water until the pH is neutral.
As a further improvement of the invention, the concentration of the sodium hydroxide solution is 0.5 to 2mol/L, the sheet diameter of the boron nitride nanosheet is 0.1 to 0.4 mu m, and the purity is 98wt%.
The invention has the beneficial effects that:
the invention prepares the nano material with high activity by chemical modification and ball milling treatment, exerts the high melting point and low thermal expansion coefficient of zirconium dioxide and improves the heat resistance of the nano composite material; the boron nitride has corrosion resistance, oxidation resistance and self-lubricating property, the surface strength of the nano composite material is improved, and the frictional wear property of the composite material can be improved due to the unique lamellar self-lubricating property; the multidimensional nano composite reinforcement prepared by coordinating the two-dimensional nano material and the ceramic particles by means of the higher coordination capacity of the lanthanum salt solution can better connect the interface bonding between the reinforcement and the resin matrix, thereby synergistically improving the comprehensive performance of the composite material; the nano composite material prepared by the method has smooth surface and high physical and chemical properties; the overall tribological, mechanical and thermal properties of the material are improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 is a Transmission Electron Microscope (TEM) image of the nanocomposite reinforcement dispersion prepared in example 1 and examples 4-6.
Fig. 2 is a schematic diagram showing the operation of the photo-curing printer according to embodiment 1 and embodiments 4 to 6.
FIG. 3 is a graph showing tribological performance curves of the acrylic-based nanocomposites prepared in example 1 and examples 4-6.
FIG. 4 is a SEM wear surface topography for the acrylic-based nanocomposites prepared in example 1 and examples 4-6.
FIG. 5 is a thermal performance curve of the acrylic-based nanocomposites prepared in example 1 and examples 4-6; wherein: (a) a TGA profile; (b) DTG curve.
FIG. 6 is a graph showing mechanical properties of the acrylic based nanocomposites prepared in example 1 and examples 4-6; wherein: (a) tensile load at break and elongation at break; (b) tensile strength and tensile modulus.
FIG. 7 is a graph of mechanical properties of the acrylic-based nanocomposites prepared in example 1 and examples 4-6: flexural strength and flexural modulus.
Fig. 8 is a Transmission Electron Microscope (TEM) image of the nanocomposite reinforcement dispersion prepared in example 2.
Fig. 9 is a Transmission Electron Microscope (TEM) image of the nanocomposite reinforcement dispersion prepared in example 3.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, embodiments accompanying the present invention are described in detail below with reference to examples.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The preparation method of the gas-sensitive material provided by the invention comprises the following steps:
(1) Carrying out modification treatment on the nano zirconia ceramic particles, specifically, carrying out carboxylation coating treatment on the nano zirconia ceramic particles, wherein a modification solution required in the coating treatment comprises an ethanol saturated solution of adipic acid, the mass volume ratio of the ethanol saturated solution of the adipic acid is 2.3g/100mL, the coated solution is a first mixed suspension, and carrying out centrifugal separation and drying treatment on the first mixed suspension to obtain modified zirconia powder;
(2) Grinding and modifying the boron nitride nanosheets, specifically, a solution used in grinding and hydroxylating modification of the boron nitride nanosheets comprises 0.5-2mol/L sodium hydroxide solution, the sheet diameter of the boron nitride nanosheets is 0.1-0.4 mu m, the purity is 98wt%, the solution after hydroxylating modification is a second mixed suspension, and the second mixed suspension is subjected to centrifugal separation and drying treatment to obtain modified boron nitride powder;
(3) Preparing lanthanum salt ethanol solution, wherein the solution used for preparing the lanthanum salt ethanol solution comprises LaCl 3 、NH 4 Cl, DEA, EDTA ammonia solution and ethanol, laCl 3 、NH 4 The concentration weight percentages of Cl, DEA, EDTA ammonia water solution and ethanol are respectively 0.1-2.0%, 0.05-1.0%, 0.02-0.4%, 5-20% and 76.6-94.83%, corresponding medicines are accurately weighed according to the corresponding concentration weight percentages, the medicines are placed in a four-opening beaker for mixing treatment, magnetic stirring is carried out at the constant temperature of 55 ℃, and the heat preservation time is 1 h; placing the mixture in an ice bath for ultrasonic dispersion, and observing the agglomeration phenomenon to obtain a lanthanum salt ethanol solution; the sum of the mass concentration percentage of the medicine is 100%;
(4) Mixing the second mixed suspension and a lanthanum salt ethanol solution for reaction, and placing the second mixed suspension in a four-opening beaker for later use; mixing and reacting the prepared lanthanum salt ethanol solution according to a certain mass ratio; the mass ratio of the lanthanum salt ethanol solution to the second mixed suspension is 1 to 1.5:3, carrying out magnetic stirring at the constant temperature of 55 ℃ for the mixing reaction, and keeping the temperature for 1 h; performing ice-bath ultrasonic dispersion, and observing an agglomeration phenomenon to obtain a lanthanum salt modified boron nitride nano solution;
(5) Mixing the first mixed suspension and the second mixed suspension under an ice bath condition, and placing the first mixed suspension into a 500mL four-opening beaker for later use; mixing the second mixed suspension according to a certain mass ratio; the mass ratio of the first mixed suspension to the second mixed suspension is 1 to 4:2, carrying out magnetic stirring at the constant temperature of 55 ℃ in the material mixing reaction, and keeping the temperature for 1 h; performing ice-bath ultrasonic dispersion, observing agglomeration to obtain a nano composite reinforcement solution, performing centrifugal separation and drying treatment to obtain a multi-dimensional nano reinforcement for later use;
(6) The method comprises the steps of pretreating a multidimensional nano reinforcement, dispersing the multidimensional nano reinforcement in deionized water in advance, adding zirconium oxide powder and boron nitride powder into acrylic photosensitive resin for mixing treatment to obtain composite slurry, and carrying out photocuring 3D printing on the composite slurry, wherein the weight percentage of the predispersed concentration of the zirconium oxide powder to 0.1% and the weight percentage of the predispersed concentration of the boron nitride powder to 0.1% to 0.5%.
And when the first mixed suspension and the second mixed suspension are dried, working parameters of a vacuum drying oven comprise the temperature of 70 to 85 ℃ and the working time of 16 to 24h.
Further, the mode of grinding the boron nitride nanosheets is wet ball milling, the rotating speed of the ball milling is 200-250r/min, and the ball milling ratio is 10:1, stopping the machine for 10 min after ball milling is carried out for 30 to 50 min, wherein the ball milling time is 16 to 24h, repeatedly centrifuging, washing and filtering a ball milling product by using dilute hydrochloric acid, wherein the rotation speed of a centrifugal machine is 1800 to 2000rpm, the centrifugation time is 0.5 to 1h during centrifuging, calibrating the washing product by using a pH test paper, and repeatedly filtering the washing product by using deionized water until the pH is neutral.
Example 1
Preparing a nano composite reinforced solution, a first mixed suspension, a second mixed suspension and LaCl 3 、NH 4 The concentration weight percentages of Cl, DEA, EDTA ammonia water solution and ethanol solution are respectively: 0.05 percent, 0.1 percent, 1.0 percent, 0.05 percent, 0.1 percent, 10 percent and 88.85 percent, weighing and preparing the raw materials, fully mixing the raw materials, and carrying out constant-temperature magnetic stirring under the conditions that the temperature is 55 ℃ and the heat preservation time is 2 hours to obtain a suspension solution, wherein the concentration of a sodium hydroxide solution is 2mol/L, the concentration of an ethanol saturated solution of adipic acid is 2.3g/100mL (25 ℃), the first mixed suspension adopts an acidic solvent activation mode, a layer of active functional layer is coated on the surface of zirconia ceramic particles, the particle size of the ceramic particles is 20 to 40 nm, the purity is 99wt percent, and the dispersion concentration between the ethanol saturated solution of the adipic acid and the nano ceramic particles is controlled to be 99wt percent1g/40mL（25℃）。
Preparing an ethanol saturated solution of adipic acid, comprising the following steps of accurately weighing 2.3g of adipic acid crystal components and 100mL of ethanol, fully mixing the raw materials, stirring at normal temperature until the raw materials are completely dissolved, and observing the transparency degree of the solution; accurately weighing 40mL of the ethanol saturated solution of the product adipic acid, accurately weighing 1g of nano zirconia powder, and carrying out magnetic stirring at the constant temperature of 55 ℃ for 2 h; placing the mixture in an ice bath for ultrasonic dispersion, and observing agglomeration to obtain a carboxylated zirconia suspension, namely a first mixed suspension;
the second mixed suspension is processed by wet ball milling, ball milling materials are NaOH solution and BNNS (boron nitride nano-sheet) powder, and the concentration of the NaOH aqueous solution is controlled to be 2mol/L; the diameter of the Boron Nitride Nanosheet (BNNS) is 0.1 to 0.4 mu m, and the purity is 98wt%; the ball milling treatment adopts inert gas protection, and the inert gas is Ar; the parameters of the ball milling treatment step comprise: adopting a vacuum planetary ball milling method, controlling the ball milling speed to be 200r/min, and controlling the ball milling ratio to be 10:1, stopping the ball milling for 40 min for 10 min, wherein the ball milling time is 24h, repeatedly washing and filtering the ball milling product with dilute hydrochloric acid, wherein the washing adopts a centrifugal mode, the working parameters of the centrifuge comprise the rotation speed of the centrifuge is 1800rpm, the centrifugal time is 1h, the washing product is calibrated by adopting a PH test paper, and the pH is repeatedly filtered by deionized water to directly keep the pH neutral; and obtaining a hydroxylated boron nitride nanosheet suspension, namely a second mixed suspension.
When the modified nano suspension is dried, the working parameters of the vacuum drying oven comprise: setting the temperature at 80 ℃ and the working time at 24h, and removing the residual solvent to obtain the modified nano material powder for later use.
The modified nano material powder is pre-dispersed in deionized water, the concentration weight percentage of the modified zirconia powder and the concentration weight percentage of the modified boron nitride powder are respectively controlled to be 0.05 percent and 0.1 percent, the solution dispersed by the modified zirconia powder is named as a first dispersion solution, and the solution dispersed by the modified boron nitride powder is named as a second dispersion solution.
A TEM micrograph of the first dispersed solution prepared using the method of this example is shown in fig. 1, with fig. 1 (a) unmodified and fig. 1 (b) modified; a TEM micrograph of the second dispersion solution is shown in an attached drawing 1, a drawing 1 (c) is unmodified, a drawing 1 (d) is modified, and it can be seen from the drawing that the dispersion stability of the nano material before modification is poor, the agglomeration phenomenon occurs, the modified ceramic particles are uniformly distributed, the large-area agglomeration phenomenon does not occur, and the boron nitride nanosheet presents a lamellar structure; this shows that the modified nano material has higher hydrophilicity, and also shows that the surface of the nano material is successfully grafted with active functional groups.
Preparing lanthanum salt modified solution, controlling the concentration weight percentage of the lanthanum salt solution as LaCl 3 ：1.0%， NH 4 Cl:0.05%, DEA:0.1%, EDTA ammonia solution: 10%, ethanol: 88.85 percent; modifying the second mixed suspension by adopting a lanthanum salt solution, wherein the mass ratio of the lanthanum salt solution to the second mixed suspension is controlled to be 1; obtaining lanthanum salt modified boron nitride nanosheet suspension;
mixing the second dispersion solution and the lanthanum salt modified boron nitride nanosheet suspension according to the proportion of 1;
the TEM micrograph of the nanocomposite reinforced solution prepared in this embodiment is shown in fig. 1 (f), from which it can be seen that the lamellar structure of the boron nitride nanosheet and the particle shape of the nano zirconia are intact, and the nanoparticles are uniformly grafted on the edge of the lamellar structure, similar to a "rivet" structure.
Mixing the nano composite reinforcement and acrylic photosensitive resin according to the proportion of 5; carrying out photocuring three-dimensional forming on the material by adopting an additive manufacturing technology; the preparation parameters related to photocuring stereolithography comprise: the exposure time of the bottom layer is 60 s, the exposure delay is 5 s, the single-layer exposure time is 4 s, the lifting height of the platform is 5mm, and the working rotating speed of the motor is 5 mm.s -1 The molding accuracy was 10 μm.
Printing and forming of the acrylic acid-based nano composite material, and the preparation parameters comprise: the single-layer printing thickness is 30 mu m, the x-axis and y-axis compensation is 0.05mm, the z-axis compensation is 1.0mm, the anti-aliasing gray scale range is 127.5, the heat treatment and the light curing are carried out on the nano composite material after the printing and forming, the heat treatment temperature is set to be 80 ℃, and the heat preservation is carried out for 2 hours; the UV curing treatment time is 1.5h.
According to the invention, the two-dimensional nano material is adopted to cooperate with the ceramic particles to prepare the multi-dimensional composite reinforcement, and the defects of pores, pits and the like existing in the product interface are improved through the filling effect of the nano particles and the self-lubricating property of the two-dimensional structure, so that the performances of the product such as tribology, thermology, mechanics and the like are comprehensively improved.
The following experimental verification proves the performance of the composite material prepared by the invention, specifically, the prepared acrylic-based nanocomposite material is subjected to tribology (a tribology tester (UMT-2, bruker Instrument, USA) is used for testing the tribology performance of a sample, the friction coefficient is automatically recorded by a system, the result data is the average value of stable friction stages, a non-contact three-dimensional optical profiler (CountourGT-K, bruker Instrument, USA) is used for observing the appearance and depth of a grinding mark and calculating the wear volume), and a high temperature synchronous thermal analyzer (Pyris 1 TGA, perkin Elmer, USA) is used for measuring the thermal stability of the sample, the temperature range is 25-650 ℃, and the atmosphere is N 2 The temperature rise rate: 5 ℃ per min; the phase change properties of the sample material are determined by differential scanning calorimetry (DSC 8500, "Perkin Elmer, USA") and mechanical properties (tensile tests are carried out in accordance with GB/T1040.2-2006 on a microcomputer single arm tensile tester (LT-5000, china) with a tester indenter of 2 mm. Min.) -1 The speed of the test is continuously loaded until the test sample is damaged, each group of tests is carried out for 5 times, effective data of the tests are taken for analysis and characterization, the mechanism of photocuring three-dimensional forming is shown as the attached figure 2, the tribological performance of the sample is shown as the figure 3, and the figure 3 (a) is a friction coefficient; (b) wear rate; (c) is the dynamic friction coefficient; (d) The dynamic friction coefficient in the stable region, FIG. 4 (d), is an SEM micrograph of the wear scar in this example.
The acrylic-based nanocomposite (PAR-4) prepared in this example was tested for initial decomposition temperature (T) 5 %) is 318.97 (figure 5),the tensile strength and modulus were 44.58MPa and 2.72GPa, respectively (FIG. 6), and the flexural strength and modulus were 152.11MPa and 4.75GPa, respectively (FIG. 7). The coefficient of friction and wear rate in this example are lowest, T 5 % and higher strength and modulus, which indicates that the acrylic-based nanocomposite prepared by the method has the best combination of properties.
Example 2
Preparing a nano composite reinforced solution, a first mixed suspension, a second mixed suspension and LaCl 3 、NH 4 The concentration weight percentages of Cl, DEA, EDTA ammonia water solution and ethanol solution are respectively: 0.075%, 0.3%, 2.0%, 0.1%, 0.5%, 5%, 92.4%, weighing and preparing raw materials, fully mixing the raw materials, and performing constant-temperature magnetic stirring at the temperature of 60 ℃ and the heat preservation time of 2h to obtain a suspension, wherein the concentration of a sodium hydroxide solution is 1mol/L, the concentration of an ethanol saturated solution of adipic acid is 4.6g/100mL (25 ℃), the surface of zirconia ceramic particles is coated with an active functional layer by adopting an acidic solvent activation mode for the first mixed suspension, the particle size of the ceramic particles is 20 to 40 nm, the purity is 99wt%, and the dispersion concentration of the ethanol saturated solution of adipic acid and the nano ceramic particles is controlled to be 1.5g/40mL (25 ℃).
Preparing an ethanol saturated solution of adipic acid, comprising the following steps of accurately weighing 4.6g of adipic acid crystal components and 100mL of ethanol, fully mixing the raw materials, stirring at normal temperature until the raw materials are completely dissolved, and observing the transparency degree of the solution; accurately weighing 40mL of the ethanol saturated solution of the product adipic acid, accurately weighing 1.5g of nano zirconia powder, and carrying out magnetic stirring at the constant temperature of 60 ℃ for 2 h; placing the mixture in an ice bath for ultrasonic dispersion, and observing agglomeration to obtain a carboxylated zirconia suspension, namely a first mixed suspension;
the second mixed suspension is processed by wet ball milling, ball milling materials are NaOH solution and BNNS (boron nitride nano-sheet) powder, and the concentration of the NaOH aqueous solution is controlled to be 1mol/L; the diameter of the Boron Nitride Nanosheet (BNNS) is 0.1 to 0.4 mu m, and the purity is 98wt%; the ball milling treatment adopts inert gas protection, and the inert gas is Ar; the parameters of the ball milling treatment step comprise: adopting a vacuum planetary ball milling method, controlling the ball milling speed to be 225r/min, and controlling the ball milling ratio to be 10:1, stopping ball milling for 50 min for 10 min, wherein the ball milling time is 24h, repeatedly washing and filtering the ball milling product with dilute hydrochloric acid, wherein the washing adopts a centrifugal mode, the working parameters of the centrifugal machine comprise 1850rpm of the rotating speed of the centrifugal machine and 1h of centrifugal time, the washing product is calibrated by using a PH test paper, and the pH is repeatedly filtered by using deionized water to directly keep the pH neutral; and obtaining a hydroxylated boron nitride nanosheet suspension, namely a second mixed suspension.
When the modified nanometer suspension is dried, the working parameters of the vacuum drying oven comprise: setting the temperature at 70 ℃ and the working time at 24h, and removing the residual solvent to obtain the modified nano material powder for later use.
The modified nano material powder is pre-dispersed in deionized water, the concentration weight percentage of the modified zirconia powder and the concentration weight percentage of the modified boron nitride powder are respectively controlled to be 0.075 percent and 0.3 percent, the solution dispersed by the modified zirconia powder is named as a first dispersion solution, and the solution dispersed by the modified boron nitride powder is named as a second dispersion solution.
A TEM micrograph of the first dispersed solution prepared using the method of this example is shown in fig. 8, in which fig. 8 (a) is unmodified and fig. 8 (b) is modified; the TEM micrograph of the second dispersion solution is shown in FIG. 8, FIG. 8 (c) shows that the second dispersion solution is not modified, and FIG. 8 (d) shows that the nanomaterial dispersion obtained by the preparation method of this example has poor dispersion and does not have the corresponding conditions for preparing an acrylic-based composite material as a nanoreinforcement.
Example 3
Preparing a nano composite reinforced solution, a first mixed suspension, a second mixed suspension and LaCl 3 、NH 4 The concentration weight percentages of Cl, DEA, EDTA ammonia water solution and ethanol solution are respectively: 0.1%, 0.5%, 1.5%, 0.15%, 0.3%, 15%, 83.05%, weighing and compounding, mixing the above raw materials, and magnetically stirring at constant temperature at 60 deg.C for 2 hr to obtain suspension solution, wherein the concentration of sodium hydroxide solution is as follows0.5mol/L, the concentration of the ethanol saturated solution of adipic acid is 6.9g/100mL (25 ℃), the first mixed suspension is activated by an acidic solvent, an active functional layer is coated on the surfaces of zirconia ceramic particles, the particle size of the ceramic particles is 20-40 nm, the purity is 99wt%, and the dispersion concentration of the ethanol saturated solution of adipic acid and the nano ceramic particles is controlled to be 3g/40mL (25 ℃).
Preparing an ethanol saturated solution of adipic acid, comprising the following steps of accurately weighing 6.9g of adipic acid crystal components and 100mL of ethanol, fully mixing the raw materials, stirring at normal temperature until the raw materials are completely dissolved, and observing the transparency degree of the solution; accurately weighing 40mL of the ethanol saturated solution of the product adipic acid, accurately weighing 3g of nano zirconia powder, and carrying out magnetic stirring at constant temperature of 85 ℃ for 2 h; placing the mixture in an ice bath for ultrasonic dispersion, and observing agglomeration to obtain a carboxylated zirconia suspension, namely a first mixed suspension;
the second mixed suspension is treated by wet ball milling, ball milling materials are NaOH solution and BNNS (boron nitride nano-sheet) powder, and the concentration of the NaOH aqueous solution is controlled to be 1mol/L; the diameter of the Boron Nitride Nanosheet (BNNS) is 0.1 to 0.4 mu m, and the purity is 98wt%; the ball milling treatment adopts inert gas protection, and the inert gas is Ar; the parameters of the ball milling treatment step comprise: adopting a vacuum planetary ball milling method, controlling the ball milling speed to be 250r/min, and controlling the ball milling ratio to be 10:1, stopping the ball milling for 45 min for 10 min, wherein the ball milling time is 24h, repeatedly washing and filtering the ball milling product with dilute hydrochloric acid, wherein the washing adopts a centrifugal mode, the working parameters of the centrifuge comprise the rotating speed of the centrifuge of 2000rpm, the centrifugal time is 1h, the washing product is calibrated by adopting a PH test paper, and the pH is repeatedly filtered by deionized water to directly keep the pH neutral; and obtaining a hydroxylated boron nitride nanosheet suspension, namely a second mixed suspension.
When the modified nanometer suspension is dried, the working parameters of the vacuum drying oven comprise: setting the temperature at 85 ℃ and the working time at 24h, and removing the residual solvent to obtain modified nano material powder for later use.
The modified nano material powder is dispersed in deionized water in advance, the concentration weight percentage of the modified zirconia powder and the concentration weight percentage of the modified boron nitride powder are controlled to be 0.1 percent and 0.5 percent respectively, the solution dispersed by the modified zirconia powder is named as a first dispersion solution, and the solution dispersed by the modified boron nitride powder is named as a second dispersion solution.
A TEM micrograph of the first dispersed solution prepared using the method of this example is shown in fig. 9, in which fig. 9 (a) is unmodified and fig. 9 (b) is modified; the TEM micrograph of the second dispersion solution is shown in fig. 9, fig. 9 (c) shows that the second dispersion solution is unmodified, and fig. 9 (d) shows that the nanomaterial dispersion obtained by the preparation method of this example is poorly dispersed, and does not have the conditions for preparing an acrylic-based composite material as a nanoreinforcement.
Example 4
Preparing a nano composite reinforced solution, a first mixed suspension, a second mixed suspension and LaCl 3 、NH 4 The concentration weight percentages of Cl, DEA, EDTA ammonia water solution and ethanol solution are respectively: 0.05 percent, 0.1 percent, 1.0 percent, 0.05 percent, 0.1 percent, 10 percent and 88.85 percent of raw materials are weighed and prepared, the raw materials are fully mixed and are stirred under the conditions of 55 ℃ and 2 hours of heat preservation to obtain a suspension solution, wherein the concentration of a sodium hydroxide solution is 2mol/L, the concentration of an ethanol saturated solution of adipic acid is 2.3g/100mL (25 ℃), the first mixed suspension is prepared by adopting an acid solvent activation mode, an active functional layer is coated on the surfaces of zirconia ceramic particles, the particle size of the ceramic particles is 20-40 nm, the purity is 99 weight percent, and the dispersion concentration between the ethanol saturated solution of adipic acid and the nano ceramic particles is controlled to be 1g/40mL (25 ℃).
The second mixed suspension is processed by wet ball milling, ball milling materials are NaOH solution and BNNS (boron nitride nano-sheet) powder, and the concentration of the NaOH aqueous solution is controlled to be 2mol/L; the sheet diameter of the Boron Nitride Nanosheet (BNNS) is 0.1 to 0.4 mu m, and the purity is 98wt%; the ball milling treatment adopts inert gas protection, and the inert gas is Ar; the parameters of the ball milling treatment step comprise: adopting a vacuum planetary ball milling method, controlling the ball milling speed to be 200r/min, and controlling the ball milling ratio to be 10:1, stopping the ball milling for 40 min for 10 min, wherein the ball milling time is 24h, repeatedly washing and filtering the ball milling product with dilute hydrochloric acid, wherein the washing adopts a centrifugal mode, the working parameters of the centrifuge comprise the rotating speed of the centrifuge of 2000rpm, the centrifugal time is 1h, the washing product is calibrated by adopting a PH test paper, and the pH is repeatedly filtered by deionized water to directly keep the pH neutral; and obtaining a hydroxylated boron nitride nanosheet suspension, namely a second mixed suspension.
When the modified nanometer suspension is dried, the working parameters of the vacuum drying oven comprise: setting the temperature at 85 ℃ and the working time at 24h, and removing the residual solvent to obtain modified nano material powder for later use.
The modified nano material powder is pre-dispersed in deionized water, the concentration weight percentage of the modified zirconia powder and the concentration weight percentage of the modified boron nitride powder are respectively controlled to be 0.05 percent and 0.1 percent, the solution dispersed by the modified zirconia powder is named as a first dispersion solution, and the solution dispersed by the modified boron nitride powder is named as a second dispersion solution.
Preparing lanthanum salt modified solution, controlling the concentration weight percentage of the lanthanum salt solution as LaCl 3 ：1.0%， NH 4 Cl:0.05%, DEA:0.1%, EDTA ammonia solution: 10%, ethanol: 88.85 percent; modifying the second mixed suspension by adopting a lanthanum salt solution, wherein the mass ratio of the lanthanum salt solution to the second mixed suspension is controlled to be 1; obtaining lanthanum salt modified boron nitride nanosheet suspension;
mixing the second dispersion solution and the lanthanum salt modified boron nitride nanosheet suspension according to two ratios of 1 to 2, respectively, to obtain two nano composite reinforced solutions, and performing centrifugal separation and drying treatment;
the TEM micrographs of the nanocomposite reinforced solution prepared in this example are shown in fig. 1 (e) and fig. 1 (g), where (e) corresponds to the ratio of 1. As can be seen from the figure, compared with FIG. 1 (f), the lamellar boron nitride nanosheets are wrapped by a large number of zirconia particles, and are distributed in a mixed manner, and the agglomeration phenomenon is serious.
The nano composite reinforced solution prepared in this example has an agglomeration phenomenon, and in this example, the dispersion stability of the nano composite reinforced solution prepared by the mixture ratio of 1 and 2 is obviously lower than that of the example 1 (the mixture ratio is 1.
Example 5
Preparing an ethanol saturated solution of adipic acid, comprising the following steps of accurately weighing 2.3g of adipic acid crystal components and 100mL of ethanol, fully mixing the raw materials, stirring at normal temperature until the raw materials are completely dissolved, and observing the transparency degree of the solution;
coating an active functional layer on the surfaces of zirconia ceramic particles in an acidic solvent activation mode, wherein the particle size of the ceramic particles is 20 to 40 nm, the purity of the ceramic particles is 99wt%, accurately measuring 40mL of an ethanol saturated solution of the product adipic acid, accurately weighing 1g of nano zirconia powder, magnetically stirring at a constant temperature of 55 ℃, and keeping the temperature for 2 hours; and placing the mixture in an ice bath for ultrasonic dispersion, observing agglomeration to obtain a carboxylated zirconia suspension, namely a first mixed suspension, and performing centrifugal separation and drying treatment on the first mixed suspension to obtain the modified zirconia powder.
When the modified nanometer suspension is dried, the working parameters of the vacuum drying oven comprise: setting the temperature at 80 ℃ and the working time at 24h, and removing the residual solvent to obtain modified nano material powder for later use.
The modified zirconia powder is pre-dispersed in deionized water, and the pre-dispersed concentration weight percentage is controlled to be 0.05 percent respectively.
Mixing the modified nano dispersion liquid and acrylic photosensitive resin according to the mixture ratio of 5; carrying out photocuring three-dimensional forming on the material by adopting an additive manufacturing technology; the preparation parameters related to photocuring stereolithography comprise: the exposure time of the bottom layer is 55 s, the exposure delay is 5 s, the single-layer exposure time is 4 s, the lifting height of the platform is 5mm, and the working rotating speed of the motor is 5 mm.s -1 The forming precision is 10 mu m;
the prepared zirconium dioxide nano composite material is subjected to tribology, thermal and mechanical property tests, each group of tests is carried out for 5 times, effective data of the tests are taken for analysis and characterization, the friction property of the nano composite material (PAR-2) prepared in the embodiment is shown in figure 3, the wear resistance is shown in figure 4 (b), the hot blood property is shown in figure 5, and the mechanical properties are shown in figures 6 and 7;
the acrylic-based nanocomposite (PAR-2) prepared in this example was tested for initial decomposition temperature (T) 5 %) was 302.98 (FIG. 5), tensile strength and modulus were 18.24MPa and 2.48GPa, respectively (FIG. 6), and flexural strength and modulus were 94.34MPa and 2.95GPa, respectively (FIG. 7). The frictional wear, thermal and mechanical properties of the acrylic-based nanocomposite prepared in the example are obviously lower than those of the acrylic-based nanocomposite prepared in the example 1, which shows that the comprehensive properties of the nanocomposite prepared in the example are obviously inferior to those of the multi-dimensional acrylic-based nanocomposite prepared in the application.
Example 6
Carrying out grinding modification treatment on the boron nitride nanosheet, specifically, carrying out wet ball milling treatment, wherein ball milling materials are NaOH aqueous solution and BNNS (boron nitride nanosheet) powder, and controlling the concentration of the NaOH aqueous solution to be 2mol/L; the diameter of the Boron Nitride Nanosheet (BNNS) is 0.1 to 0.4 mu m, and the purity is 98wt%; the ball milling treatment adopts inert gas protection, and the inert gas is Ar; the parameters of the ball milling treatment step comprise: adopting a vacuum planetary ball milling method, controlling the ball milling speed to be 200r/min, and controlling the ball milling ratio to be 10:1, stopping the ball milling for 40 min for 10 min, wherein the ball milling time is 24h, repeatedly washing and filtering the ball milling product with dilute hydrochloric acid, wherein the washing adopts a centrifugal mode, the working parameters of the centrifuge comprise the rotating speed of the centrifuge of 2000rpm, the centrifugal time is 1h, the washing product is calibrated by adopting a PH test paper, and the pH is repeatedly filtered by deionized water to directly keep the pH neutral; obtaining a hydroxylated boron nitride nanosheet suspension, namely a second mixed suspension;
drying the second mixed suspension to obtain nano modified powder for later use;
pre-dispersing the nano modified powder in deionized water, and controlling the pre-dispersing concentration to be 0.1 percent by weight;
and (3) mixing the modified nano dispersion liquid and the acrylic photosensitive resin according to the proportion of 5Mixing materials; carrying out photocuring three-dimensional forming on the material by adopting an additive manufacturing technology; the preparation parameters related to the photocuring three-dimensional forming comprise: the exposure time of the bottom layer is 55 s, the exposure delay is 5 s, the single-layer exposure time is 4 s, the lifting height of the platform is 5mm, and the working rotating speed of the motor is 5 mm.s -1 The forming precision is 10 mu m;
the prepared boron nitride nanocomposite is subjected to tribology, thermal and mechanical property tests, each group of tests is carried out for 5 times, effective data is taken for analysis and characterization, the friction property of the nanocomposite (PAR-3) prepared in the embodiment is shown in figure 3, the wear resistance is shown in figure 4 (c), the thermal property is shown in figure 5, and the mechanical property is shown in figures 6 and 7.
The initial decomposition temperature (T) of the nanocomposite (PAR-3) prepared in this example was tested 5 %) is 289.99 (FIG. 5), tensile strength and modulus are 18.74MPa and 2.50GPa (FIG. 6), respectively, and flexural strength and modulus are 95.63MPa and 2.99GPa (FIG. 7), respectively. The frictional wear, thermal and mechanical properties of the acrylic-based nanocomposite prepared in the example are obviously lower than those of the acrylic-based nanocomposite prepared in the example 1, which shows that the comprehensive properties of the composite prepared in the example are obviously lower than those of the acrylic-based nanocomposite prepared in the application.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. A method for preparing an acrylic-based nanocomposite, characterized by: comprises the following steps of (a) preparing a solution,
carrying out modification treatment on the nano zirconia ceramic particles;
grinding and modifying the boron nitride nanosheets;
preparing a lanthanum salt ethanol solution;
carrying out mixing reaction on the modified boron nitride nanosheet and a lanthanum salt ethanol solution to obtain a lanthanum salt modified boron nitride nanometer solution;
under the ice bath condition, mixing the modified zirconia ceramic particles and the lanthanum salt modified boron nitride nano solution to obtain a nano composite reinforcement solution, performing centrifugal separation and drying treatment to obtain a multi-dimensional nano reinforcement for later use;
adding the multi-dimensional nano reinforcement into acrylic photosensitive resin for mixing to obtain composite slurry, and carrying out photocuring 3D printing on the composite slurry.
2. A method for preparing an acrylic based nanocomposite as claimed in claim 1, wherein: the step of modifying the nano zirconia ceramic particles comprises,
carrying out carboxylation coating treatment on the nano zirconia ceramic particles, wherein a modification solution required in the coating treatment comprises an ethanol saturated solution of adipic acid, the mass volume ratio of the ethanol saturated solution of the adipic acid is 2.3g/100mL, and the solution after the coating treatment is a first mixed suspension;
and carrying out centrifugal separation on the first mixed suspension and drying to obtain the modified zirconia powder.
3. A method for preparing an acrylic based nanocomposite as claimed in claim 2, characterized in that: the solution used for grinding and hydroxylating the boron nitride nanosheets comprises a sodium hydroxide solution, and the solution after hydroxylating and modifying is a second mixed suspension;
and carrying out centrifugal separation on the second mixed suspension and drying to obtain the modified boron nitride powder.
4. A method for preparing an acrylic based nanocomposite as claimed in any of claims 1 to 3, characterized in that: the solution used for preparing the lanthanum salt ethanol solution comprises LaCl 3 、NH 4 Cl, DEA, EDTA ammonia solution and alcohol, laCl 3 、NH 4 Concentration weight percent of Cl, DEA, EDTA ammonia water solution and ethanolThe percentage ratio is 0.1% -2.0%, 0.05% -1.0%, 0.02% -0.4%, 5% -20% and 76.6% -94.83% respectively.
5. A method for preparing an acrylic based nanocomposite as claimed in claim 2, wherein: the mass ratio of the lanthanum salt ethanol solution to the first mixed suspension is 1 to 1.5:3.
6. a method for preparing an acrylic based nanocomposite as claimed in claim 3, wherein: the mass ratio of the first mixed suspension to the second mixed suspension is 1 to 4:2.
7. a method for preparing an acrylic based nanocomposite as claimed in claim 3, wherein: and when the first mixed suspension and the second mixed suspension are dried, working parameters of a vacuum drying oven comprise that the temperature is 70 to 85 ℃, and the working time is 16 to 24h.
8. A process for the preparation of acrylic based nanocomposites as claimed in claim 3 or 7, wherein: before adding photosensitive resin, preprocessing the multidimensional nano reinforcement, and pre-dispersing the multidimensional nano reinforcement in deionized water, wherein the pre-dispersing concentrations of the zirconium oxide powder and the boron nitride powder are 0.025-0.1% and 0.1-0.5% by weight respectively.
9. A process for preparing an acrylic-based nanocomposite as claimed in claim 3, wherein: the method for grinding the boron nitride nanosheets is wet ball milling, the ball milling rotation speed is 200-250r/min, and the ball milling ratio is 10:1, stopping the ball mill for 10 min after ball milling for 30 to 50 min, wherein the ball milling time is 16 to 24h, repeatedly centrifuging, washing and filtering a ball milling product by using dilute hydrochloric acid, and calibrating the washing product by using a pH test paper when the centrifugal washing is carried out at the rotating speed of 1800 to 2000rpm and the centrifuging time is 0.5 to 1h, and repeatedly filtering the washing product by using deionized water until the pH is neutral.
10. A method for preparing an acrylic based nanocomposite as claimed in claim 3 or 9, wherein: the concentration of the sodium hydroxide solution is 0.5-2mol/L, the sheet diameter of the boron nitride nanosheet is 0.1-0.4 mu m, and the purity is 98wt%.
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| JP2009096681A (en) * | 2007-10-18 | 2009-05-07 | Nippon Shokubai Co Ltd | Manufacturing process of zirconium oxide nanoparticle, zirconium oxide nanoparticle and composition containing zirconium oxide nanoparticle |
| JP2013144676A (en) * | 2011-12-16 | 2013-07-25 | Nippon Shokubai Co Ltd | Compound, metal oxide particles, and method for producing the same |
| US20210186822A1 (en) * | 2019-12-20 | 2021-06-24 | University Of Tabuk | Dental material containing nanosized fillers and preparation methods thereof |
| WO2021230096A1 (en) * | 2020-05-15 | 2021-11-18 | 富士フイルム株式会社 | Method for producing modified boron nitride particles, modified boron nitride particles, composition for forming heat conductive material, heat conductive material, heat conductive sheet, and device with heat conductive layer |
| WO2022107038A1 (en) * | 2020-11-18 | 2022-05-27 | 3M Innovative Properties Company | Ink composition for 3d printing, process for making a ceramic green body by 3d printing, and process for making a sintered ceramic component part |
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|---|---|---|---|---|
| JP2009096681A (en) * | 2007-10-18 | 2009-05-07 | Nippon Shokubai Co Ltd | Manufacturing process of zirconium oxide nanoparticle, zirconium oxide nanoparticle and composition containing zirconium oxide nanoparticle |
| JP2013144676A (en) * | 2011-12-16 | 2013-07-25 | Nippon Shokubai Co Ltd | Compound, metal oxide particles, and method for producing the same |
| US20210186822A1 (en) * | 2019-12-20 | 2021-06-24 | University Of Tabuk | Dental material containing nanosized fillers and preparation methods thereof |
| WO2021230096A1 (en) * | 2020-05-15 | 2021-11-18 | 富士フイルム株式会社 | Method for producing modified boron nitride particles, modified boron nitride particles, composition for forming heat conductive material, heat conductive material, heat conductive sheet, and device with heat conductive layer |
| WO2022107038A1 (en) * | 2020-11-18 | 2022-05-27 | 3M Innovative Properties Company | Ink composition for 3d printing, process for making a ceramic green body by 3d printing, and process for making a sintered ceramic component part |
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