CN111579442A - Accurate measurement of in-situ self-generated TiB in aluminum-based composite material2Method for particle size distribution - Google Patents
Accurate measurement of in-situ self-generated TiB in aluminum-based composite material2Method for particle size distribution Download PDFInfo
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume, or surface-area of porous materials
- G01N15/02—Investigating particle size or size distribution
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/32—Polishing; Etching
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/38—Diluting, dispersing or mixing samples
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/42—Low-temperature sample treatment, e.g. cryofixation
Abstract
The invention provides a method for accurately measuring in-situ self-generated TiB in an aluminum-based composite material2A method of particle size distribution comprising the steps of: (1) drying the material surface after cleaning; (2) putting the cleaned aluminum matrix composite material into an excessive hydrochloric acid solution for reaction to obtain TiB2A particle suspension A; (3) mixing TiB2The vacuum filtration operation of the particle suspension A by using a microporous filter membrane is repeated for a plurality of times until the particle suspension A is TiB2The particle suspension B is neutral; (4) TiB obtained by vacuum filtration and cleaning2Freeze-drying the particle suspension B to obtain dry TiB2A granular powder; (5) taking TiB obtained by freeze-drying2A granular powder dispersed in deionized waterIn water, chemical dispersion and/or physical dispersion are carried out; (6) using a nanometer particle size analyzer to separate the dispersed TiB2Carrying out particle size test on the particle suspension to obtain TiB2Particle size distribution data. The in-situ self-generated TiB provided by the invention2The method for measuring the particle size distribution has the advantages of strong operability, high accuracy of measurement results and high data repeatability.
Description
Technical Field
The invention relates to the technical field of aluminum-based composite materials, in particular to a method for accurately measuring in-situ self-generated TiB in an aluminum-based composite material2Method of particle size distribution.
Background
The traditional aluminum alloy material is widely applied to industry by virtue of the characteristics of high plasticity, light weight, excellent processability and the like. The existence of the reinforcing phase in the aluminum matrix composite improves the specific strength, specific rigidity, wear resistance, fatigue resistance and high-temperature performance of the material, and further widens the application range of the material. In-situ autogenous TiB in aluminum-based composites2The particle composite material has very obvious advantages and good application scenes, which are mainly benefited from the reinforcing phase particle TiB2The performance advantage of the material and the technical advantage of the in-situ autogenous method. First, TiB is compared to other reinforcing phase particles2The aluminum alloy material has excellent performances of high hardness, high melting point, high elastic modulus, high wear resistance, low thermal expansion coefficient and the like, and can well make up for the performance defects of aluminum alloy materials. Secondly, the in-situ self-generation technology for directly generating the reinforcing phase in the aluminum melt enables a more stable bonding interface and better thermodynamic stability between the matrix material and the reinforcing phase, and the size of particles of the reinforcing phase and the distribution uniformity in the matrix are greatly improved compared with the ex-situ self-generation method.
For particle-reinforced composites, the size of the reinforcing phase particles has a very large effect on the properties of the material. However, in the case of in situ techniques, there are difficulties in characterizing the particle size of the reinforcing phase: (1) due to the 'non-uniformity' of the in-situ self-generated environment, the particle size distribution is wide, and the requirement on the size characterization technology is high; (2) because the particles formed by in-situ self-generation are in a micro-nano level, the particles have strong agglomeration tendency due to high total surface energy, and a larger size measurement result can be caused if the agglomerates are not dispersed; (3) since the particles are self-generated in situ in the matrix, interference of the matrix and other secondary phases needs to be excluded during the measurement process.
Currently directed to in situ autogenous TiB2The techniques for particle size characterization can be largely divided into two categories: firstly, manual counting statistics is carried out by utilizing a scanning electron microscope or a transmission electron microscope, and the method has poor sampling representativeness, is greatly influenced by manual factors and lacks certain statistical significance; second, the TiB in the material2And extracting the particles, and performing particle size analysis by using a nanometer particle size analyzer. However, in this method, none of the techniques reported so far have been applied to TiB obtained by extraction2The particles are dispersed and the measured size is actually TiB2Size of agglomerate (i.e. secondary particle size value), not TiB2The actual size of the particles (i.e., the primary particle size value).
Through the search of the prior art, the invention patent with the application publication number of CN 103063550A accurately measures TiB in Al-Ti-B intermediate alloy2Method of particle size distribution. First according to the TiB in the alloy2The particles have the characteristic of different chemical properties from other phases, and a certain amount of TiB in the alloy is dissolved by a strong acid method2Extracting the granules to obtain clean TiB2A suspension of particles; then, a laser particle analyzer is used for carrying out accurate size statistical analysis. In the method, TiB obtained by extraction is not subjected to2The particles are dispersed and the measured size is actually TiB2Size of aggregate, not TiB2The actual size of the particles.
Therefore, the invention can accurately measure the in-situ self-generated TiB2The method of particle size is of great importance.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a methodAccurate measurement of in-situ self-generated TiB in aluminum-based composite material2Method of particle size distribution.
The purpose of the invention is realized by the following scheme:
the invention provides a method for accurately measuring in-situ self-generated TiB in an aluminum-based composite material2A method of particle size distribution comprising the steps of:
(1) cleaning the surface of the material: in-situ self-generated TiB2Polishing the aluminum-based composite material, ultrasonically cleaning, and then drying; the step is to remove the oxide film layer which is difficult to dissolve in acid on the surface of the material and prevent the oxide film layer from being applied to the subsequent TiB2The extraction process of (2) is disturbed;
(2)TiB2particle extraction: putting the aluminum matrix composite material cleaned in the step (1) into an excessive hydrochloric acid solution for reaction to obtain TiB2A particle suspension A; since the matrix Al is dissolved in hydrochloric acid, and TiB2Is insoluble in hydrochloric acid, and can finally obtain TiB after the reaction is finished2A particle suspension A;
(3)TiB2cleaning the particles: the TiB obtained in the step (2)2Carrying out vacuum filtration operation on the particle suspension A by using a microporous filter membrane, then putting the microporous filter membrane into deionized water, and enabling TiB to pass through ultrasound2The particles enter deionized water to form TiB2Repeatedly carrying out vacuum filtration on the particle suspension B for multiple times until the suspension B is TiB2The pH of the particle suspension B was equal to 7. + -. 0.5. Since the solution obtained after the end of the reaction is very acidic (pH)<0) The solution of (1), the ion concentration in the solution is very high at this time, and the TiB of the micro-nano grade2The agglomeration of the particles will be very strong and we need to do this for TiB2Cleaning the particles;
(4)TiB2obtaining of granular powder: carrying out vacuum filtration and cleaning on the TiB obtained in the step (3)2Freeze-drying the particle suspension B to obtain dry TiB2A granular powder; when this method is used, the TiB is increased because the volume expansion is caused by the conversion of water into ice2The distance between the particles is effective to prevent the particles from being agglomerated in the drying process;
(5)TiB2and (3) dispersing the particles: taking part stepStep (4) Freeze drying the TiB2Dispersing the granular powder in deionized water to obtain TiB2Suspending the particles in a suspension C, adding TiB2The particle suspension C is chemically or physically dispersed, or TiB is added2Carrying out chemical dispersion and then physical dispersion on the particle suspension C;
(6)TiB2size distribution test of particles: using a nanometer particle size analyzer to the neutral TiB obtained in the step (5)2Carrying out particle size test on the particle suspension D to obtain TiB2Particle size distribution data.
In some embodiments, the chemical dispersion method in step (5) is: in TiB2Adding cationic surfactant into the particle suspension C to obtain TiB2Suspension of particles D, then TiB2Diluting the particle suspension D, adjusting to be neutral, and then performing particle size test; the physical dispersion method comprises the following steps: mixing TiB2And (4) carrying out particle size test on the particle suspension C after carrying out ultrasonic treatment for 5-15min by using a high-energy ultrasonic instrument. The cationic surfactant can be TiB2The particles provide electrostatic and steric hindrance, and the adjustment of the pH ensures a proper ionic concentration, TiB2The particles provide further electrostatic steric hindrance effect, and sufficient repulsion between the particles is ensured;
in some embodiments, in step (5), the method of performing chemical dispersion and then performing physical dispersion comprises: in TiB2Adding cationic surfactant into the particle suspension C to obtain TiB2Suspension of particles D, then TiB2Diluting the particle suspension D and adjusting to be neutral, and adding TiB2And (4) carrying out particle size test on the particle suspension D after carrying out ultrasonic treatment for 5-15min by using a high-energy ultrasonic instrument.
In some embodiments, in the step (2), the mass fraction of the hydrochloric acid solution is 15 to 20%, and the excess hydrochloric acid solution is 3 to 4 times of the amount of the hydrochloric acid solution theoretically required for completely reacting with pure aluminum in the aluminum-based composite material.
In some embodiments, in the step (2), the later stage of the reaction of the aluminum-based composite material with the hydrochloric acid solution is performed alternately by magnetic stirring and ultrasonic operation until the Al particles are completely dissolved.
In some embodiments, in step (3), the microfiltration membrane is a strong acid resistant polytetrafluoroethylene microfiltration membrane with a pore size of 0.1 micron, and the filtration step is performed in a manner that multiple filtration membranes are overlapped to reduce particle loss caused by the filtration step.
In some embodiments, in step (5), the cationic surfactant is: cetyl trimethylammonium bromide, a polyetherimide having a weight average molecular weight of 10000 or a polyetherimide having a weight average molecular weight of 1800.
In some embodiments, in step (5), when the cationic surfactant added is cetyltrimethylammonium bromide, the cetyltrimethylammonium bromide is reacted with TiB2The mass ratio of the granular powder is mCTAB/m TiB21/30-1/10; preferably mCTAB/m TiB21/30-1/15 (optimal concentration range); most preferably mCTAB/m TiB21/30 (optimal point).
In some embodiments, when the cationic surfactant added is a polyetherimide having a weight average molecular weight of 10000, m isPEI/m TiB21/30-1/6; preferably mPEI/m TiB21/30-2/15, more preferably mPEI/m TiB21/30-1/10 (optimal concentration range); most preferably mPEI/m TiB21/15 (optimal point).
When the cationic surfactant added is a polyetherimide having a weight average molecular weight of 1800, mPEI/m TiB21/30-1/6; preferably mPEI/m TiB21/30-2/15, more preferably mPEI/m TiB21/30-1/10 (optimal concentration range); most preferably mPEI/m TiB21/30 (optimal point).
In some embodiments, in step (5), the TiB2The concentration of the diluted pellet suspension D was 0.1 mg/mL.
In some embodiments, in step (1), the aluminum-based composite material is sanded until the surface of the material is bright, then the surface of the material is cleaned by ultrasonic means sequentially with water and alcohol, and finally the surface of the material is dried by blowing air.
In some embodiments, the methods provided herein are very operable at each detection step, as compared to the prior art. In some embodiments, the freeze-drying technology is adopted to inhibit the generation of agglomeration in the drying process, and the chemical dispersion and the physical dispersion are combined to ensure that the particles have good dispersibility in the aqueous solution, and the test result has high accuracy. The currently reported method for measuring TiB by using a nanometer particle size analyzer2The particle size distribution technology does not perform good dispersion on the particles, the measured size is actually the size of the aggregate, and the accuracy of the measurement result is not high. In some embodiments, the data repeatability is high, the influence of external factors such as environment and human factors on the whole test flow is small, and the interference on the test result is small. In some embodiments, a nanometer particle size analyzer is used to test particles up to 10 particles per second3Has strong statistical significance. In the traditional method, the particle size statistics is carried out by adopting a scanning electron microscope or a transmission electron microscope, so that the total amount of samples is small, the samples are influenced by human factors, and the statistical significance is not high.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is an in situ autogenous TiB in some embodiments of the invention2A flow chart of a method for measuring particle size distribution;
FIG. 2 shows TiB under chemical dispersion conditions at different concentrations of polyetherimide (weight average molecular weight 10000) in some examples of the invention2The size distribution profile of the particles;
FIG. 3 shows TiB under chemical dispersion conditions at various concentrations of polyetherimide (weight average molecular weight of 1800) in some embodiments of the invention2The size distribution profile of the particles;
FIG. 4 shows TiB under chemical dispersion conditions of varying concentrations of cetyltrimethylammonium bromide (weight average molecular weight 364.45) in some embodiments of the invention2The size distribution profile of the particles;
FIG. 5 shows TiB obtained in example 4-1 of the present invention2The size distribution profile of the particles;
FIG. 6 illustrates TiB at different times of high-energy ultrasound in some embodiments of the present invention2The size distribution profile of the particles;
FIG. 7 is a graph of TiB at various high energy sonication times without the addition of surfactant, in accordance with certain embodiments of the present invention2Size distribution of the particles.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit of the invention. All falling within the scope of the present invention.
The invention mainly aims to solve the problem of testing TiB by using a nanometer particle size analyzer2At the particle size, due to TiB2The problem of large particle measurement size caused by particle agglomeration is solved, and the in-situ self-generated TiB with simple operation, strong repeatability and high precision is provided2Means for measuring particle size distribution.
The specific method comprises the following steps:
(1) cleaning the surface of the material: taking a certain mass of in-situ self-generated TiB2The aluminum-based composite material is polished by abrasive paper until the surface of the material is bright, the surface of the material is cleaned by water and alcohol in an ultrasonic cleaning machine in sequence, and finally the surface of the material is dried by blowing. The step is to remove the oxide film layer which is difficult to dissolve in acid on the surface of the material and prevent the oxide film layer from being applied to the subsequent TiB2The extraction process of (a) is disturbed.
(2) And (3) strong acid extraction: and (2) preparing an excess hydrochloric acid solution with the mass fraction of 15-20% (the hydrochloric acid amount is 3-4 times of the theoretical complete reaction amount) in a beaker, and slightly putting the composite material cleaned in the step (1) into the hydrochloric acid solution. Since the matrix Al is dissolved in hydrochloric acid, and TiB2Is insoluble in hydrochloric acid, and can finally obtain TiB after the reaction is finished2A particle suspension A; because the reaction is rapidly exothermic in the initial stage and the reaction speed is high,and the reaction speed is slow in the later reaction period, so that the magnetic stirring technology and the ultrasonic technology are introduced at the same time in the later reaction period, for example, the solution is stirred for 10min by magnetic force, then the beaker is placed in an ultrasonic cleaning machine for ultrasonic treatment for 5min, and the steps are carried out alternately until the Al particles are completely dissolved.
The introduction of the magnetic stirring technology can accelerate the convection of the solution in the beaker and accelerate the dissolution reaction of the Al matrix; meanwhile, the ultrasonic technology can effectively prevent TiB2The particles adhere to the undissolved Al particles; the alternation of the magnetic stirring technology and the ultrasonic technology can effectively shorten the TiB2The extraction time of (1).
(3)TiB2Cleaning the particles: and (3) carrying out vacuum filtration on the suspension A obtained in the step (2), wherein the filter membrane is a strong acid resistant polytetrafluoroethylene microporous filter membrane with the pore diameter of 0.1 micron, and the particle loss caused by the filtration can be reduced as much as possible by adopting a mode of overlapping a plurality of filter membranes during the filtration. After the first suction filtration is finished, TiB2Entrapping all the particles on the filter membrane, placing the filter membrane in a beaker, adding deionized water to submerge the filter membrane, placing the beaker in an ultrasonic cleaning machine, and placing TiB2And ultrasonically returning the particles into the water solution to obtain suspension B. The above-mentioned suction washing process was repeated again until the pH of suspension B became equal to about 7. Since the solution obtained after the end of the reaction is very acidic (pH)<0) The solution of (1), the ion concentration in the solution is very high at this time, and the TiB of the micro-nano grade2The agglomeration of particles is strong, and therefore TiB is required for the suspension A obtained in step (2)2The particles are washed.
(4)TiB2Freeze-drying of the particles: adopting a freeze drying technology to filter, filter and clean the TiB obtained in the step (3)2Placing the particle suspension B in a freeze dryer, reducing the temperature below the freezing point to convert water in the suspension B into ice, sublimating the ice under the vacuum condition, and finally obtaining dry TiB2And (3) granular powder. The TiB is dried in vacuum or common way in the traditional technical means2Drying the particle suspension to form TiB2Granular powders, which are highly susceptible to cause TiB2And (4) agglomeration of the particles. The freeze drying method adopted by the invention is characterized in that water is converted into waterThe ice causes a volume expansion, thereby increasing the TiB2The distance between the particles is effective to prevent the particles from agglomerating during the drying process.
(5)TiB2Chemical dispersion of particles: taking a certain amount of TiB after freeze drying in the step (4)2The particle powder is ultrasonically dispersed in deionized water to prepare TiB2Suspension of particles C to TiB2Dripping a certain amount of cationic surfactant into the particle suspension C to obtain TiB2Suspending the particle suspension D, and adding the TiB into deionized water2Diluting the suspension D to 0.1mg/mL (the concentration is the optimum concentration for analyzing the particle size with a nanometer particle size analyzer), adjusting the pH of the suspension D to 7 + -0.5 with hydrochloric acid and sodium hydroxide, wherein the cationic surfactant is selected from ① polyetherimide (PEI, weight average molecular weight: 10000), and adding mPEI/m TiB21/30-1/10 (the minimum peak position is less than 100nm), ② polyetherimide (PEI, weight average molecular weight is 1800), and the addition concentration mPEI/m TiB21/30-1/15 (the minimum peak position is less than 100nm), ③ cetyl trimethyl ammonium bromide (CTAB, weight average molecular weight is 364.45), and the addition concentration is mCTAB/m TiB21/30-1/15 (the minimum size peak position is less than 100 nm). Here, the cationic surfactant may be TiB2The particles provide electrostatic and steric hindrance, and the adjustment of the pH ensures a proper ionic concentration, TiB2The particles provide a further electrostatic steric hindrance effect ensuring sufficient repulsion between the particles. Cationic surfactants are chosen mainly because of their electrostatic steric hindrance effect on particle dispersion: for TiB2Particles, which are negatively charged in solution over a wide range of pH, are more attractive to cationic surfactants and therefore disperse better than other anionic surfactants or neutral dispersants.
(6)TiB2Physical dispersion of the particles: carrying out ultrasound on the suspension D obtained in the step (5) by using a high-energy ultrasonic instrument, wherein the ultrasound time is 5-15min (optimal ultrasound time range). The ultrasonic cavitation generated by the high-energy ultrasonic instrument can effectively break the formed TiB2And (4) agglomeration of the particles.
(7)TiB2Size distribution test of particles: the suspension D obtained in the step is subjected to particle size test by using a nano particle size analyzer, and TiB with reliable result can be obtained2Particle size distribution information.
Next, the method of the present invention will be described in further detail with reference to specific examples.
Examples 1 to 1
The experimental procedure was carried out according to line two of the flow chart shown in fig. 1.
(1) Taking a small block of in-situ self-generated TiB with the mass of 4g and the volume fraction of the enhanced phase of 5 percent2Polishing the surface of the aluminum-based composite material by using sand paper until the surface is smooth, sequentially washing the aluminum-based composite material by using water and alcohol, and drying the aluminum-based composite material by using a blower;
(2) preparing 100mL of 20% hydrochloric acid solution in a beaker, slightly putting the composite material obtained by cleaning in the step (1) into the beaker, introducing magnetic stirring when the reaction speed is obviously reduced, carrying out ultrasonic treatment for 5min by an ultrasonic cleaning machine every 20min, and obtaining TiB after the reaction is completely finished2An acidic suspension a of particles.
(3) TiB cleaning method by vacuum filtration2Particles 3 times, TiB left on the filter after suction filtration2Ultrasonically dispersing the particles in 50ml of deionized water by using an ultrasonic cleaning machine;
(4) the TiB obtained in the step (3)2Subpackaging the particle deionized water suspension B in 4 plastic beakers, and putting the beakers into a freeze dryer to dry for 24 hours to obtain pure TiB2A granular powder;
(5) the TiB obtained in the step (4) is treated2The particle powder is prepared into 3mg/mL suspension C by deionized water, and is dispersed by using a common ultrasonic cleaning machine (Beijing Kexi Shiji, model 1730L, power 120W) for 20min by ultrasonic. 1mL of a PEI (weight average molecular weight 10000) solution (m in this case) having a concentration of 0.3mg/mL was added dropwise to 1mL of the suspension CPEI/m TiB21/10), adding 28mL of deionized water to obtain a suspension D of 0.1mg/mL, and adding saltAdjusting the pH value to 7 by acid and sodium hydroxide;
(6) carrying out TiB on the suspension D obtained in the step (5) by using a nano-particle size analyzer2And (4) detecting the particle size distribution.
Examples 1 to 2
Example 1-2 is a modification of example 1-1 except that 1mL of a solution of PEI (weight average molecular weight 10000) having a concentration of 0.1mg/mL was added dropwise in step (5) (in this case, m isPEI/m TiB21/30), and the other steps are the same as in example 1-1.
Examples 1 to 3
Example 1-3 is a modification of example 1-1 except that 1mL of a solution of PEI (weight average molecular weight 10000) having a concentration of 0.2mg/mL (in this case m is 10000) is added dropwise in step (5)PEI/m TiB21/15), and the other steps are the same as in example 1-1.
Examples 1 to 4
Examples 1 to 4 are variations of example 1 to 1 except that 1mL of a solution of PEI (weight average molecular weight 10000) having a concentration of 0.4mg/mL (in this case m is 10000) is added dropwise in step (5)PEI/m TiB22/15), and the other steps are the same as in example 1-1.
Examples 1 to 5
Examples 1 to 5 are variations of example 1 to 1 except that 1mL of a solution of PEI (weight average molecular weight 10000) having a concentration of 0.5mg/mL was added dropwise in step (5) (in this case, m isPEI/m TiB21/6), and the other steps are the same as in example 1-1.
Comparative example 1
In comparative example 1, no surfactant was added, and the other conditions were the same as in example 1-1.
TiB at different surfactant concentrations in examples 1-1 to 1-52The particle size distribution diagram is shown in fig. 2, and the specific size distribution information is shown in table 1 below.
TABLE 1 TiB at different concentrations of PEI (weight average molecular weight 10000)2Information on the size distribution of the particles
Combining the data of FIG. 2 and Table 1, it can be seen that the concentration m for a PEI surfactant with a weight average molecular weight of 10000PEI/m TiB21/30, 1/15 or 1/10, the peaks of small-size peaks are all located at 100nm or less, and an effective dispersing effect is obtained, wherein the concentration m isPEI/m TiB21/15 has the best dispersion effect.
Example 2-1
Example 2-1 is a modification of example 1-1 except that 1mL of a PEI (weight average molecular weight 1800) solution with a concentration of 0.1mg/mL (in this case m is 1800) is added dropwise in step (5)PEI/m TiB21/30), and the other steps are the same as in example 1-1.
Examples 2 to 2
Example 2-2 is a modification of example 1-1 except that 1mL of a PEI (weight average molecular weight 1800) solution with a concentration of 0.2mg/mL (in this case m is 1800) is added dropwise in step (5)PEI/m TiB21/15), and the other steps are the same as in example 1-1.
Examples 2 to 3
Example 2-3 is a modification of example 1-1 except that 1mL of a PEI (weight average molecular weight 1800) solution with a concentration of 0.3mg/mL (in this case m is 1800) is added dropwise in step (5)PEI/m TiB21/10), and the other steps are the same as in example 1-1.
Examples 2 to 4
Example 2-4 is a modification of example 1-1 except that 1mL of a PEI (weight average molecular weight 1800) solution with a concentration of 0.4mg/mL (in this case m is 1800) is added dropwise in step (5)PEI/m TiB22/15), and the other steps are the same as in example 1-1.
Examples 2 to 5
Example 2-5 is a modification of example 1-1 except that 1mL of a PEI (weight average molecular weight 1800) solution with a concentration of 0.5mg/mL (in this case m is 1800) was added dropwise in step (5)PEI/m TiB21/6), and the other steps are the same as in example 1-1.
TiB at different surfactant concentrations2The particle size distribution diagram is shown in fig. 3, and the specific size distribution information table is shown in table 2 below.
TABLE 2 different concentrations of PEI (weight average molecule)Amount 1800) TiB2Information on the size distribution of the particles
Combining the data of FIG. 3 and Table 2, the concentration m for a PEI surfactant with a weight average molecular weight of 1800PEI/m TiB21/30 or 1/15, the peak positions of the small-size peaks are both below 100nm, and an effective dispersing effect is obtained, wherein the concentration m isPEI/m TiB21/30 has the best dispersion effect.
Example 3-1
Example 3-1 is a modification of example 1-1 except that in step (5), 1mL of a CTAB (weight average molecular weight 364.45) surfactant solution (m in this case) was added dropwise at a concentration of 0.1mg/mLCTAB/m TiB21/30), and the other steps are the same as in example 1-1.
Examples 3 to 2
Example 3-2 is a modification of example 1-1 except that 1mL of a CTAB (weight average molecular weight 364.45) surfactant solution (in this case m) having a concentration of 0.2mg/mL is added dropwise in step (5)CTAB/m TiB21/15), and the other steps are the same as in example 1-1.
Examples 3 to 3
Example 3-3 is a modification of example 1-1 except that in step (5), 1mL of a CTAB (weight average molecular weight 364.45) surfactant solution (m in this case) was added dropwise at a concentration of 0.3mg/mLCTAB/m TiB21/10), and the other steps are the same as in example 1-1.
Examples 3 to 4
Example 3-4 is a modification of example 1-1 except that in step (5), 1mL of a CTAB (weight average molecular weight 364.45) surfactant solution (m in this case) was added dropwise at a concentration of 0.4mg/mLCTAB/m TiB22/15), and the other steps are the same as in example 1-1.
Examples 3 to 5
Example 3-5 is a modification of example 1-1 except that 1mL of CTAB (heavy) with a concentration of 0.5mg/mL is added dropwise in step (5)Average molecular weight 364.45) surfactant solution (in this case mCTAB/m TiB21/6), and the other steps are the same as in example 1-1.
TiB at different surfactant concentrations2The particle size distribution chart is shown in fig. 4, and the specific size distribution information table is shown in table 3 below.
TABLE 3 TiB under CTAB conditions of different concentrations2Information on the size distribution of the particles
Combining the data in FIG. 4 and Table 3, it can be found that for CTAB surfactant, the concentration mCTAB/m TiB21/30 or 1/15 shows the most excellent dispersion effect because the peak position of the small-size peak is 100nm or less. In which the concentration mCTAB/m TiB21/30 has the best dispersion effect. When CTAB concentration m is added, the concentration is compared with the sample without dispersantCTAB/mTiB2At 1/10-1/6, the dispersibility of the particles is poor, mainly because the polymer chains of the dispersant are entangled with each other with the increase of the concentration of the dispersant, and the agglomeration tendency of the particles is increased, which results in the increase of the size characterization result.
Example 4-1
According to the line three in the flow chart shown in fig. 1:
(1) taking a small block of in-situ self-generated TiB with the mass of 4g and the volume fraction of the enhanced phase of 5 percent2Polishing the surface of the aluminum-based composite material by using sand paper until the surface is smooth, sequentially washing the aluminum-based composite material by using water and alcohol, and drying the aluminum-based composite material by using a blower;
(2) preparing 100mL of 20% hydrochloric acid solution in a beaker, slightly putting the composite material obtained by cleaning in the step (1) into the beaker, introducing magnetic stirring when the reaction speed is obviously reduced, carrying out ultrasonic treatment for 5min by an ultrasonic cleaning machine every 20min, and obtaining TiB after the reaction is completely finished2An acidic suspension a of particles.
(3) TiB cleaning method by vacuum filtration2The granules are filtered for 3 times and left after suction filtrationTiB on film2Ultrasonically dispersing the particles in 50ml of deionized water by using an ultrasonic cleaning machine;
(4) the TiB obtained in the step (3)2Subpackaging the particle deionized water suspension B in 4 plastic beakers, and putting the beakers into a freeze dryer to dry for 24 hours to obtain pure TiB2A granular powder;
(5) the TiB obtained in the step (4) is treated2Preparing the particle powder into 3mg/mL suspension C by using deionized water, and performing high-energy ultrasound on the suspension C for 10min by using a stretching high-energy ultrasonic instrument (Shanghai bio-analysis equipment, model FB-300N, power 300W);
(6) carrying out TiB on the suspension C after the high-energy ultrasonic treatment in the step (5) by using a nano-particle size analyzer2And (4) detecting the particle size distribution.
Example 4 to 2
Example 4-2 differs from example 4-1 in that high-energy sonication was used for 5min in step (5), and the remaining conditions were the same as in example 4-1.
Examples 4 to 3
Example 4-3 differs from example 4-1 in that high-energy sonication was used for 15min in step (5), and the rest of the conditions were the same as in example 4-1.
The resulting TiB2The particle size distribution diagram is shown in fig. 5, and the specific size distribution information is shown in table 4.
TABLE 4 TiB at different sonication times without addition of surfactant2Information on the size distribution of the particles
The data can be obtained by combining the data shown in fig. 5 and table 4, and the optimal dispersion effect can be achieved by high-energy ultrasound for 10 min. The dispersion effect on the particles is enhanced and then weakened along with the increase of the high-energy ultrasonic time, which is mainly because the temperature of the system is increased along with the increase of the high-energy ultrasonic time, the thermal motion of the particles is enhanced, the probability of collision among the particles is increased, and the agglomeration tendency is increased.
Example 5-1
This embodiment is the best solution of the present invention, and is performed according to the first line in the flowchart shown in fig. 1:
(1) taking a small block of in-situ self-generated TiB with the mass of 4g and the volume fraction of the enhanced phase of 5 percent2Polishing the surface of the aluminum-based composite material by using sand paper until the surface is smooth, sequentially washing the aluminum-based composite material by using water and alcohol, and drying the aluminum-based composite material by using a blower;
(2) preparing 100mL of 20% hydrochloric acid solution in a beaker, slightly putting the composite material obtained by cleaning in the step (1) into the beaker, introducing magnetic stirring when the reaction speed is obviously reduced, carrying out ultrasonic treatment for 5min by an ultrasonic cleaning machine every 20min, and obtaining TiB after the reaction is completely finished2An acidic suspension a of particles.
(3) TiB cleaning method by vacuum filtration2Particles 3 times, TiB left on the filter after suction filtration2Ultrasonically dispersing the particles in 50ml of deionized water by using an ultrasonic cleaning machine;
(4) the TiB obtained in the step (3)2Subpackaging the particle deionized water suspension B in 4 plastic beakers, and putting the beakers into a freeze dryer to dry for 24 hours to obtain pure TiB2A granular powder;
(5) the TiB obtained in the step (4) is treated2And preparing the particle powder into 3mg/mL suspension C by using deionized water, and dispersing by using a common ultrasonic cleaning machine for 20min by ultrasonic treatment. 1mL of a PEI (weight average molecular weight 10000) solution (m in this case) having a concentration of 0.3mg/mL was added dropwise to 1mL of the suspension CPEI/m TiB21/10), adding 28mL of deionized water to obtain a suspension D of 0.1mg/mL, and adjusting the pH to 7 with hydrochloric acid and sodium hydroxide;
(6) performing high-energy ultrasound on the suspension D obtained in the step (5) for 10min by using an extension-type high-energy ultrasonic instrument;
(7) carrying out TiB on the suspension D obtained after the high-energy ultrasonic treatment in the step (6) by using a nano-particle size analyzer2The size information obtained by detecting the particle size distribution is shown in FIG. 6, and TiB can be seen2The particle size exhibits a bimodal distribution with a large size peak near 292nm, a small size peak near 68nm, TiB2The number average size of the particles was 111 nm.
Examples 5 and 2
Example 5-2 is a modification of example 5-1 except that high-energy sonication was carried out for 5min in step (6), and the rest of the conditions were the same as in example 5-1.
Examples 5 to 3
Example 5-3 is a modification of example 5-1 except that high-energy ultrasound was used for 15min in step (6), and the rest of the conditions were the same as in example 5-1.
Examples 5 to 4
Example 5-4 differs from example 5-1 in that ordinary sonication was carried out for 20min in step (6), and the remaining conditions were the same as in example 5-1.
The resulting TiB2The particle size distribution diagrams are shown in (b) and (d) of fig. 7, and the specific size distribution information is shown in table 5.
TABLE 5 TiB at different sonication times2Information on the size distribution of the particles
The data in fig. 7 and table 5 are combined to obtain that the optimal dispersion effect can be achieved by high-energy ultrasound for 10min, and the reason that the effect is poor when ordinary ultrasound for 20min is compared with high-energy ultrasound is that: the power of the common ultrasonic cleaning machine is small, and compared with the work of a high-energy ultrasonic instrument which is stretched into a solution, the effect of the common ultrasonic cleaning machine on the solution is weaker.
Combining the data in tables 1-5, it can be seen that neither sonication alone nor surfactant addition alone can be used for TiB2The optimal dispersion effect is achieved. Thus, the addition of surfactant and the application of high-energy ultrasound have excellent synergistic effects, both of which are to achieve TiB2A good dispersion of the particles.
Three surfactant pairs selected by the invention2The difference in the dispersion effect of the particles is related to their molecular weight: for PEI having a weight average molecular weight of 10000, the high molecular weight provides the surfactant with greater steric hindrance for the dispersion of the particles, and thus it also has a better dispersing effect than the other two dispersants.
To sum up, this documentThe method for accurately measuring the in-situ self-generated TiB in the aluminum-based composite material2The method for particle size distribution has strong operability, high accuracy of measurement results, high data repeatability and strict statistical significance. TiB obtained by extraction is not treated by the traditional method2The particles are dispersed and the measured size is actually TiB2Size of agglomerate (i.e. secondary particle size value), not TiB2The actual size of the particles (i.e., the primary particle size value).
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.
Claims (10)
1. In-situ self-generated TiB in aluminum-based composite material is accurately measured2A method of particle size distribution, comprising the steps of:
(1) cleaning the surface of the material: in-situ self-generated TiB2Polishing the aluminum-based composite material, ultrasonically cleaning, and then drying;
(2)TiB2particle extraction: putting the aluminum matrix composite material cleaned in the step (1) into an excessive hydrochloric acid solution for reaction to obtain TiB2A particle suspension A;
(3)TiB2cleaning the particles: the TiB obtained in the step (2)2Carrying out vacuum filtration operation on the particle suspension A by using a microporous filter membrane, then putting the microporous filter membrane into deionized water, and enabling TiB to pass through ultrasound2The particles enter deionized water to form TiB2Repeatedly carrying out vacuum filtration on the particle suspension B for multiple times until the suspension B is TiB2The pH of the particle suspension B is equal to 7 +/-0.5;
(4)TiB2obtaining of granular powder: carrying out vacuum filtration and cleaning on the TiB obtained in the step (3)2Freeze-drying the particle suspension B to obtain dry TiB2A granular powder;
(5)TiB2division of the particlesPowder: taking part of TiB obtained by freeze-drying in the step (4)2Dispersing the granular powder in deionized water to obtain TiB2Suspending the particles in a suspension C, adding TiB2The particle suspension C is chemically or physically dispersed, or TiB is added2Carrying out chemical dispersion and then physical dispersion on the particle suspension C;
(6)TiB2size distribution test of particles: performing particle size test on the dispersed particle suspension obtained in the step (5) by using a nano particle size analyzer to obtain TiB2Particle size distribution data.
2. The accurate measurement of in situ self-generated TiB in aluminum matrix composites as claimed in claim 12The method for particle size distribution is characterized in that the chemical dispersing method in the step (5) is as follows: in TiB2Adding cationic surfactant into the particle suspension C to obtain TiB2Suspension of particles D, then TiB2Diluting the particle suspension D, adjusting to be neutral, and then performing particle size test; the physical dispersion method comprises the following steps: mixing TiB2And (4) carrying out particle size test on the particle suspension C after carrying out ultrasonic treatment for 5-15min by using a high-energy ultrasonic instrument.
3. The accurate measurement of in situ self-generated TiB in aluminum matrix composites as claimed in claim 12The method for particle size distribution is characterized in that in the step (5), the method for chemical dispersion and then physical dispersion comprises the following steps: in TiB2Adding cationic surfactant into the particle suspension C to obtain TiB2Suspension of particles D, then TiB2Diluting the particle suspension D and adjusting to be neutral, and adding TiB2And (4) carrying out particle size test on the particle suspension D after carrying out ultrasonic treatment for 5-15min by using a high-energy ultrasonic instrument.
4. The accurate measurement of in situ self-generated TiB in aluminum matrix composites as claimed in claim 12The method for particle size distribution is characterized in that in the step (2), the mass fraction of the hydrochloric acid solution is 15-20%, and the excessive hydrochloric acid solution is completely reacted with pure aluminum in the aluminum-based composite material theoreticallyThe amount of the hydrochloric acid solution is 3-4 times of the required amount.
5. The accurate measurement of in situ self-generated TiB in aluminum matrix composites as claimed in claim 12The method for particle size distribution is characterized in that in the step (2), the aluminum matrix composite and the hydrochloric acid solution are alternately subjected to magnetic stirring and ultrasonic operation at the later stage of the reaction until the Al particles are completely dissolved.
6. The accurate measurement of in situ self-generated TiB in aluminum matrix composites as claimed in claim 12The method for particle size distribution is characterized in that in the step (3), the microporous filter membrane is a strong acid resistant polytetrafluoroethylene microporous filter membrane with the pore diameter of 0.1 micron, and during suction filtration, a mode of overlapping a plurality of filter membranes is adopted to reduce particle loss caused by suction filtration.
7. The accurate measurement of in situ self-generated TiB in aluminum matrix composites as claimed in claim 12A method for particle size distribution, characterized in that, in step (5), the cationic surfactant is: cetyl trimethylammonium bromide, a polyetherimide having a weight average molecular weight of 10000 or a polyetherimide having a weight average molecular weight of 1800.
8. The accurate measurement of in situ self-generated TiB in aluminum matrix composites as claimed in claim 72A method for particle size distribution, characterized in that, in the step (5), when the cationic surfactant added is cetyltrimethylammonium bromide, cetyltrimethylammonium bromide is reacted with TiB2The mass ratio of the granular powder is mCTAB/mTiB2＝1/30～1/10；
When the cationic surfactant added is a polyetherimide having a weight average molecular weight of 10000, m isPEI/mTiB2＝1/30～1/6；
When the cationic surfactant added is a polyetherimide having a weight average molecular weight of 1800, mPEI/mTiB2＝1/30～1/6。
9. The accurate measurement of in situ self-generated TiB in aluminum matrix composites as claimed in claim 12A method of particle size distribution, characterized in that, in step (5), the TiB2The concentration of the diluted pellet suspension D was 0.1 mg/mL.
10. The accurate measurement of in situ self-generated TiB in aluminum matrix composites as claimed in claim 12The method for particle size distribution is characterized in that in the step (1), the aluminum-based composite material is polished by abrasive paper until the surface of the material is bright, then the surface of the material is cleaned by sequentially using water and alcohol in an ultrasonic mode, and finally the surface of the material is dried by blowing air.
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