CN110793982B - High-energy X-ray characterization method for nano crystallization kinetic process - Google Patents
High-energy X-ray characterization method for nano crystallization kinetic process Download PDFInfo
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Abstract
A high-energy X-ray characterization method for a nano crystallization kinetic process is characterized in that Fourier transform and structural function derivation are carried out on radiation data to obtain distribution density data of atoms in a nano crystal under different time conditions, a specific JMA equation is adopted for carrying out segmentation fitting to obtain an Avrami index, and accordingly crystallization kinetic analysis is carried out, so that the analysis is more accurate and reliable.
Description
Technical Field
The invention belongs to the technical field of nanocrystalline material preparation, belongs to the technical field of amorphous bodies, relates to a characterization technical method of amorphous body nanocrystalline characteristics, and particularly relates to a high-energy X-ray characterization method of a nanocrystalline dynamic process.
Background
Compared with a crystal material, the amorphous body has a long-range disordered and short-range ordered structure, has unique and excellent mechanical, physical and chemical properties such as high strength, high hardness, extremely large elastic limit at room temperature, good formability in a viscous state and the like, and has wide application prospects in the fields of military, medical equipment, sports equipment and the like. The amorphous nano crystallization is a promising process method for obtaining nano-crystalline structure materials, and the application potential and range of the amorphous are expanded to a great extent.
According to the theory of alloy crystallization kinetics, see the literature [ Ghosh, Chandrasekaran et al. Journal/Acta Metallurgica et Materialia, 1991, 39 (5): 925-]The quantitative analysis of isothermal crystallization kinetics can be described by the JMA equation: x (t) ═ 1-exp [ -k (t-t)0)n]Wherein x (t) is the volume content of the crystalline phase in the alloy after t time, t0For the induction period, associated with the non-steady state time; n is an Avrami index and is related to a crystallization mechanism and the morphology of a crystal phase; k is a thermal activation rate constant, related to nucleation and growth rate.
However, the conventional crystallization kinetic analysis method is a macroscopic and statistical description of the phase transition process, only obtains the crystal content under different crystallization conditions, does not relate to the atomic migration and diffusion law in the crystallization process, and can only study the kinetic characteristics of the crystallization nucleation period, but not accurately analyze the kinetic characteristics of the processes such as the incubation period and the like.
Therefore, a new technology capable of effectively characterizing the crystallization characteristics of the amorphous nano-crystals and describing the crystallization kinetic characteristics from a microscopic view angle, even an atomic size range, is required to be searched for so as to realize the guiding significance of kinetic research on the actual preparation and production of the nano-crystals.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the method changes the traditional method for analyzing the amorphous crystallization kinetic characteristics through thermal performance, solves the problem that the traditional thermal analysis method cannot analyze the atomic migration diffusion rule in the crystallization process, and obtains the atomic migration diffusion process, the crystal nucleus formation growth mechanism and the crystallization kinetic characteristics in the amorphous nano crystallization process by adopting a method combining a radiation analysis technology and numerical simulation, thereby representing the amorphous nano crystallization process.
The invention adopts a high-energy X-ray analysis technology to obtain ex-situ radiation experimental data in an amorphous crystallization process, and the specific method comprises the following steps: and obtaining bulk amorphous by adopting a vacuum copper mold suction casting method, and then performing ex-situ isothermal annealing treatment in a high-energy X-ray environment to obtain radiation data of ex-situ high-energy X-rays. The method comprises the steps of processing radiation data by adopting an atom distribution function to obtain a high-precision atom distribution function curve, measuring nearest neighbor Coordination Number (CN) data under corresponding experimental conditions, and carrying out numerical simulation by adopting a specific formula to obtain a corresponding crystallization kinetic curve so as to analyze amorphous crystal kinetic characteristics and an atom migration diffusion rule and mechanism of a related stage.
The specific sample preparation, detection and data analysis steps of the invention are as follows:
a. selecting an amorphous body with high amorphous forming capability as a research object, preparing a bulk amorphous body by adopting a vacuum copper mold suction casting method, and preparing a sample with phi 5 multiplied by 0.5 mm;
b. assembling a sample into a high-energy X-ray (with wavelength of about 0.01nm or less) radiation light path, connecting a heating element, and performing in-situ isothermal heat treatment on the sample at a temperature of sample crystallization temperature point TxAt 30-50 ℃ below; in the heat treatment process, taking out a sample every 5-10 min for detection to obtain the non-in-situ radiation data under the corresponding heat treatment condition, IM(2θ)；
c. And (3) correcting and calculating the numerical value of the radiation data: deducting the influence of air scattering, incoherent scattering and multiple scattering, and correcting polarization factor and absorption factor to obtain corrected radiation data IC(2 theta), then carrying out data smoothing processing, and carrying out coordinate conversion and interpolation processing on the radiation data through wave vector (Q =4 pi sin theta/lambda) to obtain corrected radiation intensity IC(Q). To IC(Q) normalization to convert to single electron scattering intensity IeIn units of single atom scattering intensity Ia(Q) is an average value to express the radiation intensity of the sample. After data processing, obtaining an interference function I (Q) of the alloy, and carrying out Fourier transform to obtain a reduced atom distribution function G (r), an atom distribution function RDF (r) and the like; calculating the nearest neighbor coordination number CN under different conditions;
d. drawing a numerical curve of CN changing along with time t, wherein the change trend of the numerical curve accords with the S curve characteristic of the crystallization kinetic theory; it can be found by analysis that there is a difference (Δ δ) between the CN and the amorphous structure of the system after the crystallization is completed, and since the CN of the crystal is a fixed value, Δ δ is also a fixed value. In addition, the CN value is calculated within a certain cut-off distance, so the CN value represents the density of atoms on the coordination sphere shell, and the larger the CN, the higher the stacking density of atoms, and vice versa. The parameter Δ δ thus represents the change in the average atomic density per unit volume after the amorphous phase has been transformed into a crystalline phase, and the value Δ δ is a constant;
e. assuming that when the annealing time of the alloy is t, the content of the crystal in the alloy is VtThen the CN of the crystalline fraction changes by Δ CNtRepresents the CN change value in the whole alloy system, and can be expressed as: Δ CNt＝VtΔ δ. Since Δ δ is a constant value, the value of Δ CN reflects the change in the crystalline content in the alloy, and thus its normalized value (Δ CN)tΔ δ) represents the change in volume fraction of crystalline phase in the alloy, and therefore can be numerically simulated using the JMA formula: i.e. Δ CNtAs function x (t), t is substituted as an argument into JMA formula ln [ ln 1/(1-x)]＝lnk+nln(t−t0) Wherein k is the thermal activation rateA rate constant; t is heat treatment time; t is t0Then represents the incubation period of the crystallization reaction; n is the Avrami index in JMA;
f. and drawing a JMA function curve according to experimental data, and performing linear fitting on different data intervals to obtain slopes of different processing stages, wherein the slope is an Avrami index n, and the parameter n is very important for researching a transformation mechanism in a crystallization process, such as analyzing nucleation and growth behavior in the crystallization process, and the like, and analyzing alloy crystallization kinetic characteristics and corresponding atom migration and diffusion rules and mechanisms in different crystallization stages by combining atom distribution function analysis.
A comparison document 1 (Chenzhenhua, Zhao Yuan, etc., Journal/Hunan university Journal (Nature science edition), 2015, 42(12): 28-32) discloses a method for determining the relation between crystallization volume fraction and crystallization time by using DSC curves at different isothermal temperatures and analyzing isothermal crystallization kinetics of amorphous alloy by using JMA equation.
Comparison 2 [ extensive Red, equal river course ] Journal/inorganic chemistry report 2015, 31(5): 892-.
The comparison document 3 (congratulatory family, Lihuiping, etc. Journal/material heat treatment science (Nature science edition), 2015, 36(10): 256-260) discloses a method for analyzing the relationship between the transition variable and the temperature in the austenite transformation process by using a physical method such as a phase transition expansion curve, and a JMA (joint growth and mass spectrometry) equation is used for analyzing, however, the expansion curve is greatly influenced by the components and the size of a sample, and the accuracy and the reliability of subsequent treatment can be influenced.
The reference 4 [ Configment. Journal/material heat treatment academic report, 2012, 33(1): 892-893] discloses a method for analyzing the crystallization temperature change of metal glass by using DTA so as to analyze the crystallization kinetic characteristics of the metal glass according to an Ozawa equation, a Kissinger equation and a JMA correction equation, however, the DTA measurement result is influenced by a plurality of factors and has poor reproducibility.
Reference 5 [ lushi red, liuqian, etc. Patent/CN102519801B, 2015.07.29] discloses a method for analyzing dynamic recrystallization kinetic characteristics of aluminum alloy by researching mechanical properties of the aluminum alloy, and represents dynamic recrystallization volume fraction by measuring strain and stress relationship, so that JMA equation is used for characterization, and the method is complex to operate.
The invention analyzes the alloy crystallization kinetic characteristics through the change of the atomic level structure, which not only reflects the statistical change rule of the crystals in the alloy crystallization process from the macroscopic view, but also directly reflects the migration and diffusion mechanism of atoms from the microscopic view, thereby solving the macroscopic and microscopic kinetic change characteristics of the crystallization process at a stroke, and being a brand new and effective crystallization kinetic analysis method. Compared with the prior art, the invention has the advantages and positive effects that: starting from the most fundamental atomic structure, the method combines the nanocrystal formation process with macroscopic production and preparation conditions, and accurately and reliably determines and analyzes the dynamic characteristics of nanocrystal formation so as to guide the production and preparation process of nanocrystal materials and achieve the purpose of practicability.
Drawings
FIG. 1 is a one-dimensional diffraction data plot.
FIG. 2 is a graph of atomic distribution density versus crystal content.
Fig. 3 is a graph of JMA fit data.
Detailed Description
Examples
The atomic percent of Zr is adopted in the test40Cu55Al5Is amorphous.
a. Selecting Zr as a nominal component40Cu55Al5(at.%) amorphous material was subjected to vacuum arc melting (repeated melting 5 times) and copper mold suction casting to obtain bulk amorphous material of phi 3X 50mm, which was then cutCutting into an alloy sample with the diameter of phi 3 multiplied by 0.5 mm;
b. placing the sample in a high-energy X-ray (wavelength of 0.01 nm) radiation light path for non-in-situ isothermal crystallization treatment at 446 deg.C for 6min to obtain non-in-situ radiation data IM(2 θ), see FIG. 1;
c. correcting and converting the obtained radiation data to obtain an interference function I (Q) of the alloy, and carrying out Fourier transform to obtain a reduced radial distribution function G (r), a radial distribution function RDF (r) and the like; calculating the nearest neighbor coordination number CN under different time conditions;
d. drawing a numerical curve of CN along with the change of time, wherein the change trend of the numerical curve accords with the S curve characteristic of the crystallization kinetic theory; calculating a delta value;
e. according to the formula Δ CNt＝VtΔ δ plotting Δ CNtThe time-dependent curve, see fig. 2, in which the data points are from experimental data for annealing every three minutes, the O position (first point) is experimental data for the as-cast amorphous sample, and the CN difference (Δ δ) before and after crystallization and the distribution intervals are identified in the graph;
f. obtaining Avrami index n through JMA formula numerical simulation, and analyzing Zr according to n value40Cu55Al5The crystallization kinetics of amorphous body at 446 deg.C, as shown in FIG. 3; and analyzing the atomic migration diffusion mechanism of different crystallization stages by combining the reduced radial distribution function G (r) and the radial distribution function RDF (r), thereby completing the analysis of amorphous crystallization kinetic characteristics.
Claims (1)
1. A method for high-energy X-ray characterization of nanocrystallization kinetics, comprising:
a. and (3) non-in-situ high-energy X-ray determination in the nano crystallization process: preparing an amorphous massive sample by using the same component alloy; performing thermal analysis in DSC to obtain the crystallization temperature T of the alloyx(ii) a At TxCarrying out isothermal crystallization treatment on the alloy below the temperature, and simultaneously carrying out ex-situ detection by adopting high-energy X rays to obtain radiation data;
b. atomic distribution function calculation: for radiation dataLine correction processing to obtain normalized coherent scattering intensity Ie(Q), obtaining a structural factor S (Q) by performing Fourier transform and structural function calculation on coherent scattering data, and finally obtaining a distribution function G (r) of atoms, thereby obtaining the distribution condition of the atoms in the structure;
c. kinetic data JMA fit: determining the quantitative relation between the coordination number CN and the time t, wherein the change trend of the quantitative relation accords with the S curve characteristic of a crystallization kinetics theory; a difference value delta is generated on a time axis of CN data before crystallization starts and after crystallization finishes, and the difference value delta is a constant value; when the annealing time is t, the crystal content in the alloy is Vt, the CN change of a crystal part is represented by a CN change value in the whole alloy system, the CN change value is represented by Vt. delta, and the change of the Vt value along with t represents the change of the volume fraction of the crystal phase in the alloy, so that the Delta CNt is taken as a function x (t), and t is taken as an independent variable and is substituted into JMA formula ln [ ln 1/(1-x) ] -lnk + nln (t-t 0), wherein k is a thermal activation rate constant; t is heat treatment time; t0 represents the incubation period of the crystallization reaction; n is the Avrami index in JMA;
d. nano crystallization kinetic characteristic analysis: and segmenting the nanocrystal forming process according to the Avrami index, analyzing the kinetic characteristics, describing the kinetic crystallization process of the nanocrystal, and forming a kinetic characteristic expression which can be directly applied to production.
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