Patent Application
20210407628
The present invention relates to the field of glass material research, and more particularly, to a method for performance prediction of a glass system.
Functional glass materials have become an essential part of modern life and are widely used in various fields including daily life, national defense construction, biological medicine, safety protection, laser weapon, laser medical treatment, etc., and play an important role in promoting development of social civilization. With the flourish of the above fields, higher requirements are put forward on research and development speeds, research and development costs and performances of the functional glass. Therefore, it is especially important to achieve efficient and low-cost research and development of the functional glass materials. However, although glass has been used for thousands of years, an essential problem on the relationship among composition, structure and performance of the glass is not fully understood yet, and the glass is still a mysterious material.
According to traditional research modes, a glass researcher roughly gives a glass formula meeting conditions firstly according to literature information and data accumulated in his or her laboratory, then fuses glass components at a high temperature to prepare the glass, tests corresponding performances of the glass, adjusts the formula according to test results, and tests repeatedly in a sequential iteration until a glass product meeting specific conditions is finally obtained. Although such mode of trial-and-error method has made multiple important achievements in the research and development of the functional glass materials, the mode has problems of insufficient understanding on a glass system structure, a long test period, high costs and a low efficiency, which seriously restrict efficient and rapid research and development of the functional glass.
The United States proposed “Materials Genome Initiative” in 2011 first, aiming at revitalizing American industry and accelerating the research and development of new materials. Subsequently, China carried out corresponding layouts actively. The material genome method is a significant leap in the research and development of the materials, and is a “propeller” for the research and development of new materials. A sequential iteration method in a traditional trial-and-error method is replaced by a high-throughput concurrent iteration method in the material genome method, and the “experience-guided experiment” is gradually changed to the “combination of theoretical prediction and test verification” in a research and development mode of the materials, so as to realize a target of “shortening a research and development cycle by half and reducing research and development costs by half” and accelerate a process of “discovery-development-production-application” of the new materials. A research concept of the material genome method is rich in contents, including modeling research, high-throughput test characterization technique, computer simulation, data mining, machine learning, artificial intelligence, etc. The proposal of the material genome method provides a brand-new research concept for the research and development of the materials, and is an innovation to the traditional trial-and-error method of the materials. However, at present, the material genome method is mainly used in fields of semiconductor materials and metal materials with relatively simple components and structures, and the material genome method is rarely used in the glass materials because of the disorder and diversity of the glass material structure.
Based on the previous researches, we have found that the structure of glass is very similar to the glassy compound in the corresponding phase diagram, and the performances of the glass can be predicted by the neighboring glassy compound. On this basis, we propose that the glassy compounds in the corresponding phase diagram of the glass are the structural genes of the glass. For a glass system with relatively complete phase diagram data, we provide a method for predicting a luminescent performance of laser glass from the perspective of a glass phase diagram, find the structural genes of the glass system by consulting a large number of literatures and searching the phase diagram database, and then predict the luminescent property of target glass by using the property of the glass genes. However, this technology has two major problems as follows. (1) Important data in the literature and the phase diagram database often undergoes the problems of inconsistent test conditions and error in a test method, and the problems are very unfavorable for judging and finding the structural genes of the glass. (2) The method is invalid for a glass system with a relatively incomplete phase diagram database. (3) The predicted performance provided by the method is single, and the predicted glass variety is single. Therefore, how to accurately and quickly predict the performance of the glass system without the phase diagram data has become a key technical problem in the field.
On this basis, it is necessary to provide a method for performance prediction of a glass system.
The present invention provides a method for performance prediction of a multiplex glass system, which includes the following steps:
determining species of atoms for structure searching according to components of the multiplex glass system;
performing structural search based on the first principle to search out compounds that can be formed by interaction between the atoms;
comparing a formation energy and a phonon spectrum of each of the compounds to obtain stable compounds;
constructing a glass structural composition diagram according to the stable compounds, microstructural units of a glassy compound adjacent to a composition point of a target glass are structural genes of the glass; and
calculating a property of the target glass according to a leverage model formula of the multiplex glass system which is P0=Σi=1nPi×Li, wherein the multiplex glass system includes n components, P0 is the property of the target glass, Pi is a property of the structural gene of the target glass, and Li is a content of the structural gene of the target glass.
The present invention provides a method for performance prediction of a binary glass system, which includes the following steps:
performing structural search based on the first principle to search out compounds that can be formed between every two atoms or among every three atoms in components of a target glass, and obtaining formation energies and phonon spectrums of the compounds by calculating;
comparing the formation energies and the phonon spectrums of the compounds respectively to obtain stable compounds;
drawing a composition triangle by taking composition atoms of the target glass as vertexes, and marking coordinates of the stable compounds in the composition triangle to obtain a binary glass system composition diagram;
finding out a composition coordinate of the target glass in the binary glass system composition diagram, microstructural units of glassy compounds corresponding to two stable compounds adjacent to the composition coordinate are structural genes of the target glass; and
calculating a property of the target glass according to a leverage model formula of the binary glass system which is P0=P1×L1+P2×L2, wherein P0 is the property of the target glass, P1 and P2 are properties of the structural genes of the target glass, and L1 and L2 are a content of the structural genes of the target glass.
In one of the embodiments, the property is at least one of a mechanical property, a magnetic property, an electrical property, a luminescent property and a thermal property.
In one of the embodiments, the property is at least one of a density, a refractive index, a fluorescence full width at half maximum, an effective line width, a absorption cross-section and a peak emission cross-section.
In one of the embodiments, performing the structural search based on the first principle calculation method is to perform high-throughput structural search calculation using a first principle structural search software.
In one of the embodiments, a local particle swarm optimization algorithm is used in the high-throughput structural search, 35 to 50 structures are calculated for each iteration, and 20 to 30 iterations are calculated in total.
In one of the embodiments, the high-throughput structural search further includes calculation of structure relaxation, a cut-off energy of the structure relaxation is 400 ev to 500 ev, and a PBE functional in a generalized gradient approximation is used as a functional.
In one of the embodiments, before performing the structural search based on the first principle calculation, the method further includes determining a number range of each atom according to the species of the atoms in the components of the target glass.
In one of the embodiments, the step of comparing the formation energies and the phonon spectrums of the compounds respectively includes:
constructing a bump map to illustrate change of formation energies of the compounds with the components, and judging thermodynamically stable compounds in the compounds according to the bump map; and
calculating phonon spectrums of the thermodynamically stable compounds, and selecting a compound that does not contain an imaginary frequency in the phonon spectrum, which is namely the stable compound.
In one of the embodiments, the target glass includes one or more of a laser glass, a optical glass, a biological glass, a nuclear technology glass, a safety glass and a ware glass.
The present invention further provides a method for performance prediction of a ternary glass system, which includes the following steps:
combining any two of three components in the target glass to obtain three binary composition systems, and performing structural search on each of the binary composition systems respectively according to the method for performance prediction of the binary glass system to obtain corresponding stable compounds in each of the binary composition systems;
combining the three components of the target glass to obtain a ternary composition system, determining a proportion of four atoms in the ternary composition system, and performing structural search based on the first principle to search out compounds that can be formed by the four atoms in the ternary composition system;
comparing formation energies and phonon spectrums of the compounds that can be formed by the four atoms in the ternary composition system with formation energies and phonon spectrums of the stable compounds in the binary composition systems to determine stable compounds in the compounds that can be formed by the four atoms in the ternary composition system;
drawing a composition triangle by taking the components in the ternary composition system as vertexes, marking coordinates of all the stable compounds in the binary composition system and all the stable compounds in the ternary composition system in the composition triangle, taking the coordinates of all the stable compounds as vertexes, and dividing a triangular region according to a minimum area principle to obtain a ternary glass system composition diagram;
finding out a composition coordinate corresponding to the target glass in the ternary glass system composition diagram, microstructural units of glassy compounds corresponding to the compounds represented by three vertexes of the triangular region where the composition coordinate is located being structural genes of the target glass; and
calculating a property of the target glass according to a leverage model formula of the ternary glass system, the leverage model formula of the ternary glass system being P0=P1×L1+P2×L2+P3×L3, wherein P0 is the property of the target glass, P1, P2 and P3 are properties of the structural genes of the target glass, and L1, L2 and L3 are contents of the structural genes of the target glass.
In one of the embodiments, the step of comparing the formation energies and the phonon spectrums of the compounds that are formed by the four atoms in the ternary composition system with the formation energies and the phonon spectrums of the stable compounds in the binary composition system includes:
constructing a bump map illustrating the formation energies of the compounds that can be formed by the four atoms in the ternary composition system which change with the components by taking the stable compounds in the binary composition system as terminal vertexes of the components, and judging the thermodynamically stable compounds according to the bump map; and
calculating phonon spectrums of the thermodynamically stable compounds, and selecting a compound that does not contain an imaginary frequency in the phonon spectrum, which is namely the stable compound.
In one of the embodiments, when no stable compound exists in the compounds that are formed by the four atoms in the ternary composition system, all the stable compounds in the binary composition system are marked in the composition triangle only.
In one of the embodiments, when the stable compound exists in the compounds that are formed by the four atoms in the ternary composition system, all the stable compounds in the binary composition system and all the stable compounds in the ternary composition system are marked in the composition triangle.
The present invention further provides a method for predicting a density of a binary glass system, which includes the following steps:
performing structural search based on the first principle to search out compounds that can be formed between every two atoms or among every three atoms in components of a target glass, and obtaining formation energies and phonon spectrums of the compounds by calculating;
comparing the formation energies and the phonon spectrums of the compounds respectively to obtain stable compounds;
drawing a composition triangle by taking composition atoms of the target glass as vertexes, and marking coordinates of the stable compounds in the composition triangle to obtain a binary glass system composition diagram;
finding out a composition coordinate of the target glass in the binary glass system composition diagram, microstructural units of glassy compounds corresponding to two stable compounds adjacent to the composition coordinate are structural genes of the target glass; and
calculating a density of the target glass according to a leverage model formula of the binary glass system which is P0=P1×L1+P2×L2, wherein P0 is the density of the target glass, P1 and P2 are densities of the structural genes of the target glass, and L1 and L2 are contents of the structural genes of the target glass in the target glass.
The present invention further provides a method for predicting a refractive index of a binary glass system, which includes the following steps:
performing structural search based on the first principle to search out compounds that can be formed between every two atoms or among every three atoms in components of a target glass, and obtaining formation energies and phonon spectrums of the compounds by calculating;
comparing the formation energies and the phonon spectrums of the compounds respectively to obtain stable compounds;
drawing a composition triangle by taking composition atoms of the target glass as vertexes, and marking coordinates of the stable compounds in the composition triangle to obtain a binary glass system composition diagram;
finding out a composition coordinate of the target glass in the binary glass system composition diagram, microstructural units of glassy compounds corresponding to two stable compounds adjacent to the composition coordinate are structural genes of the target glass; and
calculating a refractive index of the target glass according to a leverage model formula of the binary glass system, the leverage model formula of the binary glass system being P0=P1×L1+P2×L2, wherein P0 is the refractive index of the target glass, P1 and P2 are refractive indexes of the structural genes of the target glass, and L1 and L2 are contents of the structural genes of the target glass in the target glass.
The present invention further provides a method for predicting a luminescent property of a binary glass system, which includes the following steps of:
performing structural search based on the first principle to search out compounds that can be formed between every two atoms or among every three atoms in components of a target glass, and obtaining formation energies and phonon spectrums of the compounds by calculating;
comparing the formation energies and the phonon spectrums of the compounds respectively to obtain stable compounds;
drawing a composition triangle by taking composition atoms of the target glass as vertexes, and marking coordinates of the stable compounds in the composition triangle to obtain a binary glass system composition diagram;
finding out a composition coordinate of the target glass in the binary glass system composition diagram, microstructural units of glassy compounds corresponding to two stable compounds adjacent to the composition coordinate are structural genes of the target glass; and
calculating a luminescent property of the target glass according to a leverage model formula of the binary glass system, the leverage model formula of the binary glass system being P0=P1×L1+P2×L2, wherein P0 is the luminescent property of the target glass, P1 and P2 are luminescent properties of the structural genes of the target glass, and L1 and L2 are contents of the structural genes of the target glass in the target glass.
The present invention further provides a method for predicting a density of a ternary glass system, which includes the following steps:
combining any two of three components of a target glass to obtain three binary composition systems, and performing structural search on each of the binary composition systems respectively according to the method for performance prediction of the binary glass system to obtain corresponding stable compounds in each of the binary composition systems;
combining the three components of the target glass to obtain a ternary composition system, determining a proportion of four atoms in the ternary composition system, and performing structural search based on the first principle to search out compounds that can be formed by the four atoms in the ternary composition system;
comparing formation energies and phonon spectrums of the compounds that can be formed by the four atoms in the ternary composition system with formation energies and phonon spectrums of the stable compounds in the binary composition systems to determine stable compounds in the compounds that can be formed by the four atoms in the ternary composition system;
drawing a composition triangle by taking the components in the ternary composition system as vertexes, marking coordinates of all the stable compounds in the binary composition system and all the stable compounds in the ternary composition system in the composition triangle, taking the coordinates of all the stable compounds as vertexes, and dividing a triangular region according to the minimum area principle to obtain a ternary glass system composition diagram;
finding out a composition coordinate corresponding to the target glass in the ternary glass system composition diagram, microstructural units of glassy compounds corresponding to the compounds represented by three vertexes of the triangular region where the composition coordinate is located being structural genes of the target glass; and
calculating a density of the target glass according to a leverage model formula of the ternary glass system, the leverage model formula of the ternary glass system being P0=P1×L1+P2×L2+P3×L3, wherein P0 is the density of the target glass, P1, P2 and P3 are densities of the structural genes of the target glass, and L1, L2 and L3 are contents of the structural genes of the target glass in the target glass.
The present invention further provides a method for predicting a refractive index of a ternary glass system, which includes the following steps:
combining any two of three components of a target glass to obtain three binary composition systems, and performing structural search on each of the binary composition systems respectively according to the method for performance prediction of the binary glass system to obtain corresponding stable compounds in each of the binary composition systems;
combining the three components of the target glass to obtain a ternary composition system, determining a proportion of four atoms in the ternary composition system, and performing structural search based on the first principle to search out compounds that can be formed by the four atoms in the ternary composition system;
comparing formation energies and phonon spectrums of the compounds that can be formed by the four atoms in the ternary composition system with formation energies and phonon spectrums of the stable compounds in the binary composition systems to determine stable compounds in the compounds that can be formed by the four atoms in the ternary composition system;
drawing a composition triangle by taking the components in the ternary composition system as vertexes, marking coordinates of all the stable compounds in the binary composition system and all the stable compounds in the ternary composition system in the composition triangle, taking the coordinates of all the stable compounds as vertexes, and dividing a triangular region according to the minimum area principle to obtain a ternary glass system composition diagram;
finding out a composition coordinate corresponding to the target glass in the ternary glass system composition diagram, microstructural units of glassy compounds corresponding to the compounds represented by three vertexes of the triangular region where the composition coordinate is located being structural genes of the target glass; and
calculating a refractive index of the target glass according to a leverage model formula of the ternary glass system, the leverage model formula of the ternary glass system being P0=P1×L1+P2×L2+P3×L3, wherein P0 is the refractive index of the target glass, P1, P2 and P3 are refractive indexes of the structural genes of the target glass, and L1, L2 and L3 are contents of the structural genes of the target glass in the target glass.
The present invention further provides a method for predicting a luminescent property of a ternary glass system, which includes the following steps:
combining any two of three components of a target glass to obtain three binary composition systems, and performing structural search on each of the binary composition system respectively according to the method for performance prediction of the binary glass system to obtain corresponding stable compounds in each of the binary composition systems;
combining the three components of the target glass to obtain a ternary composition system, determining a proportion of four atoms in the ternary composition system, and performing structural search based on the first principle to search out compounds that can be formed by the four atoms in the ternary composition system;
comparing formation energies and phonon spectrums of the compounds that can be formed by the four atoms in the ternary composition system with formation energies and phonon spectrums of the stable compounds in the binary composition systems to determine stable compounds in the compounds that can be formed by the four atoms in the ternary composition system;
drawing a composition triangle by taking the components in the ternary composition system as vertexes, marking coordinates of all the stable compounds in the binary composition system and all the stable compounds in the ternary composition system in the composition triangle, taking the coordinates of all the stable compounds as vertexes, and dividing a triangular region according to the minimum area principle to obtain a ternary glass system composition diagram;
finding out a composition coordinate corresponding to the target glass in the ternary glass system composition diagram, microstructural units of glassy compounds corresponding to the compounds represented by three vertexes of the triangular region where the composition coordinate is located being structural genes of the target glass; and
calculating a luminescent property of the target glass according to a leverage model formula of the ternary glass system, the leverage model formula of the ternary glass system being P0=P1×L1+P2×L2+P3×L3, wherein P0 is the luminescent property of the target glass, P1, P2 and P3 are luminescent properties of the structural genes of the target glass, and L1, L2 and L3 are contents of the structural genes of the target glass in the target glass.
Compared with the prior art, the present invention has the following advantages.
(1) The present invention applies the material genome research concept to glass research, and innovatively proposes a method for researching and developing a glass material by multi-scale method, which, from an atomic level and based on the density functional theory, firstly proposes quantitative research on the properties of the glass materials realized by multi-scale method of combined atom-compound-glass structure and property from a micro level to a macro level. The structural search based on the first principle and the drawing of the composition triangle are combined to obtain the glass system composition diagram, the structural genes of the target glass are found using the glass system composition diagram, and the property of the target glass is quantitatively researched and predicted using the leverage model formula according to properties of the structural genes of the glass system, which is of great significance to the research and development of a functional glass, a special optical fiber and a fiber laser thereof.
(2) The multi-scale method proposed in the present invention is a method from a micro level to a macro level, through which rapid demand-based design of the binary, ternary and multiplex glass system materials can be realized. Compared with the traditional trial-and-error method for researching glass, the method has the advantages of a short test period, low costs, a high efficiency, etc.
(3) The present invention seeks the structural genes of the glass system from an atomic perspective according to the first principle, uses the microstructural units of the glassy compounds corresponding to two stable compounds adjacent to the composition coordinate of the target glass in the glass system composition diagram or the compounds represented by three vertexes of the triangular region where the composition coordinate is located as the structural genes of the target glass system, and predicts the property of the target glass by the found glass structural genes. Compared with a previous method of adding all oxides, the glassy compounds are closer to a real structure of a glass matrix, contain coordination polyhedron structural groups (structural genes) identical to the target glass, can reflect the structure and the property of the target glass, and can more accurately predict the density, the refractive index and the luminescent property of the target glass.
(4) According to the method for performance prediction of the glass provided by the present invention, the glass system composition diagram is drawn from the atomic perspective according to the first principle, and the structural genes of the target glass are sought using the glass system composition diagram, so that the property of the glass is predicted using the structural genes of the glass system, thus solving the problems of lack of phase diagram data and how the property of the glass is predicted for the glass system with a test error are solved, and realizing wider, accurate and efficient research and development of the glass system materials in a wider range.
To make the objectives, technical solutions, and advantages of the present invention clearer, the present invention is further described in detail hereinafter with reference to the embodiments and the accompanying drawings. It should be understood that the specific embodiments described herein are merely used to explain the present invention, but are not intended to limit the present invention.
An embodiment of the present invention provides a method for performance prediction of a multiplex glass system, which includes the following steps:
S01: determining species of atoms for structural search according to components of the multiplex glass system;
S02: performing structural search based on the first principle to search out compounds that can be formed by interaction between the atoms;
S03: comparing a formation energy and a phonon spectrum of each of the compound to obtain stable compounds;
S04: constructing a glass structural composition diagram according to the stable compounds, microstructural units of glassy compounds adjacent to a composition point of a target glass being structural genes of the glass; and
S05: calculating a property of the target glass according to a leverage model formula of the multiplex glass system, the leverage model formula of the multiplex glass system being P0=Σi=1nPi×Li, wherein the multiplex glass system has n components, P0 is the property of the target glass, Pi is a property of the structural gene of the target glass, and Li is a content of the structural gene of the target glass in the target glass.
The method for performance prediction of the multiplex glass system provided by the present invention is rapid and efficient. According to a short range order characteristic of the glass, the present invention innovatively proposes a concept of researching and developing a functional glass by multi-scale method of atom-compound-glass firstly, and predicts the property of the glass system from a micro level to a macro level, which, from an atomic level, seeks the structural genes of the glass system based on the first principle, and the property of the target glass is quantitatively researched by the structural genes of the glass system and the leverage model formula, which is of great significance to rapid, low-cost and efficient research and development of the functional glass, the special optical fiber and the fiber laser thereof.
In the present invention, the multiplex glass system is composed of a plurality of oxides, and the components are the oxides forming the multiplex glass system. The binary glass system includes two components, and the ternary glass system includes three components. For example, components of a Li2O—GeO2 binary glass system are Li2O and GeO2, and components of a BaO—La2O3.GeO2 ternary glass system are BaO, La2O3 and GeO2.
In the present invention, the compound includes a plurality of different compounds, which include compounds with different atomic compositions, and also include compounds with the same atomic composition but different structures.
An embodiment of the present invention provides a method for performance prediction of a binary glass system, which includes the following steps:
S10: performing structural search based on the first principle to search out compounds that can be formed between every two atoms or among every three atoms in components of a target glass, and obtaining formation energies and phonon spectrums of the compounds by calculating;
S20: comparing the formation energies and the phonon spectrums of the compounds respectively to obtain stable compounds;
S30: drawing a composition triangle by taking composition atoms of the target glass as vertexes, and marking coordinates of the stable compounds in the composition triangle to obtain a binary glass system composition diagram;
S40: finding out a composition coordinate of the target glass in the binary glass system composition diagram, microstructural units of glassy compounds corresponding to two stable compounds adjacent to the composition coordinate are structural genes of the target glass; and
S50: calculating a property of the target glass according to a leverage model formula of the binary glass system, the leverage model formula of the binary glass system is P0=P1×L1+P2×L2, wherein P0 is the property of the target glass, P1 and P2 are properties of the structural genes of the target glass, and L1 and L2 are contents of the structural genes of the target glass in the target glass.
The property may be at least one of a mechanical property, a magnetic property, an electrical property, a luminescent property and a thermal property. In an embodiment, the property is at least one of a density, a refractive index, a fluorescence full width at half maximum, an effective line width, an absorption cross-section and a peak emission cross-section.
The structural search based on the first principle is that the compounds that can be formed can be obtained according to properties of the atoms, which is an ab initio calculation algorithm.
In an embodiment, performing the structural search based on the first principle is to perform high-throughput structural search using the first principle structural search software, such as CALYPSO and VASP. The high-throughput structural search is performed in a concurrent mode, which is beneficial for accelerating a searching efficiency.
In an embodiment, a local particle swarm optimization algorithm is used in the high-throughput structural search, 35 to 50 structures are calculated for each iteration, and 20 to 30 iterations are calculated in total.
In an embodiment, the high-throughput structural search further includes structure relaxation calculation, a cut-off energy of the structure relaxation is 400 ev to 500 ev, and a PBE functional in a generalized gradient approximation (GGA) is used as a functional.
In an embodiment, before performing the structural search based on the first principle, the method further includes a step S00 of determining a number range of each atom for structural search according to species of the atoms in the components of the target glass.
In an embodiment, the step S20 of comparing the formation energies and the phonon spectrums of the compounds respectively includes:
S22: constructing a bump map illustrating the formation energies of the compounds obtained by calculating which change with the components, and judging thermodynamically stable compounds in the compounds according to the bump map; and
S24: calculating phonon spectrums of the thermodynamically stable compounds, and selecting a compound that does not contain an imaginary frequency (i.e. dynamically stable compound) in the phonon spectrum, which is namely the stable compound.
In the step S30, the composition triangle is a triangle drawn according to a component representation method of a multiplex phase diagram, which may also be referred to as a concentration triangle. A parallel line of each side is respectively made passing through any point in the composition triangle, and a line segment cut by the parallel line of each side of the composition triangle respectively represents a concentration or a proportion of each component at the point. The coordinates are points corresponding to a compound of a specific composition in the composition triangle. In the step S40, the composition coordinate is a point corresponding to the component of the target glass in the composition triangle.
In an embodiment, the target glass includes one or more of a laser glass, an optical glass, a biological glass, a nuclear technology glass, a safety glass and a ware glass.
An embodiment of the present invention further provides a method for performance prediction of a ternary glass system, which includes the following steps:
S100: combining any two of three components of a target glass to obtain three binary composition systems, and performing structural search on each of the binary composition systems respectively according to the method for performance prediction of a binary glass system to obtain corresponding stable compounds in each of the binary composition systems;
S200: combining the three components of the target glass to obtain a ternary composition system, determining a proportion of four atoms in the ternary composition system, and performing structural search based on the first principle to search out compounds that can be formed by the four atoms in the ternary composition system;
S300: comparing formation energies and phonon spectrums of the compounds that can be formed by the four atoms in the ternary composition system with formation energies and phonon spectrums of the stable compounds in the binary composition systems to determine stable compounds in the compounds that can be formed by the four atoms in the ternary composition system;
S400: drawing a composition triangle by taking the components in the ternary composition system as vertexes, marking coordinates of all the stable compounds in the binary composition system and all the stable compounds in the ternary composition system in the composition triangle, taking the coordinates of all the stable compounds as vertexes, and dividing a triangular region according to the minimum area principle to obtain a ternary glass system composition diagram;
S500: finding out a composition coordinate corresponding to the target glass in the ternary glass system composition diagram, microstructural units of glassy compounds corresponding to the compounds represented by three vertexes of the triangular region where the composition coordinate is located are structural genes of the target glass; and
S600: calculating a property of the target glass according to a leverage model formula of the ternary glass system, the leverage model formula of the ternary glass system being P0=P1×L1+P2×L2+P3×L3, wherein P0 is the property of the target glass, P1, P2 and P3 are properties of the structural genes of the target glass, and L1, L2 and L3 are contents of the structural genes of the target glass in the target glass.
In an embodiment, the step S300 of comparing the formation energies and the phonon spectrums of the compounds that can be formed by the four atoms in the ternary composition system with the formation energies and the phonon spectrums of the stable compounds in the binary composition system includes:
S320: constructing a bump map illustrating the formation energies of the compounds that can be formed by the four atoms in the ternary composition system which change with the components by taking the stable compounds in the binary composition system as terminal vertexes of the components, and judging the thermodynamically stable compounds according to the bump map; and
S340: calculating phonon spectrums of the thermodynamically stable compounds, and selecting a compound that does not contain an imaginary frequency in the phonon spectrum, which is namely the stable compound.
In an embodiment, when no stable compound exists in the compounds that can be formed by the four atoms in the ternary composition system, all the stable compounds in the binary composition system are marked in the composition triangle only in the step S400.
In an embodiment, when the stable compound exists in the compounds that can be formed by the four atoms in the ternary composition system, all the stable compounds in the binary composition system and all the stable compounds in the ternary composition system are marked in the composition triangle in the step S400.
According to the method for performance prediction of the glass system provided by the embodiment of the present invention, a biological gene concept and a material genome engineering research mode are used for reference to seek the structural genes of the glass system, a sequential iteration method in a traditional trial-and-error method is replaced by a high-throughput concurrent iteration method, and the “experience-guided experiment” is changed to the “combination of theoretical prediction and test verification” in a research and development mode of materials, so as to realize a target of “shortening a research and development cycle by half and reducing research and development costs by half” and accelerate a process of “discovery-development-production-application” of new materials.
The binary glass system composition diagram and the ternary glass system composition diagram reflect the glass composition, and the glass composition points can be corresponded one by one in the diagrams. In the binary glass system composition diagram and the ternary glass system composition diagram, the microstructural units of the glassy compounds corresponding to the two stable compounds adjacent to the composition coordinate of the target glass or the compounds represented by the three vertexes of the triangular region where the composition coordinate is located are the structural genes of the glass system.
The structural genes of the glass system contain a polyhedral coordination condition identical to the target glass, reflect the structure of the glass and determine the property of the glass. The composition points of the glass system can be corresponded one by one in the glass system composition diagram.
Germanate glass has attracted much attention in the field of mid-infrared fiber lasers because of having advantages such as good mid-infrared transmittance, low phonon energy, and high solubility of rare earth ions. Li2O—GeO2 and Na2O—GeO2 glass systems are researched by methods for predicting a density and a refractive index of the binary glass system provided by the present invention in the following embodiments.
Target glass was: x mol % Li2O-y mol % GeO2
A number range of each of Ge, Li and O atoms was set, wherein a number of Ge atoms ranged from 0 to 8, a number of Li atoms ranged from 0 to 8, and a number of 0 atoms ranged from 1 to 10.
According to a number ratio of every two or three atoms, structural search was performed in a first principle structural search software CALYPSO, a local particle swarm optimization algorithm was used for structure evolution, and 35 structures were generated in each iteration. Structure relaxation was performed on a structure screened out by a first principle calculation software VASP, cut-off energy was 500 ev, and a PBE functional in a generalized gradient approximation (GGA) was used as a functional. Compounds that can be formed including GeO2, Li2O.7GeO2, Li2O.4GeO2, 3Li2O.8GeO2, Li2O.2GeO2 and Li2O were obtained.
Formation energies of the compounds were also obtained.
A bump map illustrating the formation energies changed with the components was constructed based on the formation energies of the compounds, which was shown in
Phonon spectrums of the thermodynamically stable compounds were calculated, and compounds that did not contain an imaginary frequency in the phonon spectrums were selected, which were namely the stable compounds, including GeO2, Li2O.4GeO2, Li2O.2GeO2 and Li2O.
A composition triangle was drawn by taking atoms Ge, Li and O as vertexes, and coordinates of GeO2, Li2O.4GeO2, Li2O.2GeO2 and Li2O were marked in the composition triangle to obtain a Li2O—GeO2 binary glass system composition diagram as shown in
When x was 25.7 and y was 74.3, i.e., the target glass was 25.7 mol % Li2O-74.3 mol % GeO2, a composition coordinate of the target glass was found in
A density and a refractive index of the above-described target glass were calculated according to a leverage model formula of the binary glass system P0=P1×L1+P2×L2, wherein P1 was a density or a refractive index of Li2O.2GeO2, P2 was a density or a refractive index of Li2O.4GeO2, and a density and a refractive index of each glassy compound in Li2O—GeO2 and Na2O—GeO2 binary glass systems were obtained by experiments, which were shown in Table 1. L1 was a content of Li2O.2GeO2 in the target glass, L2 was a content of Li2O.4GeO2 in the target glass. L1 was 42.75 and L2 was 57.25 by calculating. The densities of Li2O.2GeO2 and Li2O.4GeO2 in the Table, i.e. P1 and P2, were substituted into the formula to obtain that P0=3.8523, and an experimental value of the density of the target glass 25.7 mol % Li2O-74.3 mol % GeO2 was 3.8612. Similarly, the refractive indexes of Li2O.4GeO2 and Li2O.2GeO2 in Table 1 were substituted into the formula as P1 and P2 to obtain that a predicted value of the refractive index of the target glass 25.7 mol % Li2O-74.3 mol % GeO2 was 1.694 by calculating.
When a series of different values of x and y were taken, predicted values of densities and predicted values of refractive indexes of Li2O—GeO2 binary glass systems with various compositions were calculated and compared with densities and refractive indexes of Li2O—GeO2 binary glass systems with corresponding compositions obtained by experiments. Results were shown in
Target glass was: x mol % Na2O-y mol % GeO2
Methods for predicting a density and a refractive index of the Na2O—GeO2 binary glass system were basically the same as those in Embodiment 1, except that the glass system was different, and a glass system composition diagram thereof was shown in
When a series of different values of x and y were taken, predicted values of densities and predicted values of refractive indexes of Na2O—GeO2 binary glass systems with various compositions were calculated and compared with densities and refractive indexes of Na2O—GeO2 binary glass systems with corresponding compositions obtained by experiments. Results were shown in
Target glass was: x mol % GeO2-y mol % BaO-z mol % La2O3 (x≥56 mol %, y≤50 mol % and z≤20 mol %)
The GeO2—BaO—La2O3 glass system is an important germanate glass matrix material. The germanate glass has attracted much attention in the field of mid-infrared fiber lasers because of having advantages such as good mid-infrared transmittance, low phonon energy, and high solubility of rare earth ions, and is an important laser glass material. The GeO2—BaO—La2O3 glass system was researched by the method for performance prediction of the ternary glass system in the following embodiment.
Any two of components GeO2, BaO and La2O3 were combined to obtain a GeO2—BaO binary composition system, a GeO2—La2O3 binary composition system and a BaO—La2O3 binary composition system. According to the steps S00 to S40, stable compounds in the GeO2—BaO binary composition system, including GeO2, BaO.4GeO2, BaO.GeO2, 2BaO.GeO2 and BaO, and stable compounds in the GeO2—La2O3 binary composition system, including La2O3 and La2O3.GeO2, were obtained respectively, and no stable compound existed in the BaO—La2O3 binary composition system.
The components GeO2, BaO and La2O3 were combined to obtain a GeO2—BaO—La2O3 ternary composition system. For the four atoms in the ternary composition system, a range of the structural search was determined to be Ge: 1-5, Ba: 1-5, La: 1-5, O: 1-10. First principle structural search software and calculation software were used to perform high-throughput structural search to search out compounds that can be formed by the atoms Ge, Ba, La and O, and calculate formation energies and phonon spectrums of the compounds.
The formation energies and the phonon spectrums of the compounds that can be formed by atoms Ge, Ba, La and O were compared with the formation energies and the phonon spectrums of GeO2, BaO.4GeO2, BaO.GeO2, 2BaO.GeO2, BaO, La2O3 and La2O3.GeO2. According to comparison results, no stable compound existed in the compounds that can be formed by the atoms Ge, Ba, La and O.
A composition triangle was drawn by taking GeO2, BaO and La2O3 as vertexes, coordinates of all the stable compounds (A: GeO2, B: BaO.4GeO2, C: BaO.GeO2, D: 2BaO.GeO2, E: BaO, F: La2O3, and G: La2O3.GeO2) were marked in the composition triangle. Using A, B, C, D, E, F, G as vertexes, a triangular region was divided according to the minimum area principle to obtain a ternary glass system composition diagram, as shown in
When x was 70, y was 20 and z was 10, i.e., a target glass 1 was 70 mol % GeO2-20 mol % BaO-10 mol % La2O3, a composition coordinate of the target glass 1 was found in
A density of the target glass above was calculated according to a leverage model formula of the ternary glass system P0=P1×L1+P2×L2+P3×L3, wherein P1 was a density of BaO.4GeO2, P2 was a density of BaO.GeO2, P3 was a density of La2O3.GeO2. A density of each glassy compound in the GeO2—BaO—La2O3 ternary glass system obtained by experiments was as shown in Table 2. It can be seen from Table 2 that P1 was 5.15 g/cm3, P2 was 5.06 g/cm3, and P3 was 5.88 g/cm3. L1 was a content of BaO.4GeO2 in the target glass, which was 66.67% by calculating, L2 was a content of BaO.GeO2 in the target glass, which was 13.33% by calculating, and L3 was a content of La2O3.GeO2 in the target glass, which was 20% by calculating. The values were substituted into the formula P0=5.15 g/cm3×66.67%+5.06 g/cm3×13.33%+5.88 g/cm3×20%=5.231 g/cm3.
When a series of different values of x, y and z were taken, predicted values of densities of GeO2—BaO—La2O3 ternary glass systems with various compositions were calculated and compared with densities of GeO2—BaO—La2O3 ternary glass systems with corresponding compositions obtained by experiments to calculate relative errors. Results were shown in Table 3. It can be seen from Table 3 that the predicted values of the glass systems calculated according to the above-described method have a relative error within 5% in comparison with experimental values, which demonstrates that the method for predicting the density of the ternary glass system is effective.
Based on the above-described method for predicting the density, refractive indexes of the GeO2—BaO—La2O3 ternary glass systems with various compositions can also be effectively predicted by replacing the density with the refractive index. The density of the glass was measured by a drainage method, and the refractive index was measured by a Metricon 2010 prism coupler.
Target glass was: x mol % GeO2-y mol % BaO-z mol % La2O3-(1-x-y-z)Tm2O3 (x≥56 mol %, y≤50 mol % and z≤20 mol %)
Tm3+ doped germanate glass, xGeO2-yBaO-zLa2O3-(1-x-y-z)Tm2O3 (x≥56 mol %, y≤50 mol % and z≤20 mol %), is an important laser glass material. A luminescent property of the Tm3+ doped xGeO2-yBaO-zLa2O3 glass was researched according to the method for performance prediction of the ternary glass system. The luminescent property is a luminescent property of 3F4→3H6 energy level transition of Tm3+ ions, including a fluorescence full width at half maximum, an effective line width and a peak emission cross-section of 3F4→3H6 transition of rare earth ion Tm3+ ions in the glass, as well as absorption cross-sections of the Tm3+ ion at 790 nm and 1610 nm.
Tm2O3 was used as a doping component, and the xGeO2-yBaO-zLa2O3-(1-x-y-z)Tm2O3 glass system was equivalent to the GeO2—BaO—La2O3 ternary glass system. An x mol % GeO2-y mol % BaO-z mol % La2O3-(1-x-y-z)Tm2O3 glass system composition diagram was obtained based on the same method in the Embodiment 3, as shown in
The luminescent property of the above-described target glass was calculated according to a leverage model formula of the ternary glass system P0=P1×L1+P2×L2+P3×L3, wherein P1 was a luminescent property of GeO2, P2 was a luminescent property of BaO.4GeO2, and P3 was a luminescent property of La2O3.GeO2; and L1 was a content of GeO2 in the target glass, which was 9.2% by calculating, L2 was a content of BaO.4GeO2 in the target glass, which was 50% by calculating, and L3 was a content of La2O3.GeO2 in the target glass, which was 40% by calculating. a luminescence property, a fluorescence full width at half maximum, an effective line width, an absorption cross-section at 790 nm, an absorption cross-section at 1610 nm, and a peak emission cross-section of each glassy compound in the Tm2O3 doped GeO2—BaO—La2O3 ternary glass system obtained by experiments were as shown in Table 4. Luminescence property data of each glassy compound in Table 4 were substituted into the formula to obtain a fluorescence full width at half maximum, an effective line width, an absorption cross-section at 790 nm, an absorption cross-section at 1610 nm, and a peak emission cross-section of the 69.2 mol % GeO2-10 mol % BaO-20 mol % La2O3-0.8 mol % Tm2O3 glass system by calculating.
Similarly, luminescence properties of x mol % GeO2-y mol % BaO-z mol % La2O3-(1-x-y-z)Tm2O3 glass systems with various compositions were calculated based on the same method when a series of different values of x, y and z were taken, and were compared with luminescence properties of glasses with corresponding compositions obtained by experiments to calculate relative errors. Results were shown in Tables 5 and Table 6. It can be seen from Table 5 and Table 6 that the predicted values of the glass systems calculated by the method above have a relative error within 11% compared with experimental values, which demonstrates that the method for predicting the luminescent property of the ternary glass system is effective.
The experimental values in Table 5 and Table 6 were obtained by experiments, glass samples prepared by fusing and cooling were ground and polished to a size of 20 mm×10 mm×1.5 mm for a spectrum test, an absorption spectrum was tested by a Perkin-ElmerL1 mbda900UV/VIS/NIR spectrophotometer, and a fluorescence spectrum was tested by a TRIAX320 fluorescence spectrometer (J-Y Company, France) under 808 pumping. A lifetime of the rare earth ions was obtained by a fluorescence intensity signal changed with time detected by an oscilloscope, and a lifetime of the fluorescence was a period of time that it took for a fluorescence intensity decayed to e−1 of the highest intensity. All the tests were performed at a room temperature. Based on the tests, a calculation formula of the effective line width was:
in the formula, Δλeff was the effective line width, Imax was a maximum light intensity in an emission spectrum, and I(λ)dλ was a product of the light intensity and a wavelength. The fluorescence full width at half maximum can be directly obtained from the emission spectrum. Based on the absorption spectrum, the absorption cross-section was calculated using a Beer-Lambert equation, and a calculation formula was:
wherein lg(I0/I) was an absorption rate (also called an optical density) in the case of a certain light wavelength, N was a concentration of the rare earth ions in the glass, and l was a thickness of the glass. A calculation formula of the peak emission cross-section was:
wherein λp was a peak wavelength, c was a speed of light in vacuum (3×108), n was a refractive index of the glass, Δλeff was the effective line width, A was a probability of radiative transition, and A is calculated by a Judd-Ofelt theory.
Methods for predicting a density and a refractive index of the Na2O—MgO—P2O5 ternary glass system were basically the same as those in Embodiment 3, except that the glass system was different. Predicted values of the glass systems have a relative error within 5% in comparison to the experimental values, which demonstrates that the methods for predicting the density and the refractive index of the ternary glass system are effective.
Methods for predicting a density and a refractive index of the TeO2—BaO—Li2O ternary glass system were basically the same as those in Embodiment 3, except that the glass system was different. Predicted values of the glass systems have a relative error within 5% in comparison to the experimental values, which demonstrates that the methods for predicting the density and the refractive index of the ternary glass system are effective.
Methods for predicting a density and a refractive index of the SiO2—B2O3—Al2O3 ternary glass system are basically the same as those in the Embodiment 3, except that the glass system is different. Predicted values of the glass systems have a relative error within 5% in comparison to the experimental values, which demonstrates that the methods for predicting the density and the refractive index of the ternary glass system are effective.
The methods for performance prediction of the binary and ternary glass systems provided by the present invention can be extended to a quaternary glass system, a quinary glass system and even a glass system with more components, such as a SiO2—B2O3—CaO—Al2O3 glass system.
All the technical features of the above-described embodiments can be arbitrarily combined. In order to simplify the description, not all possible combinations of each of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combinations of these technical features, these combinations should be considered as the scope recorded in this specification.
The above-described embodiments only express several implementations of the present invention, which are described more specifically and in details, but the embodiments cannot be understood as limiting the scope of protection of the present invention. It should be pointed out that several modifications and improvements can be made by those skilled in the art without deviating from the concept of the present invention, and all the modifications and improvements shall fall within the scope of protection of the present invention. Therefore, the scope of protection of the present invention shall be determined by the appended claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 201910566855.3 | Jun 2019 | CN | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2019/097785 | 7/25/2019 | WO | 00 |
