Assessment method and classification method for activity of amorphous aluminosilicate material

Abstract

The invention relates to the technical field of inorganic new material analysis, in particular to an amorphous aluminosilicate material activity evaluation method and an amorphous aluminosilicate material activity classification method. The evaluation method comprises the following steps: preparing a plurality of single-phase amorphous aluminosilicate standard samples according to different molar ratios of Si, Al and M, and carrying out alkali excitation treatment and maintenance treatment on the amorphous aluminosilicate standard samples under the same condition to obtain a plurality of hardened samples; the microhardness of the hardened sample is detected, and mapping processing is conducted on the corresponding relation between the molar ratio of Si, Al and M of the amorphous aluminosilicate standard sample and the microhardness; selecting a plurality of positions in the to-be-evaluated amorphous aluminosilicate material to detect the molar contents of Si, Al and M, and obtaining the microhardness of each position according to the mapping processing result; performing first statistical treatment on the microhardness to obtain a distribution proportion of the microhardness; and evaluating the alkali-activated activity to be evaluated according to the distribution proportion of the microhardness in the amorphous aluminosilicate material to be evaluated.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of inorganic new material analysis, in particular to a method for evaluating and classifying amorphous silico-aluminate materials. BACKGROUND

[0002] Large industrial solid wastes not only occupy land resources and destroy the ecological environment, but also have great safety hazards. Solid wastes are typical mispositioned resources, and generally contain a certain reaction activity potential. The active components (mainly amorphous silico-aluminate) in solid wastes can react to form (Ca, Na, etc.) -Al-Si (-H) gel under the action of alkali activator, thereby having cementitious properties, and having a certain strength after curing, which can be used in the fields of construction, civil engineering, etc. Developing solid waste-based alkali-activated concrete using solid wastes as building materials is not only an important means to alleviate the shortage of building materials, but also an important way out for the sustainable development of the construction industry.

[0003] However, the solid waste building materialization faces fundamental difficulties and challenges, i.e., the complexity of solid waste components, the variety of solid waste types, and the difficulty in measuring the alkali-activated activity of solid waste. The performance of building materials prepared by alkali-activated solid waste shows great fluctuations, such as the compressive strength and flexural strength, which cannot be scaled to serve actual projects. To address this difficulty and challenge, the fundamental solution is to establish a method for quantitatively identifying, evaluating, and classifying amorphous silico-aluminate in solid waste. Traditional characterization methods mainly include X-ray diffraction, Fourier infrared change, and nuclear magnetic resonance, but all of them face the problem of interference of crystalline and amorphous signals, as well as the interference of inherent amorphous phase and newly generated amorphous products in solid waste, which cannot be effectively quantified. In addition, the current research also has obvious limitations: (1) There are significant differences in clustering methods and results in different studies; (2) The research objects are mainly fly ash, and the applicability of clustering methods and results across solid waste types is unknown; (3) There is a lack of a systematic verification framework for evaluating clustering methods and results. SUMMARY

[0004] The purpose of the present application is to provide a method for evaluating and classifying the activity of amorphous silico-aluminate materials, aiming to solve the problem of difficulty in accurately evaluating and classifying the alkali-activated activity of amorphous silico-aluminate materials in the prior art.

[0005] Another purpose of the present application is to provide a method for evaluating the activity of solid waste, aiming to solve the problem of difficulty in accurately evaluating and classifying the alkali-activated activity of solid waste in the prior art.

[0006] To achieve the above application purposes, the technical solutions adopted by the present application are as follows:

[0007] In a first aspect, the present application provides a method for evaluating the activity of amorphous silico-aluminate materials, comprising the following steps:

[0008] A plurality of single-phase amorphous silicate aluminate standard samples are prepared according to different molar ratios of Si, Al and M, and the amorphous silicate aluminate standard samples are subjected to alkali activation treatment and curing treatment under the same conditions to obtain a plurality of hardened samples; wherein M includes alkali metal elements and / or alkaline earth metal elements;

[0009] The hardened samples are detected for microhardness, and a first mapping relationship between the molar ratios of Si, Al and M of the amorphous silicate aluminate standard sample and the microhardness is obtained;

[0010] A plurality of first positions are selected in the amorphous silicate aluminate material to be evaluated, the molar contents of Si, Al and M at each first position are detected, and the microhardness at each first position is obtained according to the first mapping relationship; and then the microhardness of the amorphous silicate aluminate material to be evaluated is first statistically processed to obtain a distribution ratio of the microhardness;

[0011] The alkali activation activity of the amorphous silicate aluminate material to be evaluated is evaluated according to the distribution ratio of the microhardness of the amorphous silicate aluminate material to be evaluated.

[0012] The existing evaluation system investigates macroscopic parameters such as compressive strength, which can be affected by pores and structural defects. The evaluation method of the present application starts from the microhardness, which can more accurately reflect the true alkali activation activity of the amorphous silicate aluminate standard sample and the amorphous silicate aluminate material to be evaluated. The amorphous silicate aluminate standard sample is prepared, and the microhardness is detected after alkali activation treatment and curing treatment. After the first mapping processing, an evaluation system is established from the phase level, i.e., the mapping relationship between the molar ratio of Si, Al and M in the standard sample and the microhardness. Then, regardless of the form of the amorphous silicate aluminate material to be evaluated or the chemical formula, as long as the molar contents of Si, Al and M at multiple positions are detected, the microhardness at each position of the amorphous silicate aluminate material to be evaluated can be obtained according to the above mapping relationship, and the first statistical processing is performed to obtain the distribution ratio of the microhardness. Then, the alkali activation activity of the amorphous silicate aluminate material to be evaluated can be evaluated according to the distribution ratio. A reference can be preset for the distribution ratio of the microhardness according to the demand, and the amorphous silicate aluminate material to be evaluated with a microhardness greater than the reference can be evaluated as having higher alkali activation activity. The amorphous silicate aluminate material to be evaluated with a greater distribution ratio of microhardness can be evaluated as having higher alkali activation activity. In summary, the evaluation method of the present application has high accuracy, wide applicability and simple process.

[0013] In a second aspect, the present application provides a classification method for amorphous silicate aluminate materials, comprising the following steps:

[0014] The amorphous silicate aluminate material to be evaluated is evaluated according to the above application evaluation method, and according to the first statistical processing result, the evaluated amorphous silicate aluminate material is classified according to the distribution ratio of microhardness.

[0015] Since the above application evaluation method establishes an evaluation system for the alkali-activated activity of amorphous silicate aluminate materials, the evaluated amorphous silicate aluminate materials can be classified, and materials with similar alkali-activated activity can be classified into one category, obtaining multiple activity level categories. Therefore, the classification method of the amorphous silicate aluminate material of the application can accurately, scientifically and quickly classify the amorphous silicate aluminate material according to the alkali-activated activity, and can be used in the fields of geopolymerization reaction research and new geopolymer building material research.

[0016] In a third aspect, the application provides a solid waste activity evaluation method, comprising the following steps:

[0017] Providing a solid waste containing an amorphous silicate aluminate material, and evaluating the solid waste according to the above application evaluation method.

[0018] Since the above application evaluation method establishes an evaluation system for the alkali-activated activity of amorphous silicate aluminate materials, it can be used for the activity evaluation of solid waste rich in amorphous silicate aluminate materials. Compared with the prior art evaluation method, the solid waste activity evaluation method is more accurate, and can also be used for evaluation and comparison across solid waste types, so that the solid waste resources can be scientifically evaluated, which is conducive to the further rational use of solid waste resources. BRIEF DESCRIPTION OF DRAWINGS

[0019] In order to more clearly illustrate the technical solutions in the embodiments of the application, the following will briefly introduce the drawings needed to be used in the embodiments or prior art description. Obviously, the drawings in the following description are only some embodiments of the application, and other drawings can also be obtained by those skilled in the art without creative labor.

[0020] Figure 1 is a BSE image in step S1 of embodiment A1 of the application;

[0021] Figure 2 is a probability statistical diagram of the occurrence of different molar ratios of (Si+Al) / Ca in step S3 of embodiment A1 of the application;

[0022] Figure 3 is a probability statistical diagram of the occurrence of different molar ratios of Si / Al in step S3 of embodiment A1 of the application;

[0023] Figure 4 is a mapping relationship between the molar ratio of the standard sample and the microhardness of the hardened sample in step S6 of embodiment A1 of the application;

[0024] Figure 5 is a stack chart of Si, Al, Ca and other elements obtained after solid waste testing in step S7 of embodiment A1 of the present application;

[0025] Figure 5 , wherein (a) is a BSE image obtained by solid waste testing;

[0026] (b) is an element distribution chart of Si obtained by solid waste EDS testing;

[0027] (c) is an element distribution chart of Al obtained by solid waste EDS testing;

[0028] (d) is an element distribution chart of Ca obtained by solid waste EDS testing;

[0029] (e) is an element distribution chart of Fe obtained by solid waste EDS testing;

[0030] (f) is an element distribution chart of Na obtained by solid waste EDS testing;

[0031] (g) is an element distribution chart of K obtained by solid waste EDS testing;

[0032] (h) is an element distribution chart of Mg obtained by solid waste EDS testing;

[0033] (i) is a percentage diagram of total atoms of each element obtained by solid waste EDS testing;

[0034] Figure 6 is a statistical result diagram of the proportion of microhardness size distribution in the first fly ash in step S8 of embodiment A1 of the present application;

[0035] Figure 7 is a statistical result diagram of the proportion of microhardness size distribution in the second fly ash in step S8 of embodiment A2 of the present application;

[0036] Figure 8 is a statistical result diagram of the proportion of microhardness size distribution in the third fly ash in step S8 of embodiment A3 of the present application;

[0037] Figure 9 is a statistical result diagram of the proportion of microhardness size distribution in the fourth fly ash in step S8 of embodiment A4 of the present application;

[0038] Figure 10 is a statistical result diagram of the proportion of microhardness size distribution in the granulated blast furnace slag in step S8 of embodiment A5 of the present application;

[0039] Figure 11 is a statistical result diagram of the proportion of microhardness size distribution in the circulating fluidized bed ash in step S8 of embodiment A6 of the present application. DETAILED DESCRIPTION

[0040] In order to make the technical problems, technical solutions and beneficial effects of the present application clearer, the present application will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are only intended to explain the present application and not to limit the present application.

[0041] In the present application, the term "and / or" describes the association relationship of the associated objects, which means that there can be three kinds of relationships, for example, A and / or B can mean that A exists alone, A and B exist together, and B exists alone. Wherein A and B can be singular or plural. The character " / " generally represents that the front and rear associated objects are in an "or" relationship.

[0042] In the present application, "at least one" means one or more, and "multiple" means two or more. "At least one" or similar expressions mean any combination of these items, including any combination of single item or multiple items.

[0043] It should be understood that in various embodiments of the present application, the size of the sequence number of the above processes does not mean the order of execution, and part or all of the steps can be executed in parallel or in sequence, and the execution order of the processes should be determined according to its function and inherent logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.

[0044] The terms "first", "second" are only for descriptive purposes and are used to distinguish objects such as substances from each other, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. For example, without departing from the scope of the embodiments of the present application, the first certain something can also be called the second certain something, and similarly, the second certain something can also be called the first certain something. Therefore, the features limited by "first" and "second" can explicitly or implicitly include one or more of the features.

[0045] For alkali-activated activity, the solid waste generally contains active ingredients and inert ingredients. The active ingredients are amorphous silicate materials (active silicate materials, amorphous silicate materials), and the inert ingredients are often crystalline silicate materials and other chemical substances. The amorphous silicate materials in the solid waste are often in the form of composite materials or mixtures of multiple silicate substances. The amorphous silicate materials described in the present application can be in the above two forms or a certain amorphous silicate substance, and the alkali-activated activity thereof can be accurately and effectively evaluated and classified. Compared with the rough classification method of the prior art, the present application proposes a method and idea of constructing an evaluation system for the alkali-activated activity of amorphous silicate materials from the phase level.

[0046] The computer technology processing involved in the specification includes basic operations such as four arithmetic operations, set mapping processing, and numerical occurrence ratio, and can be processed by using computer technology due to large data volume, which is clear and realizable for those skilled in the art. The specification also involves statistical processing, and those skilled in the art know that the more samples collected by statistical processing, the more accurate the statistical processing result, or in other words, the more representative the result.

[0047] The first aspect of the embodiment of the present application provides a method for evaluating the activity of amorphous silicate aluminate material, comprising the following steps S10-S40:

[0048] S10: A plurality of single-phase amorphous silicate aluminate standard samples are prepared according to different molar ratios of Si, Al and M, and the amorphous silicate aluminate standard samples are subjected to alkali activation treatment and curing treatment under the same conditions to obtain a plurality of hardened samples; wherein M includes alkali metal elements and / or alkaline earth metal elements;

[0049] S20: The hardened samples are detected for microhardness, and the corresponding relationship between the molar ratio of Si, Al and M of the amorphous silicate aluminate standard sample and the microhardness is subjected to first mapping processing;

[0050] S30: A plurality of first positions are selected in the amorphous silicate aluminate material to be evaluated, the molar content of Si, Al and M at each first position is detected, and according to the result of the first mapping processing, the microhardness of each first position is obtained; and the microhardness of the amorphous silicate aluminate material to be evaluated is subjected to first statistical processing to obtain the distribution ratio of the microhardness;

[0051] S40: The alkali activation activity of the amorphous silicate aluminate material to be evaluated is evaluated according to the distribution ratio of the microhardness in the amorphous silicate aluminate material to be evaluated.

[0052] The macroscopic parameters such as compressive strength investigated by the existing evaluation system can be affected by pores and structural defects, and the evaluation method of the embodiment of the application is changed to start from the microscopic parameter of microhardness, which can more accurately reflect the real alkali-activated activity of the amorphous silicate aluminate standard sample and the amorphous silicate aluminate material to be evaluated. First, the amorphous silicate aluminate standard sample is prepared, then the microhardness is detected after alkali-activated treatment and curing treatment, and a set of evaluation system is established from the phase level after the first mapping treatment, that is, the mapping relationship between the molar ratio of Si, Al and M in the standard sample and the size of the microhardness. Then, no matter what form the amorphous silicate aluminate material to be evaluated is or what chemical formula it is, as long as the molar content of Si, Al and M at multiple positions is detected, the microhardness at each position of the amorphous silicate aluminate material to be evaluated can be obtained according to the above mapping relationship, and the first statistical processing is performed to obtain the size distribution ratio of the microhardness, and then the alkali-activated activity of the amorphous silicate aluminate material to be evaluated can be evaluated according to the size of the distribution ratio. A reference can be preset for the size of the distribution ratio of the microhardness according to the demand, and the amorphous silicate aluminate material to be evaluated higher than the reference can be evaluated as having higher alkali-activated activity. The amorphous silicate aluminate material to be evaluated can also be compared, and the material with a larger distribution ratio of microhardness value can be evaluated as having higher alkali-activated activity. In summary, the evaluation method of the embodiment of the application has high accuracy, wide applicability and simple process.

[0053] Steps S10-S20 are steps for first establishing a set of alkali-activated activity evaluation system.

[0054] Step S10 is a step of preparing an amorphous silicate aluminate standard sample and then preparing a hardened sample. The above-mentioned amorphous silicate aluminate standard sample is a single phase, that is, M in each standard sample is an element, and the element is uniformly distributed, the molar ratio of Si, Al and M at each position is the same, and the chemical formula is consistent. Different standard samples are different from each other in the molar ratio of Si, Al and M, or the element M. In some embodiments, M includes at least one of Ca, Na and K, which can be Ca. The amorphous silicate aluminate of these elements has typical alkali-activated activity. In the demonstration example, the prepared standard sample can include amorphous silicate calcium with different molar ratios, and can also include amorphous silicate sodium and amorphous silicate potassium with different molar ratios, or a composite material. Generally, the more the number and types of prepared standard samples, the better the evaluation and analysis accuracy, and it is also beneficial to cross-type evaluation.

[0055] The "Si, Al, M molar ratio" includes two aspects: one is the type of Si, Al, M molar ratio, and the other is the numerical value of the molar ratio. First, there are various types of Si, Al, M molar ratio, such as Si / Al ratio, Si / M ratio, Al / M ratio, etc. In addition, four arithmetic operations can be performed to obtain ratios such as (Si+Al) / M ratio, (Si+M) / Al ratio, etc. Generally, the more types of standard samples, the better. Only one type of molar ratio can be investigated, or two or more types of molar ratio can be investigated. However, if various types of molar ratio are investigated blindly, the number of standard samples is too large and the time is too long. In the examples, the (Si+Al) / M ratio and the Si / Al ratio can be investigated, which are representative. Second, for statistics and evaluation, the more the numerical value of the Si, Al, M molar ratio, the better, and the more the number of standard samples, the better. However, if each molar ratio value is investigated blindly, it will take too long and it will not be able to completely cover the (0, +∞) interval, so a plurality of typical values can be selected. In some embodiments, before preparing the amorphous silicon aluminates standard sample, the following steps S11-S12 can be included:

[0056] S11: Selecting a plurality of second positions in the amorphous silicon aluminates material to be evaluated, detecting the Si, Al, M molar content of each second position, and calculating the (Si+Al) / M molar ratio of each position;

[0057] S12: The calculation results are subjected to second statistical processing to obtain the probability of the occurrence of different (Si+Al) / M molar ratios, and a plurality of raw materials with (Si+Al) / M molar ratio are selected according to the probability for preparing the amorphous silicon aluminates standard sample; and / or, the Si, Al molar content of each second position is detected, the Si / Al molar ratio of each position is calculated, the calculation results are subjected to third statistical processing to obtain the probability of the occurrence of different Si / Al molar ratios, and a plurality of raw materials with Si / Al molar ratio are selected according to the probability for preparing the amorphous silicon aluminates standard sample.

[0058] The second position selected in step S11 can be selected randomly or according to a certain rule, and the size of the space occupied by each position can be different or the same. Generally, the position is preferably random, and the smaller the size of each position and the more the total number of selected positions, the more representative they are. In step S12, the probability of the occurrence of the mole ratio is preferably selected as the typical value. In this way, the amorphous silicon aluminate material to be evaluated is first detected, and then the mole ratio value is selected according to the results of the second statistical processing and / or the third statistical processing, which is beneficial to selecting a representative mole ratio value and guiding the subsequent preparation of the standard sample step, and is beneficial to improving the efficiency and accuracy of the evaluation. Moreover, the steps of selecting the second position, detecting the mole content, and performing the second statistical processing and / or the third statistical processing can be completed once to establish the corresponding evaluation system in cooperation with the subsequent step S20.

[0059] This way of selecting a typical value is suitable for different types of solid waste, and for solid waste containing amorphous silicon aluminate materials such as fly ash, blast furnace slag, and fluidized bed ash, the evaluation can be performed across industrial solid waste types. In the example, as shown in Figure 2 When M is Ca, according to the results of the second statistical processing, the (Si+Al) / M mole ratio has a higher probability of appearing as 1, 1.5, 2.3, 4, 9, +∞, and the corresponding raw materials can be selected for the preparation of the amorphous silicon aluminate standard sample according to the above mole ratio. +∞ represents that the M element content of some second positions is extremely low, almost 0. In the example, as shown in Figure 3 When M is Ca, according to the results of the third statistical processing, the Si / Al mole ratio has a higher probability of appearing as 0.3, 0.7, 1, 1.5, 2.3, 4, +∞, and the corresponding raw materials can be selected for the preparation of the amorphous silicon aluminate standard sample according to the above mole ratio. +∞ represents that the Al element content of some second positions is extremely low, almost 0. In the example, the typical values of both the (Si+Al) / M mole ratio and the Si / Al mole ratio can also be considered, and the mole ratios are arranged and combined to prepare the amorphous silicon aluminate standard sample. In this way, one standard sample can consider the typical values of both mole ratios, further improving the representativeness of the standard sample.

[0060] In some embodiments, after the second statistical processing and the third statistical processing in step S12, the following steps S13-S14 can be performed:

[0061] S13: According to the results of the second statistical processing in step S11, the (0, +∞) set is divided into A first intervals that are mutually disjoint according to the (Si+Al) / M mole ratio, and according to the results of the third statistical processing in step S11, the (0, +∞) set is divided into B second intervals that are mutually disjoint according to the Si / Al mole ratio, A≥2, B≥2;

[0062] S14: select a number of (Si+Al) / M molar ratios for each first interval, select a number of Si / Al molar ratios for each second interval, and perform permutation and combination processing on the selected (Si+Al) / M molar ratios and Si / Al molar ratios to obtain at least AxB kinds of combinations, and prepare at least AxB amorphous silico-aluminate standard samples.

[0063] The step S13 and the step S14 further divide the (Si+Al) / M and Si / Al molar ratios into multiple intervals. The principle of division can be that the values with higher probability of occurrence are distributed in each interval, and a number of molar ratios are selected from each interval for permutation and combination processing. In this way, each interval can be considered, and the more molar ratios selected in each interval, the more the overall situation of the interval can be reflected, and the more standard samples obtained, and the higher the evaluation accuracy. At least AxB amorphous silico-aluminate standard samples can be obtained.

[0064] In some embodiments, when M is Ca and A is 6, the first intervals in step S13 are (0, 1], (1, 1.5], (1.5, 2.3], (2.3, 4], (4, 9], (9, +∞) in turn. When M is Ca, the end point values of these first intervals have higher frequency of occurrence, and dividing the (Si+Al) / M molar ratio into the above six first intervals is conducive to improving the representativeness and accuracy of the evaluation, as shown in FIG. 1. Figure 2 In some embodiments, when M is Ca and B is 7, the second intervals in step S13 are (0, 0.3], (0.3, 0.7], (0.7, 1], (1, 1.5], (1.5, 2.3], (2.3, 4], (4, +∞) in turn. When M is Ca, the end point values of these second intervals have higher frequency of occurrence, and dividing the Si / Al molar ratio into the above second intervals is conducive to improving the representativeness and accuracy of the evaluation, as shown in FIG. 2. Figure 3

[0065] The above steps S11-S14 are optional steps. These steps can be referred to to make the amorphous silico-aluminate standard samples prepared in step S10 more representative, and reduce the time required to establish the evaluation system. The above steps S11-S14 can also not be performed, and a large number of single-phase amorphous silico-aluminate standard samples with different molar ratio types and values can be directly prepared.

[0066] In some embodiments, the preparation method of the amorphous silico-aluminate standard sample can include a sol-gel method, which has good accuracy and consistency in preparing amorphous standard samples. In an exemplary embodiment, an Al salt, an M salt, and tetraethyl orthosilicate can be provided according to a molar ratio, the Al salt and the M salt can be prepared into a solution with ethanol and deionized water, the tetraethyl orthosilicate and the ethanol can be prepared into a solution, and then mixed and heated to make the sol gelate. The gel is subjected to aging treatment, drying treatment, grinding treatment, and calcination treatment to obtain a powder-like amorphous silico-aluminate standard sample.​

[0067] After the preparation of the standard sample, the step of alkali activation treatment is performed, the amorphous silicate standard sample reacts with the alkali activator, and a dissolution-polymerization reaction occurs to generate a M-Al-Si(-H) chain microstructure, which is macroscopically in the form of a gel, that is, a geopolymer. Due to the different types / amounts of alkali activators, the actual performance of the alkali activation effect is different, and the alkali activation activity of some standard samples may not be fully activated. Therefore, the same conditions need to be used for alkali activation treatment, that is, the same alkali activator is used for the standard sample, and the same mass ratio of the standard sample to the alkali activator is maintained to improve the accuracy of the evaluation. In addition, in addition to using one condition to perform alkali activation treatment on one set of standard samples, another set of standard samples can also be subjected to alkali activation treatment under other conditions of different types / amounts of alkali activators, and an evaluation system for amorphous silicate materials under different alkali activation conditions can be established to fully reflect the complete alkali activation activity of the materials.

[0068] In the embodiments, the alkali activator for alkali activation treatment can include at least one of sodium silicate, sodium hydroxide, potassium hydroxide, and sodium carbonate. Optionally, the alkali activator for alkali activation treatment includes sodium silicate, the modulus of the sodium silicate can be 1, the mass ratio of each amorphous silicate standard sample to the sodium silicate can be (0.5-1.6):1, and the sodium silicate can be a solution with a concentration of 25wt%. The range here represents an optional mass ratio, but when performing alkali activation treatment, a specific mass ratio point value needs to be selected, and each standard sample is subjected to alkali activation treatment according to the mass ratio. The selection of sodium silicate as the alkali activator and the above mass ratio is beneficial to the full performance of the alkali activation activity of the amorphous silicate standard sample and improves the accuracy of the evaluation.

[0069] After the alkali activation treatment, the step of curing treatment is performed to gradually solidify the re-aggregated geopolymer to obtain a hardened sample with a certain strength. Since the microhardness gradually changes during the solidification process of the geopolymer, the properties under different curing conditions and curing times also differ. Therefore, the curing treatment also needs to be performed under the same conditions. In some embodiments, the curing treatment includes 28-day standard curing, that is, 28-day curing under standard temperature and standard humidity, the temperature is 18-22℃, and the relative humidity RH≥95%.

[0070] Step S20 is the step of detecting the microhardness of the hardened sample and performing first mapping treatment, which can be divided into steps S21-S22:

[0071] S21: detecting the microhardness of the hardened sample;

[0072] S22: performing first mapping treatment on the corresponding relationship between the Si, Al, and M molar ratio of the amorphous silicate standard sample and the microhardness.

[0073] In step S21, since the compressive strength and other indicators reflect macroscopic performance, they are affected by pores, sample structural defects, and the like, and it is difficult to truly reflect the level of the alkali-activated activity of the amorphous silico-aluminate after being activated by alkali. Therefore, the indicators are not suitable for evaluation. Microhardness is a micro strength, and reflects the mechanical properties of the chemical product obtained by the reaction of the amorphous silico-aluminate standard sample and the alkali activator. The microhardness can truly reflect the alkali-activated activity potential of the substance, and is more suitable for evaluation of the micro phase alkali-activated activity. Microhardness is tested under the condition of a small load on a micro scale, and the load is generally less than 10 Newtons. In the embodiments, a microhardness tester can be used for testing, and the unit of microhardness can be Pa, MPa, or the like.

[0074] In step S22, the first mapping processing is performed on the corresponding relationship between the Si, Al, and M molar ratios of the standard sample and the microhardness of the corresponding hardened sample. The higher the microhardness, the higher the alkali-activated activity of the standard sample with the Si, Al, and M molar ratio under the alkali-activated condition. After the mapping processing, the microhardness corresponding to the Si, Al, and M molar ratio is obtained. When evaluating the amorphous silico-aluminate material to be evaluated, only the Si, Al, and M molar contents at each position need to be detected. The microhardness corresponding to each position can be obtained according to the mapping relationship, and the alkali-activated activity of the material can be evaluated.

[0075] In some embodiments, the first mapping processing in step S22 can include steps S221-S222 as follows:

[0076] S221: dividing the set of (0, +∞) into a plurality of third intervals that are mutually disjoint, and the lengths of the third intervals are the same;

[0077] S222: according to the corresponding relationship between the Si, Al, and M molar ratios of the amorphous silico-aluminate standard sample and the microhardness of the corresponding hardened sample, and the third interval to which the microhardness belongs, mapping the Si, Al, and M molar ratios of the amorphous silico-aluminate standard sample to the corresponding third interval.

[0078] In step S221, the third intervals can be divided according to the microhardness values of the hardened sample. The length of each third interval can include, but is not limited to, 5 MPa, 10 MPa, 15 MPa. According to these lengths, the microhardness can be divided into multiple third intervals. In step S222, the microhardness of the hardened sample can be attributed to a third interval, and then the Si, Al, and M molar ratios of the corresponding amorphous silico-aluminate standard sample can be mapped to the third interval. In the exemplary embodiment, when steps S13-S14 are included, the length of the third interval in step S221 can be 10 MPa, the microhardness physical quantity can be H, and the unit can be MPa. H∈[5, 15) can be defined as H10, H∈[15, 25) can be defined as H20, and so on, until H∈[125, 135) is defined as H130, and so on. The mapping relationship in step S222 can be as shown in Table 1. Figure 4 The beneficial effects of steps S221-S222 are that similar microhardness values are divided into the same interval, which actually represents the activity of the corresponding phase in the amorphous silico-aluminate material, and is more conducive to subsequent evaluation and comparison, overcoming the problem of difficult evaluation due to too many microhardness values.

[0079] After the above steps S10-S20 are completed, an evaluation system has been established. Subsequent steps S30-S40 are steps for detecting and evaluating specific amorphous silico-aluminate materials to be evaluated.

[0080] Step S30 can include steps S31-S32 as follows:

[0081] S31: Select multiple first positions in the amorphous silico-aluminate material to be evaluated, detect the Si, Al, and M molar contents of each first position, and obtain the microhardness of each first position according to the first mapping processing result;

[0082] S32: Then, the microhardness of the amorphous silico-aluminate material to be evaluated is subjected to first statistical processing to obtain the distribution ratio of the microhardness;

[0083] The first positions selected in step S31 can be random or selected according to a certain rule. The size of each position can be different or the same. Optionally, all positions in the material can be detected to improve the statistical sample size and improve the evaluation accuracy.

[0084] In some embodiments, detecting the Si, Al, and M molar content at each first position can include the following steps: subjecting the amorphous silico-aluminate material to be evaluated to backscattered electron imaging to obtain a BSE image, and to X-ray energy dispersion testing to obtain an EDS element distribution map; sequentially performing noise reduction processing, gray value statistical processing, and threshold segmentation processing on the BSE image, and mapping back to the EDS element distribution map to obtain the Si, Al, and M molar content at each first position. With the aid of backscattered electron imaging and X-ray energy dispersion testing, the element content and type of the amorphous silico-aluminate material to be evaluated can be comprehensively analyzed, and the comprehensiveness of the test position detection analysis can be improved. Then, the microhardness at each first position can be obtained according to the results of the first mapping processing in step S20.

[0085] In the embodiments, the detection of the Si, Al, and M molar content at each second position in step S11 can also refer to the manner of step S31, and after step S11 is performed, step S31 can directly use the detection results of step S11 or can perform detection again.

[0086] Step S32 is a step of first statistical processing of the microhardness at each first position, and the distribution proportion of the microhardness size is counted. In the exemplary embodiment, the total number of occurrences of each microhardness value can be counted, and the number of occurrences of a certain microhardness value can be counted, and then the distribution proportion of the microhardness can be obtained, such as the distribution proportion of the microhardness of 30 MPa being 5%, and the like. In the exemplary embodiment, the microhardness can also be divided into a plurality of third intervals in the manner of steps S221-S222 described above, and the distribution proportion of each interval can be counted.

[0087] In some embodiments, step S32 can also preset a plurality of boundary values, and the distribution proportion of a set higher than the value or a set lower than the value can be counted. In the exemplary embodiment, the first statistical processing includes the following steps S321-S322:

[0088] S321: The microhardness in MPa is divided into the following sets:

[0089] The first microhardness (0, 35];

[0090] The second microhardness (35, +∞);

[0091] S322: According to the results of the first mapping processing, the distribution proportions of the first microhardness and the second microhardness in the amorphous silico-aluminate material to be evaluated are counted.

[0092] The step S321-S322 divides the microhardness into the first microhardness interval and the second microhardness interval by setting 35 MPa as the demarcation value, and then the alkali-activated activity of the material can be evaluated according to the distribution proportion of the second microhardness interval, and the evaluation efficiency is improved. In the demonstration example, the second microhardness interval can be further divided into a medium microhardness interval and a high microhardness interval. The distribution of these microhardness intervals can reflect the alkali-activated activity level of each phase in the amorphous silicate aluminate material.

[0093] The step S40 is a step of performing specific evaluation. In some embodiments, one solid waste can be evaluated. For example, a threshold value of the distribution proportion of the microhardness size can be preset, and if the threshold value is higher, it is considered that the alkali-activated activity meets the requirements. For example, the sum of the distribution proportions of the microhardness higher than 60 MPa in the first statistical result of step S30 reaches 40% as the threshold value, and it is considered to meet the requirements. For example, the sum of the distribution proportions of the microhardness higher than 50 MPa in the first statistical result of step S30 reaches 50% as the threshold value, and it is considered to meet the requirements.

[0094] In some embodiments, more than two amorphous silicate aluminate materials to be evaluated can also be compared and evaluated. In the demonstration example, when the steps S321-S322 are included, at least two amorphous silicate aluminate materials to be evaluated can be provided, and the step S40 can evaluate the alkali-activated activity of each amorphous silicate aluminate material to be evaluated according to the following steps S41-S42 evaluation method:

[0095] S41: comparing the distribution proportions of the first microhardness and the second microhardness of each amorphous silicate aluminate material to be evaluated;

[0096] S42: the higher the distribution proportion of the second microhardness, the higher the alkali-activated activity of the corresponding amorphous silicate aluminate material.

[0097] The values of the second microhardness interval are all higher than the values of the first microhardness interval, and the higher the distribution proportion of the second microhardness interval, the higher the content of the higher-activity amorphous silicate aluminate phase in the amorphous silicate aluminate material to be evaluated, and the higher the alkali-activated activity, thereby realizing the comparison and evaluation between two or more amorphous silicate aluminate materials. In the demonstration example, in addition to 35 MPa as the demarcation value, 30 MPa, 40 MPa, 45 MPa, etc. can also be included but are not limited to as the demarcation value.

[0098] The second aspect of the embodiments of the present application provides a classification method of an amorphous silicate aluminate material, which includes the following step G10:

[0099] G10: The non-crystalline silicate aluminate material to be evaluated is evaluated according to the evaluation method of the above application embodiment, and according to the results of the first statistical processing, the non-crystalline silicate aluminate material after evaluation is classified according to the distribution ratio of the microhardness size.

[0100] Since the above application embodiment evaluation method establishes an evaluation system for the alkali-activated activity of non-crystalline silicate aluminate materials, the non-crystalline silicate aluminate materials after evaluation can be classified, and materials with similar alkali-activated activity can be classified into one category, obtaining multiple activity level categories. Therefore, the classification method of the non-crystalline silicate aluminate material of the application embodiment can accurately, scientifically and quickly classify the non-crystalline silicate aluminate material according to the alkali-activated activity, and can be used in the fields of geopolymerization reaction research, new geopolymer building material research, etc.

[0101] The third aspect of the application embodiment provides a solid waste activity evaluation method, which includes the following step H10:

[0102] H10: Provide solid waste, the solid waste contains non-crystalline silicate aluminate material, and evaluate the solid waste according to the above application embodiment evaluation method.

[0103] Since the above application embodiment evaluation method establishes an evaluation system for the alkali-activated activity of non-crystalline silicate aluminate materials, it can be used for the activity evaluation of solid waste rich in non-crystalline silicate aluminate materials. Compared with the prior art evaluation method, the solid waste activity evaluation method is more accurate, and can also be used for evaluation and comparison across solid waste types, so that the solid waste resources can be scientifically evaluated, which is conducive to the further rational use of solid waste resources.

[0104] The following will be described in conjunction with specific embodiments.

[0105] Embodiment A1

[0106] The embodiment provides a solid waste activity evaluation method, which includes the following steps S1-S6 for constructing the evaluation system, and steps S7-S8 for evaluating specific solid waste. In the embodiment A1, the selected solid waste is fly ash, specifically the first fly ash, denoted as FAI:

[0107] Step S1, first collect BSE-EDS data:

[0108] Sample a large amount of solid waste such as fly ash, blast furnace slag, and circulating fluidized bed, and take BSE images under backscattered electron imaging mode, 5 images for each sample, and more than 10,000 solid waste particles are included in the 5 BSE images. One of the BSE images is as shown in Figure 1 Step of simultaneously performing area scanning on the regions shown in the image by EDS to collect the atomic percentage results of Si, Al, Ca, Fe, Na, K and Mg elements in each pixel.

[0109] The specific steps involved polishing the sample, then spraying a 20 nm thick carbon layer onto the polished sample surface and performing analysis using a scanning electron microscope (APREO S, Thermoscientific, Netherlands) equipped with a silicon drift detector (X-Max, Oxford Instruments, UK). Appropriate testing parameters were set to obtain high-quality elemental images. The electron microscope accelerating voltage was 15 kV, and the working distance was 10 mm. The imaging field of view was 252 × 189 μm, and the resolution was 1024 × 832 (i.e., pixel size approximately 0.25 μm). The dwell time for each pixel was 256 μs, and 32 frames were acquired for each BSE image, with a total scanning time of approximately 125 min. EDS area scan matrices of Si, Al, Ca, Fe, Na, K, and Mg in each BSE image were simultaneously collected.

[0110] Step S2, then perform BSE-EDS data processing:

[0111] A series of image processing steps are performed on the BSE image in step S1, including noise reduction, grayscale value statistics and threshold segmentation, to obtain only the solid waste particle region; then the location information of the solid waste particles is mapped back to the EDS element matrix to obtain only the EDS data of the solid waste particles, and the element molar content of each pixel in each solid waste particle in the image is obtained.

[0112] Step S3, select the elemental molar ratio for preparing the standard sample:

[0113] Based on the test results of step S2, computer technology is used to calculate the (Si+Al) / Ca molar ratio at each location in the sample. The calculation results are then subjected to a second statistical processing to determine the probability of different (Si+Al) / Ca molar ratios occurring. Figure 2 As shown, to facilitate interval division during the statistical process, the total molar amount of Si+Al+Ca was set at 100%. The molar amount of Si+Al increased by 10% each time, and the molar amount of Ca decreased by 10% each time, adjusting in a 10% gradient. The probability of different molar ratios of (Si+Al) / Ca was observed. Statistical analysis revealed that the probability of the minimum (Si+Al) / Ca ratio approaching 1 was relatively high. Additionally, the probabilities of 1.5, 2.33, 4, 9, and values ​​rapidly exceeding 10 (approaching +∞) were also relatively high. Based on these six typical values, the set (0, +∞) was divided into six first intervals: (0, 1], (1, 1.5], (1.5, 2.3], (2.3, 4], (4, 9], and (9, +∞).

[0114] Based on the test results of step S2, computer technology is used to calculate the Si / Al molar ratio at each location in the sample. The calculation results are then subjected to a third statistical processing to determine the probability of different Si / Al molar ratios occurring.Figure 3 As shown in the statistical process, in order to facilitate the division of intervals, according to the total amount of Si+Al is 100%, the molar amount of Si is increased by 10% each time, and the molar amount of Al is reduced by 10% each time, the probability of the occurrence of different molar ratios of Si / Al is observed by adjusting the gradient of 10%. After statistics, it is found that the probability of the occurrence of Si / Al minimum value close to 0.3 is relatively high (when the sum of the molar fractions of Si and Al is 1, Si accounts for about 20% to 26%, and Al accounts for about 74% to 80%), and the probabilities of the occurrence of Si / Al molar ratio of 0.25 and 0.43 are close, and the latter appears less frequently, so 0.43 is not taken as a typical value, and the second typical value is set as Si / Al is 0.67, that is, about 0.7. In addition, when the molar ratio of Si / Al is greater than 4, the ratio rises sharply to about 30 (actually close to +∞), so the molar ratio of Si / Al is 9 is not taken as a typical value. Finally, 0.3, 0.7, 1, 1.5, 2.3, 4 and +∞ are taken as typical values. Based on the 7 typical values, the (0, +∞) set is divided into 7 second intervals, which are (0, 0.3], (0.3, 0.7], (0.7, 1], (1, 1.5], (1.5, 2.3], (2.3, 4], (4, +∞) respectively. (In some embodiments, when M is Ca and B is 7, the second intervals are (0, 0.3], (0.3, 0.7], (0.7, 1], (1, 1.5], (1.5, 2.3], (2.3, 4], (4, +∞) respectively.

[0115] Step S4, preparation of amorphous silicon aluminate standard sample:

[0116] According to the results of statistical processing and interval division in step S3, 6 typical values of (Si+Al) / Ca molar ratio 1, 1.5, 2.33, 4, 9, +∞ (not including Ca) and 7 typical values of Si / Al molar ratio 0.3, 0.7, 1, 1.5, 2.3, 4, +∞ (not including Al) are arranged and combined to obtain 42 groups of coupled data. For example, in the first interval, the molar ratio of 1 represents the interval (0, 1], and the same applies to the molar ratio of +∞, that is, the calcium content of 0 represents the interval (9, +∞), and the second interval is the same. Further, a number of typical values can be selected in each interval to better represent each interval, and of course the amount of coupled data will further increase. According to the above at least 42 groups of coupled data, the corresponding raw materials are selected for the preparation of amorphous silicon aluminate standard sample, and the specific preparation method is as follows:

[0117] First, prepare the silicon precursor solution. Provide raw materials, including tetraethyl orthosilicate, abbreviated as TEOS. Anhydrous ethanol, abbreviated as EtOH. The aluminum source is aluminum nitrate nonahydrate, abbreviated as ANN. The calcium source is calcium nitrate tetrahydrate, abbreviated as CN. The above raw materials are all analytical pure, purchased from Macklin.

[0118] Then add 100g of tetraethyl orthosilicate to an appropriate amount of anhydrous ethanol in a 1L beaker, seal with plastic wrap and stir uniformly with a magnetic stirrer.

[0119] The aluminum and calcium precursor solutions were prepared. The mass of the aluminum source and the calcium source was calculated according to the molar ratio of each element in the target phase, and then was weighed and placed in a beaker. EtOH and deionized water were added respectively, sealed with plastic wrap and stirred until completely dissolved, to obtain an aluminum ion solution and a calcium ion solution respectively. For the synthesis of most target phases, the total molar ratio n(EtOH) / n(TEOS)=6, n(H2O) / n(TEOS)=9 was controlled, but for a few target phases, anhydrous ethanol was additionally added to ensure that it could be completely dissolved, and the amount of the additive was appropriately adjusted to the critical dissolution state. Excessive addition would delay the gelation time, but would not significantly affect the reactivity of the final product.

[0120] Then the sol-gel process was carried out. The aluminum ion solution and the calcium ion solution were added into the silicon solution in turn under stirring. The containers containing the aluminum solution and the calcium solution were repeatedly rinsed to ensure that as much aluminum and calcium as possible entered the tetraethyl orthosilicate solution, so as to avoid the reduction of the content of Al and Ca in the final synthesis phase. After sealing, it was placed in a 70°C water bath for 5-12h, and then taken out after it was converted from sol to gel. The gel was aged at room temperature for 12h.

[0121] Finally, the heat treatment was carried out. The aged gel was crushed and placed in an evaporating dish, dried in a 105°C oven for 12h, cooled and ground, then transferred to a corundum crucible and placed in a 700°C muffle furnace for calcination for 4.5h, to obtain at least 42 kinds of white powder samples. For each molar ratio of the sample, a part of it was subjected to structural characterization to verify whether the molar ratio met the sample, and the other part was used for alkali activation treatment.

[0122] Step S5, alkali activation treatment and curing treatment were carried out.

[0123] The above at least 42 kinds of samples were mixed with an alkali activator, which was a sodium silicate solution with a modulus of 1 and a concentration of 25wt%, and the mass ratio of the sample to sodium silicate in the sodium silicate solution was 0.89:1. Then the samples were cured under standard curing conditions of temperature 20°C and relative humidity 95% for 28 days, to obtain at least 42 kinds of hardened samples.

[0124] Step S6, microhardness detection and first mapping treatment were carried out.

[0125] The above hardened samples were detected by a FALCON 600 type microhardness tester with a load pressure of 1kgf and a dwell time of 10s, to obtain the microhardness of each hardened sample. Then the first interval, the second interval and the microhardness of the hardened sample were subjected to first mapping treatment, and the results are shown in Figure 4 and the corresponding mapping relationship can be seen in Figure 4 .

[0126] The (0, +∞) is divided into several intervals by microhardness (physical quantity H, unit MPa). Considering the actual measurement, H∈[5, 15) is defined as the activity level of H10, H∈[15, 25) is defined as the activity level of H20, and so on until H∈[125, 135) is defined as H130. Referring to the probability of these activity levels, 42 groups of standard samples are optimized and integrated to obtain the final microhardness of the hardened sample, which is divided into nine activity levels: H20, H30, H40, H50, H60, H70, H80, H90 and H130.

[0127] The above steps S1-S6 have constructed an evaluation system. When evaluating a specific amorphous silicate aluminate material, there is no need to construct an evaluation system from scratch. Only the molar content of the amorphous silicate aluminate material to be evaluated needs to be detected, and the (Si+Al) / Ca molar ratio and Si / Al molar ratio are calculated according to the detection results. Then, according to the corresponding mapping relationship, the microhardness can be obtained. For example, for a single-phase amorphous calcium silicate aluminate material, the (Si+Al) / Ca molar ratio is calculated to be 3, and the Si / Al molar ratio is calculated to be 1.3. The first interval is (2.3, 4], and the second interval is (1, 1.5]. According to the mapping relationship, the microhardness obtained is 36.8 MPa, which belongs to H40. The microhardness belongs to the lower middle, indicating that the alkali activation activity of the single-phase amorphous calcium silicate aluminate material belongs to the lower middle level. The evaluation of composite or mixed amorphous silicate aluminate materials can be referred to below. Figure 4 Figure 4 The following are steps S7-S8 for testing and evaluating specific solid wastes. The specific solid waste in this embodiment A1 is the first fly ash, denoted as FAI.

[0128] The following are steps S7-S8 for testing and evaluating specific solid wastes. The specific solid waste in this embodiment A1 is the first fly ash, denoted as FAI.

[0129] Step S7, testing and data processing:

[0130] Referring to the BSE-EDS data acquisition method and data processing method in steps S1 and S2, the first fly ash to be evaluated is tested and processed. At least 5 BSE images are taken, and the element molar content of each pixel point in each solid waste particle is obtained by EDS surface scanning. The stack plot of Si, Al, Ca and other elements in one image is shown in Figure 5 If the first fly ash is already in the selected solid waste in step S1, the data can be directly used.

[0131] S8, first statistical processing:

[0132] ​The statistical results of step S7 are processed by computer technology, the molar contents of Si, Al and Ca elements at each position are calculated as the (Si+Al) / Ca molar ratio and the Si / Al molar ratio, and then the activity level corresponding to each position is obtained according to the mapping relationship in step S6, and the probability of occurrence of each activity level is calculated, wherein the visualization result of one figure is shown in Figure 4 , and Table 1. It can be seen that Figure 6 the sum of each activity level in Figure 6 is 93.1%, not 100%, because the solid waste also contains crystal phase, inert phase and the like, which do not have alkali-activated activity, so the 93.1% is the proportion of the active phase in the amorphous state.

[0133] According to the results of Figure 6 and Table 1, the distribution proportion of each microhardness can be seen, and the results are further analyzed below.

[0134] Example A2

[0135] This embodiment provides a method for evaluating the activity of solid waste, which is different from example A1 only in that steps S1-S6 remain unchanged, and the evaluation system constructed by steps S1-S6 in example A1 can also be directly used, and steps S7-S8 are changed to evaluate another specific solid waste, which is the second fly ash, denoted as FAII, and the other steps are the same, wherein the visualization result of one figure is shown in Figure 7 , and Table 1.

[0136] Example A3

[0137] This embodiment provides a method for evaluating the activity of solid waste, which is different from example A1 only in that steps S1-S6 remain unchanged, and the evaluation system constructed by steps S1-S6 in example A1 can also be directly used, and steps S7-S8 are changed to evaluate another specific solid waste, which is the third fly ash, denoted as FAIII, and the other steps are the same, wherein the visualization result of one figure is shown in Figure 8 , and Table 1.

[0138] Example A4

[0139] This embodiment provides a method for evaluating the activity of solid waste, which is different from example A1 only in that steps S1-S6 remain unchanged, and the evaluation system constructed by steps S1-S6 in example A1 can also be directly used, and steps S7-S8 are changed to evaluate another specific solid waste, which is the fourth fly ash, denoted as FAIV, and the other steps are the same, wherein the visualization result of one figure is shown in Figure 9 , and Table 1.

[0140] Example A5

[0141] The embodiment provides an evaluation method for solid waste activity, which is only different from the embodiment A1 in that steps S1-S6 are unchanged, and the evaluation system constructed by steps S1-S6 in the embodiment A1 can be directly used, and steps S7-S8 are changed to evaluate another specific solid waste, that is, granulated blast furnace slag, denoted as GGBS, and other steps are the same, and the visualization result of one figure is as shown in Table 1. Figure 10

[0142] Embodiment A6

[0143] The embodiment provides an evaluation method for solid waste activity, which is only different from the embodiment A1 in that steps S1-S6 are unchanged, and the evaluation system constructed by steps S1-S6 in the embodiment A1 can be directly used, and steps S7-S8 are changed to evaluate another specific solid waste, that is, circulating fluidized bed ash, denoted as CFBA, and other steps are the same, and the visualization result of one figure is as shown in Table 1. Figure 11

[0144] Table 1

[0145] FAI FAII FAIII FAIV GGBS CFBA H20 1.1％ 1.1％ 1.6％ 1.7％ 0.2％ 0.9％ H30 50.2％ 40.0％ 66.0％ 64.9％ 3.7％ 71.6％ H40 3.7％ 8.1％ 5.1％ 6.8％ 26.5％ 2.3％ H50 3.8％ 11.6％ 4.3％ 6.2％ 54.0％ 2.2％ H60 2.8％ 3.8％ 2.7％ 3.0％ 4.4％ 1.9％ H70 1.5％ 3.2％ 0.9％ 1.6％ 6.4％ 0.6％ H80 2.6％ 3.9％ 1.2％ 1.6％ 0.7％ 1.0％ H90 6.8％ 3.5％ 7.2％ 3.4％ 1.0％ 4.6％ H130 20.6％ 19.7％ 8.4％ 8.9％ 1.8％ 10.1％

[0146] Evaluation of alkali activation and verification of evaluation accuracy

[0147] Preliminary evaluation:

[0148] After obtaining the results in Table 1, the alkali activation of each solid waste can be evaluated according to the distribution proportion of each microhardness. For example, the alkali activation of different solid wastes is evaluated, and the distribution proportion in Table 1 is observed. The evaluation principle is that the higher the distribution proportion of high microhardness value and the lower the distribution proportion of low microhardness value, the higher the alkali activation of the solid waste. According to the principle and the data in Table 1, it can be qualitatively judged that the alkali activation is GGBS>FA>CFBA, which is consistent with the existing experience. The activity of granulated blast furnace slag (GGBS) is high, the components are relatively simple, and it is extremely representative. The activity of fly ash (FA) is moderate, the components are complex, and it is one of the most well-known industrial solid wastes in the industry. The activity of circulating fluidized bed ash (CFBA) is low, the components are complex, and it is also extremely representative.

[0149] In addition to the above evaluation of different solid wastes, a single solid waste can also be evaluated. For example, a threshold of the distribution proportion of microhardness can be preset, and if it is higher than the threshold, it is considered that the alkali activation meets the requirements. For example, it is found that the strength of a solid waste after alkali activation meets the requirements, and the sum of the distribution proportion of H60-H130 obtained by the above evaluation method is 40%. Therefore, as long as the sum of the distribution proportion of H60-H130 obtained by the above evaluation method of other solid wastes after detection reaches 40%, the requirements can be met. ​​

[0150] Of course, the solid waste can also be classified, and the distribution proportion of microhardness size is pre-set as multiple categories according to the above evaluation method, and then the molar content of the solid waste is detected, and the distribution proportion of microhardness size is obtained after mapping and statistics, so that the solid waste can be better classified.

[0151] Further evaluation:

[0152] The phase corresponding to H20-H30 microhardness is defined as a low-strength grade phase, the phase corresponding to H40-H70 microhardness is defined as a medium-strength grade phase, and the phase corresponding to H80-H130 microhardness is defined as a high-strength grade phase. The results of Table 1 above are summarized in Table 2, and the "medium + high" in Table 2 is the sum of the distribution proportions of the medium-strength grade phase and the high-strength grade phase, that is, H40-H130.

[0153] Table 2

[0154] FAI FAII FAIII FAIV GGBS CFBA Low intensity phase 51.3％ 41.1％ 67.6％ 66.6％ 3.9％ 72.5％ Medium intensity phase 11.8％ 26.7％ 13.0％ 17.6％ 91.3％ 7.0％ High intensity phase 30.0％ 27.1％ 16.8％ 13.9％ 3.5％ 15.7％ Medium + high 41.8％ 53.8％ 29.8％ 31.5％ 94.8％ 22.7％

[0155] Observing the values of "medium + high" of Examples A1-A6 in Table 2, the relationship of GGBS>FAII>FAI>FAIV>FAIII>CFBA is shown, and FAIV and FAIII are very close.

[0156] Of course, the above data is the statistical result in one BSE image of each example, but the above mentioned that at least 5 BSE images are taken for each example. In order to reduce sampling error and instrument error and improve the accuracy of statistical results, the 5 BSE images of each example are mapped, calculated and counted to obtain the average value as the distribution proportion of microhardness size, and the results are recorded in Table 3.

[0157] Table 3

[0158] FAI FAII FAIII FAIV GGBS CFBA Low intensity phase 54.8％ 47.6％ 73.1％ 71.6％ 21.8％ 74.5％ Medium intensity phase 8.3％ 20.2％ 9.5％ 12.6％ 73.4％ 5.0％ High intensity phase 30.0％ 27.1％ 16.8％ 13.9％ 3.5％ 15.7％ Medium + high 38.3％ 47.3％ 26.3％ 26.5％ 76.9％ 20.7％

[0159] Observing the values of "medium + high" of Examples A1-A6 in Table 3, the relationship of GGBS>FAII>FAI>FAIV>FAIII>CFBA is shown, and FAIV and FAIII are very close, which is consistent with the results of Table 2.

[0160] The data of Table 3 above is analyzed in detail. Although the high-strength grade phase of CFBA accounts for 15.7% of the medium interval, its low-strength grade phase accounts for 74.5%, which is the highest value in the test group, and its medium-strength grade phase accounts for only 5.0%, which is the lowest value, resulting in the weakest reactivity. Comparative analysis shows that although GGBS has the lowest high-strength grade phase of 3.5%, it has a medium-strength grade phase of 73.4% and a low-strength grade phase of only 21.8%, and its active phase abundance is significantly better than other solid wastes, so the alkali activation effect is the most significant.

[0161] Further analysis of the FAs system:

[0162] The low-strength grade phase of FAII accounts for the lowest 47.6%, the medium-strength grade phase accounts for the highest 20.2%, and the high-strength grade phase accounts for 27.1% close to the peak, so its performance is the best among the FA class;

[0163] The low-strength grade phase of FAI is 7.2% higher than that of FAII, but 18.3% and 16.8% lower than that of FAIII and FAIV, respectively, although the medium-strength grade phase is the lowest, the high-strength grade phase is 13.2% and 16.1% higher than that of FAIII and FAIV, respectively, and the performance is suboptimal;

[0164] Comparing FAIII and FAIV, the low-strength grade phase of the former is 1.5% higher than that of the latter, the medium-strength grade phase is 3.1% lower, but the high-strength grade phase is 2.9% higher, so the performance of the two is equivalent.

[0165] Of course, in general, the faster evaluation method is to directly observe the distribution ratio of "medium + high", and similar conclusions can also be obtained from Table 1 and Table 2.

[0166] Accuracy verification:

[0167] In order to verify the accuracy of the above evaluation method, the solid waste of Examples A1-A6 is subjected to alkali activation treatment, and the conditions of alkali activation treatment and curing conditions are the same as those of Examples A1-A6. The hardened geopolymer after alkali activation of the solid waste is obtained, and the FALCON 600 type microhardness tester is used to detect the above hardened sample, the loading pressure is 1 kgf, and the residence time is 10 s. Under the image magnification of x10, 30 points randomly selected in the hardened sample are tested, the average value of each is calculated to reduce the error, and the average value of the microhardness of the hardened geopolymer prepared from each solid waste is obtained.

[0168] The average microhardness of the hardened geopolymer prepared by GGBS is taken as a benchmark, denoted as Z MPa, the average microhardness of the hardened geopolymer prepared by FAII is 0.89xZ MPa, the average microhardness of the hardened geopolymer prepared by FAI is 0.83xZ MPa, the average microhardness of the hardened geopolymer prepared by FAIV is 0.75xZ MPa, the average microhardness of the hardened geopolymer prepared by FAIII is 0.74xZ MPa, and the detection result of the hardened geopolymer prepared by CFBA exceeds the lower limit of the instrument detection, and the microhardness is too low, denoted as 0. This is consistent with the above evaluation results, that is, GGBS>FAII>FAI>FAIV>FAIII>CFBA, and FAIV and FAIII are similar.

[0169] It is proved that the above evaluation method, evaluation result and classification method are consistent with the actual result.

[0170] In addition, since the actual activation degree and performance effect of alkali activation have certain relationship with the type and amount of alkali activator, the above examples A1-A6 actually establish a solid waste alkali activation evaluation system under the condition that the alkali activator is a sodium silicate solution with a modulus of 1 and the mass ratio of solid waste to sodium silicate in the alkali activator is 0.89:1. The ratio can be further adjusted, or the type of alkali activator can be adjusted, to establish a solid waste alkali activation evaluation system under other treatment conditions, such as examples B1, C1 and the like. In addition, during alkali activation, in addition to amorphous calcium silicate aluminum, amorphous sodium silicate aluminum, amorphous potassium silicate aluminum and the like also have certain alkali activation activity, and an evaluation system can be established with respect to these amorphous silicate aluminates, such as example D1 and the like.

[0171] Example B1

[0172] The present example provides an evaluation method of solid waste activity, which is different from example A1 only in that the alkali activator in step S5 is replaced by sodium hydroxide solution, and the mass ratio of standard sample to sodium hydroxide in sodium hydroxide solution is unchanged, and the other steps are the same. Thus, another evaluation system is established.

[0173] Example C1

[0174] The present example provides an evaluation method of solid waste activity, which is different from example A1 only in that the mass ratio of standard sample to sodium silicate in sodium silicate solution in step S5 is changed from 0.89:1 to 0.5:1, and the other steps are the same. Thus, another evaluation system is established.

[0175] Example D1 and the like

[0176] The present example provides an evaluation method of solid waste activity, which is different from example A1 only in that all the calcium elements in the steps are replaced by sodium elements, iron elements, magnesium elements and a combination of at least two of them, and a combination of calcium elements and at least one of them, and the other steps are the same. Thus, a series of evaluation systems are established.

[0177] The above examples embody the method and idea of the application for constructing and evaluating the alkali-activated activity system of amorphous silicate-aluminate materials, and do not constitute a specific limitation on the scheme. Routine adjustments made on the basis of the above examples also belong to the scope of the idea of constructing and evaluating the system.

[0178] Finally, a plurality of solid waste alkali-activated activity evaluation systems can be established by comprehensively considering the types of amorphous silicate-aluminate materials in solid waste and alkali-activated treatment conditions, and a complete set of databases can be formed.

[0179] The above only describes the preferred embodiments of the application and is not used to limit the application. Any modifications, equivalent replacements and improvements made within the spirit and principle of the application should be included in the protection scope of the application.

Claims

1. A method for evaluating the activity of amorphous aluminosilicate materials, characterized in that, Includes the following steps: Multiple single-phase amorphous aluminosilicate standards were prepared according to different molar ratios of Si, Al, and M. The amorphous aluminosilicate standards were subjected to alkali activation and curing treatments under the same conditions to obtain multiple hardened samples. Among them, M includes alkali metal elements and / or alkaline earth metal elements. The hardened sample was tested for microhardness, and the relationship between the Si, Al, and M molar ratio of the amorphous aluminosilicate standard and the magnitude of microhardness was processed by a first mapping process. Multiple first locations are selected in the amorphous aluminosilicate material to be evaluated, and the molar content of Si, Al, and M at each first location is detected. Based on the results of the first mapping process, the microhardness of each first location is obtained. Then, the microhardness of the amorphous aluminosilicate material to be evaluated is subjected to a first statistical process to obtain the distribution ratio of the microhardness magnitude. The alkali-activated activity of the amorphous aluminosilicate material to be evaluated is assessed based on the distribution ratio of microhardness magnitudes in the material.

2. The evaluation method according to claim 1, characterized in that: The M includes at least one of Ca, Na, and K; and / or Before preparing the amorphous aluminosilicate standard sample, the following steps are also included: Multiple second positions are selected in the amorphous aluminosilicate material to be evaluated, and the molar content of Si, Al, and M at each second position is detected. The (Si+Al) / M molar ratio at each position is calculated. The calculation results are subjected to a second statistical processing to obtain the probability of different (Si+Al) / M molar ratios. Based on the probability, multiple raw materials with (Si+Al) / M molar ratios are selected for preparing the amorphous aluminosilicate standard sample. And / or, the molar content of Si and Al at each second position is detected, the Si / Al molar ratio at each position is calculated, and the calculation results are subjected to a third statistical processing to obtain the probability of different Si / Al molar ratios. Based on the probability, multiple raw materials with Si / Al molar ratios are selected for preparing the amorphous aluminosilicate standard sample.

3. The evaluation method according to claim 2, characterized in that, After performing the second and third statistical processing, the following steps are also performed: Based on the results of the second statistical processing, the set (0, +∞) is divided into A mutually non-overlapping first intervals using the (Si+Al) / M molar ratio. Based on the results of the third statistical processing, the set (0, +∞) is divided into B mutually non-overlapping second intervals using the Si / Al molar ratio, where A≥2 and B≥2. For each first interval, select several (Si+Al) / M molar ratios, and for each second interval, select several Si / Al molar ratios. Arrange and combine the selected (Si+Al) / M molar ratios and Si / Al molar ratios to obtain at least A×B combinations, and prepare at least A×B amorphous aluminosilicate standard samples.

4. The evaluation method according to claim 3, characterized in that: When M is Ca and A is 6, the first interval is (0, 1], (1, 1.5], (1.5, 2.3], (2.3, 4], (4, 9], (9, +∞) in sequence; And / or, when M is Ca and B is 7, the second interval is (0, 0.3], (0.3, 0.7], (0.7, 1], (1, 1.5], (1.5, 2.3], (2.3, 4], (4, +∞).

5. The evaluation method according to any one of claims 1 to 4, characterized in that, The first mapping process includes the following steps: The set (0, +∞) is divided into multiple non-overlapping third intervals based on the magnitude of microhardness, and each third interval has the same length. Based on the correspondence between the Si, Al, and M molar ratios of the amorphous aluminosilicate standard and the corresponding microhardness of the hardened sample, and the third interval to which the microhardness belongs, the Si, Al, and M molar ratios of the amorphous aluminosilicate standard are mapped to the corresponding third interval.

6. The evaluation method according to any one of claims 1 to 4, characterized in that, The first statistical processing includes the following steps: The set (0, +∞) is divided into the following categories based on microhardness in MPa: First microhardness (0, 35]; Second microhardness (35, +∞); Based on the results of the first mapping process, the distribution ratios of the first microhardness and the second microhardness in the amorphous aluminosilicate material to be evaluated are statistically analyzed.

7. The evaluation method according to claim 6, characterized in that, Provide at least two samples of the amorphous aluminosilicate material to be evaluated, and evaluate the base-activated activity of each sample of the amorphous aluminosilicate material to be evaluated according to the following evaluation method: The distribution ratios of the first microhardness and the second microhardness of each sample of the amorphous aluminosilicate material to be evaluated are compared. The higher the distribution ratio of the second microhardness, the higher the alkali-activated activity of the corresponding amorphous aluminosilicate material.

8. The evaluation method according to any one of claims 1 to 4, 7, characterized in that: The preparation method of the amorphous aluminosilicate standard includes the sol-gel method; And / or, the alkaline activator for the alkaline activation treatment comprises sodium silicate, and the mass ratio of each amorphous aluminosilicate standard to the sodium silicate is (0.5-1.6):1; And / or, the maintenance treatment includes 28 days of standard maintenance; And / or, detecting the molar content of Si, Al, and M at each of the first positions includes the following steps: The amorphous aluminosilicate material to be evaluated was subjected to backscattered electron imaging to obtain BSE images, and X-ray energy dispersive X-ray chromatography was performed to obtain EDS elemental distribution maps. The BSE image is sequentially subjected to noise reduction, grayscale value statistical processing, and threshold segmentation, and then mapped back to the EDS element distribution map to obtain the molar content of Si, Al, and M at each of the first positions.

9. A method for classifying amorphous aluminosilicate materials, characterized in that, Includes the following steps: The amorphous aluminosilicate material to be evaluated is evaluated according to the evaluation method described in any one of claims 1 to 8. Based on the results of the first statistical processing, the evaluated amorphous aluminosilicate material is classified according to the distribution ratio of its microhardness.

10. A method for evaluating the activity of solid waste, characterized in that, Includes the following steps: Provide solid waste containing amorphous aluminosilicate materials, and evaluate the solid waste according to the evaluation method described in any one of claims 1 to 8.

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