Patent Application
20240109809
This application claims the benefit of priority from China patent applications No. 202211153096.6, filed on Sep. 21, 2022, which is incorporated herein by reference in their entirety.
The present application relates to the technical field of solid waste utilization and material engineering, in particular, the present application related to a precise ion implantation type modified geopolymer and an efficient preparation method thereof.
Coal gangue, slag, sedimentary mud in river and lake and other industrial wastes are facing the difficulty of disposal, and there are some vital problems like hidden danger of piling, pollution of the soil and ground water nearby, serious harm to the natural ecological environment. Therefore, the problem of how to effectively dispose coal gangue and other industrial waste is urgently to solve.
Geopolymer is a new type of green inorganic silica-aluminum gel material, and the major raw material of which are active silica-aluminum raw materials and alkaline activator, then obtained by the appropriate process of solution-monomer reconstruction-polycondensation reaction and so on. The raw materials of geopolymer can widely use industrial wastes rich in silicon and aluminum elements (calcined coal gangue powder, activated sedimentary mud powder, steel slag powder, slag powder, fly ash, boiler slag, etc.). The properties of obtained geopolymer are similar to cement materials, but compared with cement, it has a series of advantages such as good durability and low energy consumption, which is an ideal material to replace cement and other traditional grouting materials.
However, as the content of active silicon and aluminum in existing raw materials mainly composed of industrial wastes is unstable, the mineral composition and elemental composition between different raw materials are obvious differences, and the same raw materials will also have the above differences due to the different producing area or source. As a result, it is difficult to accurately control the mechanical properties of the geopolymer materials obtained from different raw materials, and the mixing ratio design of multi-source solid waste raw materials is relatively blind. Now, when preparing the geopolymer of different raw materials precursors in China, most of them use the orthogonal experiment method for test mixing. This method has obvious blindness and low repeatability, and the conclusion is not universal, which significantly affects the popularization and application of geopolymer. Based on this situation, the patentee has carried out a series of studies and provides a new technology that can be used to guide the efficient preparation of multi-source geopolymers. The method has high reliability and excellent comprehensive efficiency, which is helpful to promote this type of new material to popularize and use in the engineering field, and is of great significance to realize the organic combination of the areas of energy, environmental protection, and construction engineering.
Based on this situation, the embodiments of the present application provide a gel material of precise ion implantation type modified geopolymer, and provide an efficient preparation of multi-source geopolymer.
The present application provides a gel material of precise ion implantation type modified geopolymer, which consists of a geopolymer source material with a preset size that implanted by Si ion and Al ion with a designated dose by an ion implanter.
Furtherly, the source material consists of a mixture of solid waste, alkali activator, and water.
Furtherly, solid waste comprises one or any combination of high-calcium solid waste raw materials (such as steel slag powder, slag powder, boiler slag and the like), low-calcium solid waste raw materials (such as calcined coal gangue powder, activated sediment powder, fly ash and the like) and other industrial wastes rich in active silicon and aluminum elements.
Furtherly, the alkali activator is formed by mixing sodium hydroxide and sodium silicate according to a certain proportion, the modulus is 1.2˜1.8.
Furtherly, the mass ratio of the alkali activator to the water is 0.08˜0.12:1; the mass ratio of water to solid waste is 0.25˜0.65:1; the implanting dose of Si and Al ions implanted by the ion implanter is 1×1016˜ 2×1017 ions/cm2.
Furtherly, the accelerating voltage of the ion implanter is 40˜80 keV.
The present application also provides an efficient preparation of multi-source geopolymer which comprises the following steps:
The above-mentioned geopolymer gel material can be fully activated by adding a small amount of alkali excitant to accelerate the polymerization reaction in the solid waste rich in silicon and aluminum, and the generated polymerization products are filled with each other, the porosity is reduced, and the strength is improved.
Under the action of alkali activator, the geopolymer undergoes a process of breaking and recombining silicon-oxygen bonds and aluminum-oxygen bonds, and finally a stable three-dimensional polyaluminate structure is generated. The reaction equations are as follow:
According to the precise ion implantation type modified geopolymer, a high-energy ion implanter is used for implanting Si and Al ions with specified concentrations into the geopolymer source material, so that can achieve the goal of modifying the material surface. By implanting a dose of 1×1016˜2×1017 ions/cm2 Si and Al ions, the composition of silicon and aluminum elements in the geopolymer source material is quantitatively adjusted, and comparing to the concentrations before implantation, the concentrations of Si and Al ions can be increase by 1.6%˜32%, and finally directly change the mechanical properties of the geopolymer gel material.
In the above nano-indentation test, the influence of ion concentration adjustment on the mechanical properties of geopolymer can be intuitively obtained by testing the surface hardness and elastic modulus (referring to the ratio of stress and strain of the material under the state of stress) of the matrix before and after ion implantation treatment. Compared with that before implantation, the index of nano-indentation hardness of the matrix will change correspondingly.
In the above ICP-OES test, the leaching concentration of the Si and Al ions in the solid waste rich in silicon and aluminum is obtained by testing, and is used as the concentration of the active silicon and aluminum elements of this solid waste; furtherly, the concentration of active silicon and aluminum elements in the solid waste rich in silicon and aluminum can be adjusted by adding other mineral or chemical additive, according to the result of Step 3.
Implementing the embodiment of the present application can bring the following benefits: according to the technical scheme provided by the invention, the ion implantation technology is innovatively introduced to carry out the research on the geopolymer precise implantation technology and method, which changes the blind premix method in the prior geopolymer preparation process, and is helpful to greatly improve the preparation efficiency of the target geopolymer and reduce the preparation cost. Meanwhile, the source materials used by the method are mainly related industrial solid wastes such as sediment, steel slag, fly ash and the like. The prepared geopolymer can be used for various application scenes such as municipal administration, geotechnical engineering construction, field of grouting reinforcement and the like, which can greatly improve the dissipation capacity of multi-source industrial solid wastes and promote the sustainable development of related industries, and it is of great significance to the organic combination of energy, environmental protection and construction engineering.
In order to specifically explain the technical solutions in the embodiments of the present application, the figures required in the description of the embodiments will be briefly introduced below. However, it is to be appreciated that the following figures are some embodiments of the present application, and those ordinary skilled in the art can imply other figures based on the provided ones with the premise of no creative effort.
Hereinafter, the technical solutions in the embodiments of the present application will be clearly and completely described in combination with the drawings in the embodiments of the present application. Obviously, the described embodiments are some embodiments of the present application, but not all embodiments. Based on the embodiments of the present application, all other embodiments obtained by a person skilled in the art with the premise of no creative effort belong to the protection scope of the present application.
The terms “first,” “second,” “third,” and “fourth,” etc. in the description and claims of the present application and in the accompanying drawings are used for distinguishing between different objects and not for describing a particular order. In addition, that term “include” and “have,” as well as any variations thereof, are intend to cover a non-exclusive inclusion. For example, a process, method, system, product, or equipment that comprises a series of steps or elements is not limited to the mentioned steps or elements, but may alternatively include other steps or elements not mentioned, or may alternatively include other steps or elements inherent to such process, method, product, or equipment.
Reference herein to “an embodiment” means that a particular feature, result, or characteristic described in connection with the embodiment can be included in at least one embodiment of the present application. The appearances of this term in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. It is explicitly and implicitly understood by those skill in the art that the embodiments describe herein may be combined with other embodiments.
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The embodiments of the present application further provide a precise ion implantation type modified geopolymer, which may specifically include: a geopolymer source material with a preset size, and one or a combination of Si and Al ions with a designated dose implanted by an ion implanter.
Illustratively, the above preset size may specifically be: 3˜8 mm thick sheet with a cross-sectional area of not more than 2500 mm2 and flat upper and lower surfaces. The above preset size can be set by the user, and the application is not limited to the above preset size.
Illustratively, the ion implantation dose of Si and Al ions implanted by the above-mentioned ion implanter is 1×1016˜2×1017 ions/cm2. That is, the number of ions in unit area (square centimeter) is 1×1016˜2×1017.
Illustratively, the above-mentioned geopolymer source material consists of a mixture of solid waste, alkali activator, and water; wherein the solid waste comprises one or any combination of high-calcium solid waste raw materials (such as steel slag powder, slag powder, boiler slag and the like), low-calcium solid waste raw materials (such as calcined coal gangue powder, activated sediment powder, fly ash and the like) and other industrial wastes rich in active silicon and aluminum elements.
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Illustratively, the above-mentioned certain mixing ratio is implemented as follows: the modulus (molar ratio) of the alkali activator is 1.2˜1.8 (the modulus of the alkali activator can specifically represent the molar ratio of silicon dioxide to sodium oxide in the alkali activator); the mass ratio of the alkali activator to the water is 0.08˜0.12:1; the mass ratio of water to solid waste is 0.25˜0.65:1.
Illustratively, the above-mentioned pretreatment is performed as follows: firstly, process the prepared source material into a thin sheet having a cross-sectional area of not more than 2500 mm2 and a thickness of 3 to 8 mm with flat upper and lower surfaces, and perform grinding, polishing, cleaning, and drying treatments in sequence. Specifically, an automatic grinding machine is used in the grinding treatment and silicon carbide abrasive paper of 400 meshes, 800 meshes, 1200 mesh, 2000 meshes and 5000 meshes is sequentially selected to grind the surface of the sample, and the grinding time of each grade of abrasive paper is 3˜5 minutes. In the polishing process, the test surface is polished by 1˜5 μm ultrafine alumina suspension and a polishing disk, and the polishing time is controlled in 5˜10 minutes. In the cleaning treatment, absolute ethanol is used for washing the sample for 3˜5 times; while in the drying treatment, the sample is dried in the condition of 50 degrees for 24 hours.
Illustratively, the above-mentioned precise implantation refers to control the type of implanted ion, the dose of implanted ion, and the acceleration voltage, to realize precise control of the element type, the element concentration, and the implantation depth range in the geopolymer matrix, wherein the dose of implanted ion is 1×1016 to 2×1017 ions/cm2; The accelerating voltage is 40 to 80 keV.
Illustratively, the above-mentioned nano-indentation test is specifically performed as follows: the maximum indentation depth sets as 1000 nm, and the lattice spacing uses 50 μm. Displacement control is adopted in the loading process. When the thermal drift value of the testing machine drops to <0.05 nm/s, the test is automatically started. The Berkovich indenter is loaded to the set maximum depth at a strain rate of 0.05 s−1, and then enters the holding stage of 10 s. Finally, the indenter is away from the test surface of the sample at a constant unloading rate (dF/dt) until complete unloading.
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Illustratively, the effect of the above-mentioned element concentration adjustment on the mechanical properties of geopolymer is specifically reflected as follows: for the using high calcium raw material slag-based (chemical composition content (mass percentage): SiO2 34.5%, Al2O3 17.7%, CaO 34.0%, MgO 6.0%, Fe2O3 1.0%); concerning the geopolymer matrix, the average hardness of the gel on the matrix surface before injection is 3.46 GPa; after the implantation of Al ions with a dose of 1×1016 ions/cm2, the average hardness of the gel on the matrix surface is 3.89 GPa. After implantation of Si ions with a dose of 1×1016 ions/cm2, the average hardness of the gel on the matrix surface is 3.02 GPa. For the using low calcium raw material activated sediment powder (SiO2 49.7%, Al2O322.2%, CaO 5.6%, MgO 1.8%, Fe2O3 8.0%;), concerning the geopolymer matrix, the average hardness of the gel on the matrix surface before injection is 3.12 GPa; after the implantation of Al ions with a dose of 1×1016 ions/cm2, the average hardness of the gel on the matrix surface is 3.54 GPa. After implantation of Si ions with a dose of 1×1016 ions/cm2, the average hardness of the gel on the matrix surface is 2.63 Gpa.
Illustratively, the above-mentioned ICP-OES leaching concentration test is specifically performed as follows: mix the solid waste rich in silicon and aluminum with an alkali activator solution according to the ratio of 0.025 g/mL, wherein the concentration of OH− in the alkali activator solution is 5 mol/L; filter and dilute the filtrate to 0.02 mol/L after magnetically stirring the solution for 1˜2 hour and further adding 37% dilute hydrochloric acid to neutralize the filtrate. The concentrations of Si and Al in the filtrate are measured by ICP-OES.
According to the technical scheme provided by the application, the ion implantation technology is innovatively introduced to carry out the research on the geopolymer precise implantation technology and method, which changes the blind premix method in the prior geopolymer preparation process, and is helpful to improve the preparation efficiency of the target geopolymer and reduce the preparation cost. Meanwhile, the source materials used by the method are mainly related industrial solid wastes such as calcined coal gangue powder, activated sediment powder, steel slag powder and the like. The prepared geopolymer can be used for various application scenes such as municipal administration, geotechnical engineering construction, field of grouting reinforcement and the like, which can greatly improve the dissipation capacity of multi-source industrial solid wastes and promote the sustainable development of related industries, and it is of great significance to the organic combination of energy, environmental protection and construction engineering.
It should be noted that, for the sake of simple description, the foregoing method embodiments are described as a series of action combinations, but those skilled in the art should understand that the present application is not limited by the order of the described actions, as some steps may be performed in other orders or simultaneously according to the present application. Secondly, those skilled in the art should also know that the embodiments described in the specification are all alternative embodiments, and the acts and modules involved are not necessarily required by the present application.
In the above embodiments, the description of each embodiment is focused on each other. For the parts that are not described in detail in a certain embodiment, please refer to the relevant description of other embodiments.
The embodiments of the present application are described in detail above, and the principles and implementation modes of the present application are illustrated by specific examples herein, and the description of the above embodiments is only used to help understand the method and core idea of the present application. Meanwhile, for those skilled in the art, according to the concept of the present application, there may be changes in the specific embodiment and application scope. Therefore, the description should not be construed as limiting the present application.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202211153096.6 | Sep 2022 | CN | national |
