CN115124245A - One-step process for preparing microcrystalline glass from chromium-containing stainless steel slag - Google Patents

One-step process for preparing microcrystalline glass from chromium-containing stainless steel slag Download PDF

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CN115124245A
CN115124245A CN202210616874.4A CN202210616874A CN115124245A CN 115124245 A CN115124245 A CN 115124245A CN 202210616874 A CN202210616874 A CN 202210616874A CN 115124245 A CN115124245 A CN 115124245A
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chromium
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steel slag
microcrystalline glass
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金会心
郭育良
谢红艳
吴复忠
肖媛丹
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Guizhou University
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    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0063—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing waste materials, e.g. slags

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Abstract

The invention discloses a process for preparing microcrystalline glass from chromium-containing stainless steel slag by a one-step method. The invention takes chromium-containing stainless steel slag as a raw material, and diopside is generated according to the theory: the anorthite is a crystal phase component with the ratio of 1:1, and pure substances are added, so that the ratio of CaO in the raw materials is as follows: SiO 2 2 ：Al 2 O 3 : MgO is 2:4:1: 1; and carrying out heat treatment on the prepared raw materials to obtain the microcrystalline glass. Compared with the traditional two-step heat treatment process, the one-step method for preparing the microcrystalline glass from the chromium-containing stainless steel slag shortens the industrial process, saves the energy and improves the chromium fixation property of the material.

Description

Process for preparing microcrystalline glass from chromium-containing stainless steel slag by one-step method
Technical Field
The invention relates to the field of microcrystalline glass, in particular to a process for preparing microcrystalline glass from chromium-containing stainless steel slag by a one-step method.
Background
Glass ceramics are a silicate material with good physical and chemical properties. The raw material components for preparing the microcrystalline glass are very similar to those of stainless steel slag, wherein Cr is 2 O 3 And Fe 2 O 3 Can be used as nucleating agent of microcrystalline glass. Therefore, when the chromium-containing stainless steel slag is used for producing the microcrystalline glass, no additional nucleating agent needs to be added. Studies have indicated diopside (Diop)side，CaMgSi 2 O 6 ) The base microcrystalline glass has good chromium fixing performance. The diopside phase microcrystalline glass prepared from the chromium-containing material can lead chromium element to generate MgCr 2 O 4 This insoluble phase prevents leaching of chromium from the stainless steel slag. Al (Al) 2 O 3 Is a common component in stainless steel slag, Anorthite (CaAl) 2 Si 2 O 8 ) May also be possible target crystalline phases. But the study on the microcrystalline glass system with anorthite and diopside coexisting is only reported at present.
Disclosure of Invention
The invention aims to provide a process for simultaneously separating out two crystal phases of anorthite and diopside in the preparation of microcrystalline glass by one-step heat treatment of Cr-containing stainless steel waste.
The technical scheme of the invention is as follows: a one-step method of preparing microcrystalline glass from chromium-containing stainless steel slag comprises the following steps of using the chromium-containing stainless steel slag as a raw material, generating diopside according to a theory: the anorthite is a 1:1 crystal phase component, and is added with a pure substance ratio, so that the ratio of CaO: SiO 2 2 ：Al 2 O 3 : MgO is 2:4:1: 1; and carrying out heat treatment on the prepared raw materials to obtain the microcrystalline glass.
In the process for preparing the microcrystalline glass by the one-step method from the chromium-containing stainless steel slag, the heat treatment is to put the prepared raw materials into a furnace at the speed of 4-6 ℃/min, raise the temperature to 900-1600 ℃, preserve the temperature for 2-4h, then lower the temperature to 400-600 ℃, preserve the temperature for 1.5-2.5h, anneal, cool and obtain the microcrystalline glass.
In the process for preparing the microcrystalline glass from the chromium-containing stainless steel slag by the one-step method, the prepared raw materials are put into a furnace at the speed of 5 ℃/min, heated to 1090 ℃ and kept for 4 hours, then cooled to 500 ℃ and kept for 2 hours for annealing and cooling to obtain the microcrystalline glass.
In the process for preparing microcrystalline glass from chromium-containing stainless steel slag by one-step method, 0.5-2 wt% of Na is added into the stainless steel slag 2 O、0.5-2wt％K 2 O and 0.5-2 wt% CaF 2 。
Foregoing description of the inventionIn the process for preparing microcrystalline glass from chromium-containing stainless steel slag by one-step method, 1 wt% of Na is added into the stainless steel slag 2 O、1wt％K 2 O and 1 wt% CaF 2 。
Advantageous effects
1. The invention is based on the components CaO and SiO of the actual chromium-containing steel slag 2 、MgO、Fe 2 O 3 、Al 2 O 3 、Cr 2 O 3 MnO, proposing theoretical generation of diopside: the anorthite is a 1:1 crystal phase component, and is added with a pure substance ratio, so that the ratio of CaO: SiO 2 2 ：Al 2 O 3 : MgO is 2:4:1:1, and the microcrystalline glass prepared by the method contains MnO and Fe which are common components in chromium-containing steel slag 2 O 3 The product of the doping still takes the spinel phase as the main component, so the microcrystalline glass prepared by the method has good chromium fixing performance.
2. Under the condition of heat preservation for 4 hours at the preferable heat treatment temperature of 1090 ℃ in the invention, even if the raw materials contain 5 percent of chromium after the preparation, a chromium-containing phase still does not appear in the product, chromium ions enter crystal lattices of diopside and anorthite, and magnesium ions and aluminum ions enter the crystal lattices of diopside and anorthite. The original lattice combines to form a new phase. This indicates that the formulation has better chromium fixation properties. In actual conditions, the chromium-containing steel slag does not contain more than 5% of chromium after being proportioned, so that the invention is carried out by only adding pure substances for proportioning without any treatment, the method is simple, and then the microcrystalline glass can be prepared by a one-step method.
3. Under the conditions of heat treatment temperature of 1090 ℃ and heat preservation for 4h, the prepared microcrystalline glass has good alkali resistance, no weight loss occurs in an alkali resistance experiment, and the alkali resistance is not influenced by chromium content. In addition, the acid resistance of the microcrystalline glass is not influenced by the content of chromium, and the weight loss rate can be reduced to 1.37% under the heat treatment condition.
4. Under the condition of 1090 ℃ in the invention, the temperature is kept for 4h, no fluxing agent is added, MnO and Fe 2 O 3 The doping of (2) hardly influences the hardness of the product, and the hardness of the product reaches 1447.1 HV.
5. In the present invention, if an excessive amount of flux is added, the melting point of the raw material is rather increased, and the amount of Na added is 1 wt% in the present invention 2 O，1wt％K 2 O，1wt％CaF 2 The melting point of the raw materials is the lowest under the condition of the composite fluxing agent, so that the energy consumption can be reduced.
6. Compared with the microcrystalline glass completely prepared from stainless steel slag, the microcrystalline glass prepared from the steel slag after the preparation of the invention is added with the fluxing agent, and then Cr 2 O 3 When the mass fraction of the chromium-containing phase reaches 5%, the chromium-containing phase only has a spinel phase, the chromium-fixing efficiency is good, and no chromium element is detected in a chromium leaching experiment.
7. The fluxing agent disclosed by the invention not only has the effect of reducing the melting point, but also has the effect of improving the hardness of the microcrystalline glass, and tests show that the hardness of the product is improved from 1447.1HV to 3049HV, and the hardness is improved by 110.7%.
8. The fluxing agent disclosed by the invention not only has the effect of reducing the melting point, but also has better acid resistance of a product using the fluxing agent than a product without the fluxing agent, and has the effect of improving the corrosion resistance of the microcrystalline glass. The weight loss rate of the product is increased from 1.37 percent to 0.667 percent.
10. Compared with the traditional two-step heat treatment process, the one-step method for preparing the microcrystalline glass from the chromium-containing stainless steel slag shortens the industrial process, saves the energy and improves the chromium fixation property of the material.
Drawings
FIG. 1 is an experimental scheme;
FIG. 2 is a view showing a heat treatment step;
FIG. 3 is a quaternary isothermic projection equilibrium phase diagram;
FIG. 4 is a graph of the resulting phase content of anorthite-diopside system calculated using factSage 7.2;
FIG. 5 is a plot of the resulting phase content for various chromium contents calculated using FaceSage 7.2;
FIG. 6 is a graph showing the change of a chromium-containing phase in a formed phase at 1400 ℃;
FIG. 7 is Fe 2 O 3 A generated phase content diagram of the doping system;
FIG. 8 is a graph of the content of the forming phase of the MnO doping system;
FIG. 9 is Fe 2 O 3 A generated phase content diagram of a MnO doping system;
FIG. 10 shows Na 2 O and K 2 A generated phase content diagram of an O doping system;
FIG. 11 is Na 2 O、K 2 O and CaF 2 A generated phase content diagram of the doping system;
FIG. 12 is P 2 O 5 Production phase content diagram of the doping system;
FIG. 13 is TiO 2 Production phase content diagram of the doping system;
FIG. 14 is P 2 O 5 With TiO 2 Production phase content diagram of the doping system;
FIG. 15 is a graph showing the results of DTA detection of a sample;
FIG. 16 is a macro topography of a sample;
FIG. 17 is a graph of XRD results of samples as a function of heat treatment temperature;
FIG. 18 is a graph of XRD measurements of samples affected by incubation time;
FIG. 19 is a microstructure diagram of samples at different incubation times, a: 3h, b: 4 h;
FIG. 20 is a block diagram of XRD detection of samples of different chromium content;
fig. 21 is a microstructure diagram of samples with different chromium contents, a: 2%, b: 3%, c: 4%, d:5 percent;
FIG. 22 is an enlarged view of the microstructure of 5 wt% chromium content;
FIG. 23 is a schematic diagram of a mechanism of crystallization;
FIG. 24 is a XRD detection result diagram of MnO and Fe2O3 doping;
FIG. 25 shows MnO and Fe 2 O 3 The microstructure of the doped sample, a is MnO; b is Fe 2 O 3 ；c:MnO,Fe 2 O 3 A drawing;
FIG. 26 is a graph of the results of acid resistance testing of samples; a: the influence of the heat treatment temperature; b: influence of incubation time; c: the effect of chromium content; d: influence of doping
FIG. 27 is a graph of hardness test results for samples; a: the influence of the heat treatment temperature; b: influence of incubation time; c: the effect of chromium content; d: the effect of doping;
FIG. 28 is a graph showing the results of DSC measurements of different temperature rise rates of a sample; a: is not doped; b: 3% MnO; c: 3% Fe 2 O 3 ；d：3％MnO、3％Fe 2 O 3 ；
Fig. 29 is a schematic diagram of data fitting, a: undoped; b: 3% MnO; c: 3% Fe 2 O 3 ；d：3％MnO、3％Fe 2 O 3 ；
FIG. 30 is Na 2 O+K 2 Graph of the effect of O on melting point;
FIG. 31 is CaF 2 Graph of the effect on melting point;
FIG. 32 is a graph of XRD detection results of different compositions;
FIG. 33 is a semi-quantitative analytical chart of XRD detection;
FIG. 34 is a microstructure of steel slag (a) and steel slag (b);
FIG. 35 is a micro-topography of a glass ceramic with the addition of a composite flux, b is a partial enlargement of a;
FIG. 36 is a plot of XRD measurements for samples of different chromium content;
FIG. 37 is a semi-quantitative analysis of the results of XRD measurements;
fig. 38 is a micro-topography of microcrystalline glasses with different chromium contents, a: 0.6 wt%, b:2 wt%, c:4 wt%, d:5 wt%;
FIG. 39 is TiO 2 And P 2 O 5 An XRD detection result graph of the added sample;
FIG. 40 is a semi-quantitative analysis of the results of XRD measurements;
fig. 41 is a microstructure diagram of a different doped sample, a: undoped, b: TiO 2 2 ，c：P 2 O 5 ，d：TiO 2 And P 2 O 5 ；
FIG. 42 is a graph of the effect of chromium content on sample hardness and acid and alkali resistance;
Detailed Description
The present invention will be described in further detail with reference to specific examples. The experimental procedures used below are, unless otherwise specified, all conventional procedures known in the art and the ingredients or materials used, if not specified, are all commercially available ingredients or materials. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention.
Example 1, a process for preparing microcrystalline glass from chromium-containing stainless steel slag by a one-step method.
The process takes chromium-containing stainless steel slag as a raw material, and generates diopside according to the theory: the anorthite is a crystal phase component with the ratio of 1:1, and pure substances are added, so that the ratio of CaO in the raw materials is as follows: SiO 2 2 ：Al 2 O 3 : MgO is 2:4:1:1, and 0.5 wt% of Na is added according to the amount of raw materials after preparation 2 O、0.5wt％K 2 O and 0.5 wt% CaF 2 And (3) putting the prepared raw materials into a tube furnace, heating to 1600 ℃ at the speed of 4 ℃/min, preserving heat for 2h, then cooling to 400 ℃, preserving heat for 2.5h, annealing, and cooling to obtain the microcrystalline glass.
Embodiment 2, a process for preparing microcrystalline glass from chromium-containing stainless steel slag by a one-step method.
The process takes chromium-containing stainless steel slag as a raw material, and generates diopside according to the theory: the anorthite is a crystal phase component with the ratio of 1:1, and pure substances are added, so that the ratio of CaO in the raw materials is as follows: SiO 2 2 ：Al 2 O 3 : MgO is 2:4:1:1, and 2 wt% Na is added according to the raw material amount after preparation 2 O、2wt％K 2 O and 2 wt% CaF 2 And (3) putting the prepared raw materials into a tube furnace, heating to 900 ℃ at the speed of 6 ℃/min, preserving heat for 4h, then cooling to 600 ℃, preserving heat for 1.5h, annealing, and cooling to obtain the microcrystalline glass.
Embodiment 3, a process for preparing microcrystalline glass from chromium-containing stainless steel slag by a one-step method.
The process takes chromium-containing stainless steel slag as a raw material, and generates diopside according to the theory: the anorthite is a 1:1 crystal phase component, and is added with a pure substance ratio, so that the ratio of CaO: SiO 2 2 ：Al 2 O 3 : MgO is 2:4:1:1, and 1 wt% of Na is added according to the amount of raw materials after preparation 2 O、1wt％K 2 O and 1 wt% CaF 2 The prepared raw materials are put into a tube furnace at a speed of 5 ℃/minAnd (3) raising the temperature to 1090 ℃ at a speed, preserving heat for 4h, then lowering the temperature to 500 ℃, preserving heat for 2h, annealing, and cooling to obtain the microcrystalline glass.
Examples of the experiments. To study the present invention, the inventors made a number of experiments, some of which are reported below:
content of study
Referring to fig. 1, a research idea of the experiment is made for the process of preparing microcrystalline glass from chromium-containing stainless steel slag.
(1)CaO-SiO 2 -Al 2 O 3 -MgO-Cr 2 O 3 Thermodynamic analysis of the System
The isothermal projection equilibrium phase diagram and the generated phase content of the microcrystalline glass prepared from the stainless steel slag are calculated by utilizing a thermodynamic software FactSage7.2 simulation, the influence of the chromium element content on the generated phase, the occurrence rule of the chromium element in the crystal phase and the influence of other doping agents including a fluxing agent and a crystal nucleating agent on the generated phase content are analyzed. So as to play a role in guiding the subsequent experiments theoretically.
(2) Experimental study on one-step preparation of microcrystalline glass by pure substance simulation chromium-containing stainless steel slag component
And with the calculation result as guidance, a microcrystalline glass experiment prepared by simulating the chromium-containing stainless steel slag component with pure substances is designed. According to the test result of the differential thermal analysis of the mother phase glass, the influence of the heat treatment system and the heat preservation time on the crystallization performance of the material is researched. After selecting the optimal heat treatment system, the chromium content, MnO and Fe are respectively researched as the common components in the stainless steel slag 2 O 3 The influence of doping on the crystallization and physical properties of the material. Finally, the part also analyzes MnO and Fe by using a crystallization kinetic method 2 O 3 And (4) doping. These glass-ceramics were tested for physical properties including hardness and chemical stability.
(3) Experimental research on one-step preparation of microcrystalline glass by actual steel slag
Under the guidance of thermodynamic calculation, according to the optimal heat treatment conditions, the actual electric furnace slag is used as a main component to prepare the microcrystalline glass. On the basis, the influence of the fluxing agent, the chromium content and the crystal nucleating agent on the crystallization performance of the microcrystalline glass is researched. The physical properties of the microcrystalline glass are tested, including a chromium leaching test, a hardness test and the like.
Second, experiment and characterization method
2.1 Experimental materials
The chemical reagents used in this experiment and their specifications are shown in Table 1
TABLE 1 main chemistry of the experiment
Figure BDA0003673608830000061
Figure BDA0003673608830000071
2.2 Experimental procedures
2.2.1 Steel slag and sample Components
Taking into account MgO and Al 2 O 3 The stainless steel slag is a common component of the stainless steel slag, the microcrystalline glass has better chromium fixation performance, and the experiment designs the theoretical generation of Diopside (CaMgSi) 2 O 6 ): anorthite (CaAl, Anorthite) 2 Si 2 O 8 )1:1, i.e., mol (CaO: SiO 2 2 ：Al 2 O 3 : MgO) ═ 2:4:1: 1. The actual steel slag used in the experiment was EAF stainless steel slag, and the chemical composition of the steel slag was determined by X-ray fluorescence spectroscopy (XRF, shimadzu XRF1800) as shown in table 2. The components of the actual steel slag are slightly different from those of the components, so that proper pure substances are added into the actual steel slag. The adjusted actual steel slag components and the components of the pure substance simulated steel slag are shown in the table 2-2.
TABLE 2 chemical composition of the subjects
Figure BDA0003673608830000072
2.2.2 one-step sintering
The weighed medicines are fully and uniformly mixed and placed in a corundum crucible (actual steel slag needs to be firstly ground to the granularity of 74 mu m), as shown in figure 2, part of samples are heated to 1400 ℃ at the speed of 5 ℃/min in a tube furnace (air atmosphere) and are kept warm for 4h, so that the samples are fully melted. And then cooling to the heat treatment temperature, preserving the temperature for a period of time, completing the nucleation and crystallization process of the sample in one step, and cooling to the room temperature to obtain the sample.
For analysis and kinetic analysis, another part of the uniformly mixed medicine is heated to 1400 ℃ and is kept warm for 4h in a muffle furnace at the speed of 5 ℃/min, and after the sample is fully melted, the sample is quickly cooled to 500 ℃ and is kept warm for 2h for annealing, and then the sample is cooled to room temperature to obtain the mother phase glass.
2.3 test and characterization methods
2.3.1X-ray diffraction analysis
And (4) grinding the sample, and then performing phase detection by using an X-ray diffraction analyzer. The apparatus is an X-ray diffractometer (D8 Advance) from AXS, Bruker, Germany. Testing parameters: the tube current is 40mA, and the tube voltage is 40 KV; a Cu target; light pipe type: a ceramic light pipe; scanning speed: 5 deg/min.
2.3.2 scanning Electron microscopy analysis
And (3) polishing the surface of the block sample to be smooth, placing the block sample in 1% HF to corrode a glass phase in the sample, and carrying out scanning electron microscope analysis after gold spraying. The apparatus used was a german ZEISS field emission scanning electron microscope (ZEISS Gemini 300).
2.3.3 differential thermal analysis
The sample is ground and then placed in a differential thermal analyzer for differential thermal analysis. The device is a Japanese precision nanometer high temperature type differential thermal-thermogravimetric synchronous analyzer (TG/DTA 7300). The experiment was carried out in an argon atmosphere and the sample was ramped up to 1200 ℃ at a ramp rate of 5 ℃/min and the mass change during the process was recorded.
2.3.4 microhardness test
And (3) polishing the surface of the block sample, and measuring the Vickers hardness of the material by a digital display microhardness instrument (DHV-1000Z), wherein the pressure head used for the experiment is a 136-degree positive diamond pressure head. And calculating the average pressure born by the conical surface area of the indentation to obtain the Vickers hardness value. The test conditions were: the test pressure was 9.8N, dwell time 15 s.
2.3.5 acid and alkali resistance test
Cleaning the prepared block sample, drying the block sample in a blast drying oven to constant weight, and weighing the mass M of the block sample 1 The unit: g. completely soaking the block sample with constant weight in 5% HCl or 5% NaOH for 1h, taking out, cleaning, drying in an air-blast drying oven to constant weight, and weighing to obtain the mass M 2 The unit: g. namely according to the formula:
Figure BDA0003673608830000081
calculating to obtain the mass loss rate C of the sample in acid-base environment Medicine for treating chronic hepatitis B 。
2.3.6 chromium leach test
Chromium leaching experiments were analyzed by measuring the amount of Cr in the leachate by ICP-oes (thermo ICAP pro). Preparation of the leachate according to the relevant regulations in GB/T33999-2017, the sample is ground to a particle size of 74 μm, and 10g of the sample is soaked in deionized water at room temperature. Stirring for 8h on a magnetic stirrer, and standing for 64h to obtain the leaching solution.
2.3.7 melting Point test
Grinding the sample into powder, making the powder into a cylinder, placing the cylinder in a muffle furnace, rapidly heating the cylinder in an air atmosphere, and judging the molten state of the sample by observing the shape of the sample in the heating process. The melting point of the sample is recorded and photographed when the sample reaches the hemispherical temperature.
Third, CaO-SiO 2 -Al 2 O 3 -MgO-Cr 2 O 3 Thermodynamic analysis of the System
The part uses thermodynamic software FactSage7.2 to CaO-SiO 2 -Al 2 O 3 the-MgO system is subjected to isothermal phase diagram equilibrium phase diagram and generated equilibrium phase content calculation. On the basis, Cr with different contents is added into the calculated raw materials 2 O 3 And other additives that may be used in subsequent experiments to investigate the effect of these ingredients on the system.
3.1 CaO-SiO 2 -Al 2 O 3 -MgO quaternary system heatLearning and calculating
3.1.1 Quaternary isothermal projection equilibrium phase diagram
To analyze the phase change of the experimental system at high temperature, the thermodynamic software, FactSage7.2, was used for CaO-SiO 2 -Al 2 O 3 The calculation of isothermal projection phase diagram is carried out by the MgO quaternary system, and the equilibrium phase composition and the composition value of the equilibrium point in the isothermal projection phase diagram are shown in Table 3. As shown, the calculated temperature range is 1000-1500 deg.C, where the mole fraction of MgO is fixed at 0.126.
TABLE 3 equilibrium phase composition at phase equilibrium Point
Figure BDA0003673608830000091
Figure BDA0003673608830000101
The calculation results showed that an equilibrium state in which anorthite and diopside coexist was generated at the equilibrium points 16 and 17, that is, at the composition X (SiO) 2 )＝0.53735，X(Al 2 O 3 ) 0.09796, X (cao) 0.36469 at 1244.04 ℃, and when component X (SiO) 2 )＝0.69960，X(Al 2 O 3 ) When the temperature is 1208.91 ℃, 0.09228, x (CaO) ═ 0.20812, mol (CaO: SiO 2 2 ：Al 2 O 3 : MgO) ═ 2:4:1:1 system, the points marked in the figure, show in the calculations that Melilite (Ca) may also form 2 (Al,Mg)[(Si,Al)SiO 7 ]) And SiO 2 。
3.1.2 Quaternary generated phase content calculation
Based on the above calculation results, as shown in FIG. 4, the component Mol (CaO: SiO) was calculated using the thermodynamic software FactSage7.2 2 :MgO:Al 2 O 3 ) The system 2:4:1:1 was subjected to the 900-sand 1600 ℃ phase formation calculation. The calculation result shows that the diopside and anorthite phases are generated in the system, and the diopside and the anorthite phases are all melted into liquid phase at 1400 ℃. Because of the phenomenon of homogeneous, the system also generatesOther monoclinic pyroxene phases. The system also has a wollastonite phase and SiO which does not completely participate in the reaction 2 。
3.2CaO-SiO 2 -Al 2 O 3 -MgO-Cr 2 O 3 Thermodynamic calculation of the system
3.2.1 influence of chromium content on the phase formation of the System
The reactant is added with Cr on the basis of the system 2 O 3 The increment and the calculation result are shown in fig. 5. Wherein the main component of spinel phase is Al 3 O 4 [1+]，AlO 4 [5-]，MgAl 2 O 4 ，AlMg 2 O 4 [1-]，Mg 3 O 4 [2-]，MgO 4 [6-]，MgCr 2 O 4 ，CrCr 2 O 4 [1+]，CrMg 2 O 4 [1-]，AlCr 2 O 4 [1+]，CrAl 2 O 4 [1+]，CrO 4 [5-]The main component of the monoclinic pyroxene phase is CaMgSi 2 O 6 ，MgMgSi 2 O 6 ，CaAl 2 SiO 6 ，MgAlAlSiO 6 ，CaAlSi 2 O 6 [1+]，MgAlSi 2 O 6 [1+]，CaMgAlSiO 6 [1-]，MgMgAlSiO 6 [1-]The main component of calcium chromium garnet is Ca 3 Cr 2 Si 3 O 12 。
Formed crystalline phase and no addition of Cr 2 O 3 The systems of (a) are substantially the same. With increasing chromium content, both systems were able to form anorthite and diopside phases, and tended to form anorthite. The content of spinel in the system is also Cr 2 O 3 The increase of (b) is remarkably increased, and in the calculation result, spinel phase and Cr are in 2 O 3 A clear negative correlation is shown, which can indicate that a large amount of chromium element is enriched in the spinel phase. Chromium element not enriched in spinel phase as Cr 2 O 3 And calcium aluminum garnet is present in the system.
3.2.2 distribution of chromium-containing phases
As shown in FIG. 6, the calculated Cr is different at 1400 deg.C 2 O 3 The existence phase of chromium element at the content. The results show that the bodyMost of chromium elements in the system are enriched in a spinel phase, so that the system has better chromium fixing performance. When Cr is present 2 O 3 When the content reaches 20 percent, the content of spinel phase in the system is not increased any more, and Cr 2 O 3 The content begins to increase, probably to a maximum value for the occurrence of the spinel phase of the system.
3.3 Effect of various additives on the phases formed
On the basis of the foregoing calculations, the ratio of various additives to anorthite was calculated using FactSage 7.2: influence of the formation phase of the microcrystalline glass prepared by high-temperature sintering of a system with the diopside ratio of 1: 1. Cr added in the calculation 2 O 3 All are 1 wt%.
3.3.1MnO、Fe 2 O 3 Influence on the phase formation
Doping with 3 wt% Fe as calculated by the thermodynamic software FactSage7.2, as shown in FIG. 7 2 O 3 The content of the generated phase of the latter system. Wherein the spinel phase is increased by Fe 3 O 4 [1+，1+，2-]，FeO 4 [5-，6-]，FeAl 2 O 4 ，Al 3 O 4 [1+]，AlFe 2 O 4 [1-]，FeAl 2 O 4 [1+]，AlFe 2 O 4 [1+]，MgFe 2 O 4 ，FeMg 2 O 4 [1-]，FeMg 2 O 4 [2-]，MgFe 2 O 4 [2-]，FeCr 2 O 4 ，CrFe 2 O 4 [1-]，FeCr 2 O 4 [1+]，CrFe 2 O 4 [1+]，CrFe 2 O 4 [2-]，CrFe 2 O 4 . In contrast to the undoped system, i.e., FIGS. 3-3, the system is in Fe 2 O 3 Under the action of (1), a corundum phase is newly generated, wherein the corundum phase comprises Al 2 O 3 、Cr 2 O 3 And Fe 2 O 3 The chromium-containing phase of the system is present in the corundum phase in addition to the spinel, as Cr 2 O 3 Exist in the form of (1).
From the phase content, the contents of the anorthite phase and the diopside phase are relatively close, and the anorthite phase is taken as a main crystal phase. In the range of 1200-1450 ℃, the dominant phase containing chromium in the system is spinelAnd (4) phase(s). Therein, it is noted that SiO 2 There may be a quantitative relationship of negative correlation between the content of diopside and anorthite.
FIG. 8 shows the content of the generated phase of the system doped with MnO of 3 wt% calculated by the thermodynamic software FactSage 7.2. Compared with the undoped system, namely figure 5, the system newly generates wollastonite, olivine, multiflower hectorite and corundum under the action of MnO. The main component of wollastonite is MgSiO 3 、CaSiO 3 And MnSiO 3 The main component of olivine is MgMgMgMgSiO 4 ，CaCaSiO 4 ，CaMgSiO 4 ，MgCaSiO 4 ，MnMnSiO 4 ，MnCaSiO 4 ，CaMnSiO 4 ，MnMgSiO 4 ，MgMnSiO 4 The main component of the rose pyroxene is MnSiO 3 ，CaSiO 3 ，MgSiO 3 The corundum is mainly composed of Al 2 O 3 ，Cr 2 O 3 And Mn 2 O 3 . In addition, spinel has a tetragonal system in addition to the aforementioned cubic system. The chromium-containing phase of the system appears in the corundum phase besides the spinel, and is Cr 2 O 3 Exist in the form of (1).
On the whole, before 1200 ℃, the system mainly precipitates an anorthite phase, the olivine phase and the multiflower hectorite phase in the system are obviously reduced at 1030 ℃, and the diopside and the anorthite are greatly increased relatively.
Doping with 3 wt% Fe as calculated by the thermodynamic software FactSage7.2, as shown in FIG. 9 2 O 3 And 3 wt% MnO. In contrast to the undoped system, i.e. FIG. 5, the system is in Fe 2 O 3 With MnO, olivine, corundum and multiflora rose pyroxene phases are formed. Olivine is increased by FeFeSiO 4 ，MgFeSiO 4 ，FeMgSiO 4 ，CaFeSiO 4 ，FeCaSiO 4 ，FeMnSiO 4 ，MnFeSiO 4 . The main component of the corundum phase comprises Al 2 O 3 ，Cr 2 O 3 ，Fe 2 O 3 ，Mn 2 O 3 . The main component of the rose pyroxene is MnSiO 3 ，CaSiO 3 ，FeSiO 3 ，MgSiO 3。 Similar to fig. 8, the spinel phase in the system appears tetragonal in addition to the cubic system. The chromium-containing phase of the system appears in the corundum phase in addition to the spinel, as Cr 2 O 3 Exist in the form of (1).
Before 1200 ℃, the system mainly precipitates anorthite phase. Combining the first two groups of calculated structures, the doping of MnO mainly influences the reaction of the system at 1030 ℃, the doping of MnO can lead the system to generate a spodumene phase, wollastonite and olivine phases, and Fe 2 O 3 The doping of (2) has less influence on the generated phase of the system.
3.3.2Na 2 O、K 2 O、CaF 2 Influence on the phase formation
As shown in FIG. 10, it is calculated by the thermodynamic software FactSage7.2 and doped with 1 wt% Na 2 O and K 2 Content of generated phase of post-O system. In contrast to the undoped system, i.e. FIG. 5, the system is in Na 2 O and K 2 Wollastonite, melilite, corundum, garnet, pyroxene and feldspar phases are also formed under the action of O. Wherein the main component of the wollastonite is MgSiO 3 ，CaSiO 3 The main component of melilite is Ca 2 Al 3 O 7 [1-]，Ca 2 AlSi 2 O 7 [1+]，Ca 2 MgSi 2 O 7 ，Ca 2 MgAl 2 O 7 [2-]The corundum is mainly composed of Al 2 O 3 And Cr 2 O 3 Garnet of Ca as the main component 3 Cr 2 Si 3 O 12 ，Ca 3 Al 2 Si 3 O 12 The main component of pyroxene is NaAlSiO 4 ，KAlSiO 4 ，Si 2 O 4 ，CaAl 2 O 4 ，CaAl 2 Si 2 O 8 The main component of feldspar is NaAlSi 3 O 8 ，KAlSi 3 O 8 ，CaAl 2 Si 2 O 8 . The chromium-containing phase of the system is present in the corundum phase and in the garnet phase in addition to the spinel, with Cr 2 O 3 And Ca 3 Cr 2 Si 3 O 12 Shape ofThe formula (I) exists.
As shown in FIG. 11, it is calculated by the thermodynamic software FactSage7.2 and doped with 1 wt% Na 2 O、K 2 O and CaF 2 The content of the generated phase of the latter system. In contrast to the undoped system, i.e. FIG. 5, the system is in Na 2 O、K 2 O and CaF 2 Under the action of the catalyst, melilite, corundum, pyroxene and feldspar phases are generated, and in addition, KAlSi is also generated 2 O 6 ，Ca 4 Si 2 F 2 O 7 . The corundum content is less than that listed in the figure. Wherein the yellow feldspar contains Ca as main component 2 AlSi 2 O 7 [1-]，Ca 2 AlSi 2 O 7 [1+]，Ca 2 MgSi 2 O 7 ，Ca 2 MgAl 2 O 7 [2-]The corundum component is Al 2 O 3 And Cr 2 O 3 The main component of pyroxene is NaAlSiO 4 ，KAlSiO 4 ，Si 2 O 4 ，CaAl 2 O 4 ，CaAl 2 Si 2 O 8 The main component of feldspar is NaAlSi 3 O 8 ，KAlSi 3 O 8 ，CaAl 2 Si 2 O 8 . The chromium-containing phase of the system appears in the corundum phase in addition to the spinel, as Cr 2 O 3 Exist in the form of (1).
3.3.3TiO 2 、P 2 O 5 Influence on the formation of phases
Doping with 3 wt% P as calculated by the thermodynamic software FactSage7.2, as shown in FIG. 12 2 O 5 The content of the generated phase of the latter system. In contrast to the undoped system, i.e. FIG. 5, the system is at P 2 O 5 Also produces the clinoptilolite, protoporphyrin, corundum and Ca 3 P 2 O 8 ，Mg 3 P 2 O 8 ，Ca 3 Mg 3 P 4 O 16 ，Mg 3 Mg 3 P 4 O 16 . The minor of which are not listed in figure 12. The main component of the clinoptilolite phase is CaMgSi 2 O 6 ，MgMgSi 2 O 6 ，CaAl 2 SiO 6 ，MgAlAlSiO 6 ，CaAlSi 2 O 6 [1+]，MgAlSi 2 O 6 [1+]，CaMgAlSiO 6 [1-]，MgMgAlSiO 6 [1-]The protophorite phase comprising CaMgSi 2 O 6 ，MgMgSi 2 O 6 ，CaAl 2 SiO 6 ，MgAlAlSiO 6 ，CaAlSi 2 O 6 [1+]，MgAlSi 2 O 6 [1+]，CaMgAlSiO 6 [1-]，MgMgAlSiO 6 [1-]The main component of corundum phase is Al 2 O 3 And Cr 2 O 3 . The chromium-containing phase of the system appears in the corundum phase in addition to the spinel, as Cr 2 O 3 Exist in the form of (1).
It can be seen from the figure that around 1030 ℃ there may be some conversion of the orthorhombic pyroxene to other pyroxene and quartz phases. It is noteworthy that the system was producing anorthite phase under the calculation conditions.
FIG. 13 shows the doping of 3 wt% TiO as calculated by the thermodynamic software FactSage7.2 2 The content of the generated phase of the latter system. In contrast to the undoped system, i.e. FIG. 5, the system is on TiO 2 Under the action of the catalyst, corundum and CaSiTiO are also generated 5 . Wherein the corundum phase contains Al as main component 2 O 3 And Cr 2 O 3 . The chromium-containing phase of the system is mainly spinel, and besides, the chromium-containing phase also appears in the corundum phase, and is Cr 2 O 3 Exist in the form of (1).
Doping with 3 wt% P as calculated by the thermodynamic software FactSage7.2, as shown in FIG. 14 2 O 5 And TiO 2 The content of the generated phase of the latter system. In contrast to the undoped system, i.e. FIG. 5, the system is at P 2 O 5 And TiO 2 Under the action of the catalyst, corundum and CaSiTiO are also generated 5 ，Ca 3 Mg 3 P 4 O 16 ，Mg 3 Mg 3 P4O 16 And a protophorite phase (the less abundant phases are not listed in the figure). Wherein the main component of the protoporphyrinite phase is CaMgSi 2 O 6 ，MgMgSi 2 O 6 ，CaAl 2 SiO 6 ，MgAlAlSiO 6 ，CaAlSi 2 O 6 [1+]，MgAlSi 2 O 6 [1+]，CaMgAlSiO 6 [1-]，MgMgAlSiO 6 [1-]. The main component of corundum phase is Al 2 O 3 And Cr 2 O 3 . The chromium-containing phase of the system is mainly spinel, and besides, the chromium-containing phase also appears in the corundum phase, and is Cr 2 O 3 Exist in the form of (1). From the content, the system mainly precipitates anorthite phase. The chromium-containing spinel phase and the chromium-containing corundum phase show obvious negative correlation.
3.4 nodules
Thermodynamic software FactSage7.2 for mol (CaO: SiO) is used in this chapter 2 ：Al 2 O 3 : the MgO) -2: 4:1:1 system is subjected to isothermal projection equilibrium phase diagram and generated phase calculation, and the influence of the chromium content on the generated phase content and other various dopings including Fe are analyzed and calculated by the method 2 O 3 ，MnO，Na 2 O，K 2 O，CaF 2 ，TiO 2 And P 2 O 5 Influence of doping on the content of the generated phases. The main conclusions can be summarized as follows:
(1) in the absence of Cr 2 O 3 In the system of (a), an isothermal projection equilibrium phase diagram shows that in the case of the experimental components, a crystalline phase in which mol (diopside: anorthite) is 1:1 can be generated as expected. The results in the generated phase simulation calculations show that wollastonite, silica and other monetites are present in addition to diopside and anorthite in the generated phase.
(2) Different contents of Cr are added in the calculation conditions 2 O 3 To investigate the effect of chromium content on the generated phase. The results show that the addition of chromium makes the system appear spinel phase and calcium-chromium-garnet phase. From the phase content point of view, the system is more prone to precipitate anorthite phases. Added Cr 2 O 3 Mainly exists in a spinel phase in the system. Simulation calculation results show that the maximum enrichment degree of the system to Cr is 10-20 wt% at 1400 ℃. The rest of the chromium is Cr 2 O 3 And calcium chromium garnet.
(3) Other usual additives were added to the calculation conditions. MnO and Fe 2 O 3 The doping of (A) causes corundum, olivine andmultiflora rose pyroxene; na (Na) 2 O，K 2 O and CaF 2 The addition of the component (A) enables the system to generate other phases such as melilite, wollastonite, garnet, corundum and the like; TiO 2 2 And P 2 O 5 The addition of (a) mainly results in the formation of protophordeines and orthodiopsides from the system. The chromium-containing phase in the additives of the above groups still takes the spinel phase as the main component, which can ensure the chromium-fixing performance of the material.
Fourth, experimental study of microcrystalline glass crystallization prepared by one-step method by using pure substance to simulate steel slag components
Through the calculation of the thermodynamics of the system, the method obtains the content of the SiO 2 ：CaO：Al 2 O 3 : MgO) ═ 4:2:1:1 theoretical melt balance phase composition of the experimental formulation. In the part, the pure substances are used for simulating the components of the steel slag to study the heat treatment temperature and the heat preservation time. The influence of the Cr content was investigated according to a determined heat treatment schedule to analyze the mechanism of action of Cr element in the system. The crystallization kinetics method was used to analyze Fe 2 O 3 And MnO. Finally, the physical properties of the material are characterized.
4.1 influence of Heat treatment temperature and holding time on devitrification of glass ceramics
In order to research the one-step preparation of the microcrystalline glass by the actual steel slag, the microcrystalline glass is prepared by using pure substances to simulate the components of the chromium-containing stainless steel slag by the one-step method on the basis of the thermodynamic calculation, and the components in the experiment are shown in Table 4.
TABLE 4 chemical composition of the experimental samples
Figure BDA0003673608830000151
The prepared mother phase glass was subjected to differential thermal analysis, and the results are shown in fig. 15. As shown, there is an endothermic peak at 760 ℃, i.e., glass transition temperature T G (ii) a The curve has obvious crystallization exothermic peak and crystallization peak temperature T P And about 1030 deg.c. The exothermic peak is sharp, which indicates that the alkali glass has strong tendency of spontaneous transformation into crystal, and has strong crystallization capacity in the crystallization process, mainly bulk crystallization. Due to the fact thatAccording to the DTA result, the technical requirements of simultaneously completing nucleation and crystallization by a one-step method are met, the temperature of one-step heat treatment is 780 ℃, 880 ℃, 960 ℃, 1000 ℃, 1030 ℃ and 1090 ℃, and the heat preservation time is 2 hours. The temperature rise rate is controlled at 5 ℃/min.
4.1.1 Heat treatment temperature
The prepared mother phase glass is fired according to the heat treatment temperature to obtain the microcrystalline glass. Fig. 16 shows the macro morphology of the microcrystalline glass at heat treatment temperatures of 780 ℃ and 1090 ℃. It is clear that with the increase of the heat treatment temperature, the crystal phase gradually precipitates, the sample becomes dense, and the glass gloss gradually disappears. The bubbles in fig. 16 may indicate that the formulation has too high a viscosity at high temperature, so that the melt spreads slowly and the internal bubbles cannot be discharged in time.
Fig. 17 shows XRD test results of the glass-ceramics prepared at different heat treatment temperatures. As the heat treatment temperature increases, it can be seen that crystallization is best at 1090 ℃. The higher crystallization temperature compared to other diopside-based microcrystalline glasses may be due to the higher crystallization temperature of anorthite. For the sample with the heating temperature of 1090 ℃, the crystallization peaks with the XRD scanning angle smaller than 30 degrees are anorthite, which indicates that the crystallization peak temperature of the anorthite is higher. In semi-quantitative analysis of the XRD detected structure, the relative content of diopside and anorthite was about 4:6, indicating that anorthite precipitates more easily than diopside during crystallization.
4.1.2 incubation time
As previously described, a heat treatment temperature of 1090 ℃ was determined. This section investigated the effect of different holding times during the heat treatment stage on crystallization.
FIG. 17 shows XRD test results for samples with incubation times of 1h, 2h, 3h and 4 h. It can be seen that the sample crystallized incompletely for 1h, and the crystallization peak was not evident. Table 5 shows the results of semi-quantitative analysis of samples incubated for 2h, 3h and 4 h. Wherein, SiO 2 Only detected in the 2h sample, and not in the 3h and 4h samples. This may be due to incomplete 2h crystallization, resulting in a portion of SiO 2 There was no reaction. In addition, as the incubation time was extended, Mg was also detected 2 Si 2 O 6 And (4) generating. Semi-quantitative analysis from XRDThe proportion of anorthite to diopside shows that more anorthite is separated out with the prolonged heat preservation time. FIG. 19 is SEM pictures of incubation for 3h and 4h, respectively, with the grains growing gradually as the incubation time is prolonged.
TABLE 5 semi-quantitative analysis of XRD results
Figure BDA0003673608830000161
4.2 chromium content, MnO and Fe 2 O 3 Effect of doping on devitrification of microcrystalline glasses
Samples with chromium contents of 2%, 3%, 4% and 5% (wt%) were prepared according to the above-described base glass chemistry. The heat treatment process is carried out at 1090 ℃ for 4 h.
4.2.1 chromium content
Four groups of samples having a chromium content distribution of 2%, 3%, 4% and 5% were prepared according to the heat treatment regime determined in the previous experiment, i.e. heat preservation at 1090 ℃ for 4 h. Fig. 20 shows XRD detection results of the samples, and table 6 shows semi-quantitative analysis of the XRD results. From the results of the examination, it can be seen that the main crystal phase of the sample did not change with the increase of the chromium content. When the chromium content in the sample increased to 2%, new MgAl appeared 2 O 4 And (4) phase(s). As the chromium content continues to increase, the proportions of the phases in the sample do not change. Compared with the calculation results of the thermodynamic software, the crystal phase of the sample is basically consistent with the calculation results.
TABLE 6 semi-quantitative analysis of XRD assay structures
Table 4-3 Semi-quantitative analysis of structure detected by XRD
Figure BDA0003673608830000171
As the chromium content increased, a large number of bubbles appeared on the sample. Mills believes that it is possible for unreacted SiO in the silicate system 2 Formation of a large amount of interconnected crystal structure of silicon tetroxide, resulting in an increase in melt viscosity [78] 。
Fig. 21 is an SEM photograph of the sample. The chromium content of the samples was 2%, 3%, 4% and 5% from left to right and top to bottom, respectively. It can be seen from the figure that as the chromium content increases, finer and non-uniform grains appear in the sample, which is consistent with the trend of the XRD test results in decreasing the strength of the main crystal phase. The single diopside crystal phase should exhibit a dendritic morphology, which indicates that bulk grains appear in addition to some dendritic grains. Fig. 22 is a partial enlarged view of a sample having a chromium content of 5%. It can be seen that some grains in the sample exhibited a tendency to fuse.
Shuai Zhang states that this observation can be explained in two ways. First, Cr 3+ The characteristic behavior in the crystal field is believed to determine Cr 2 O 3 The solubility of (a). In short, Cr 3+ More common transition metal ions such as Fe 2+ And Mn 3+ Has higher OPSE (octahedral site preference) (Cr) 3+ ＝195523J/mol，Fe 2+ ＝16328J/mol，Mn 3+ 105926J/mol), i.e. Cr 3+ Preferentially occupying octahedral sites of the crystal field.
On the other hand, in the previous analysis of diopside, it was found to have a chain silicate structure whose silica skeleton is [ Si 2 O 6 ]. The oxygen at the top of the silicon oxygen chain forms a small octahedral space, while the oxygen at the bottom of the silicon oxygen chain forms a large distorted octahedral space. Also, when adding Cr to diopside system 2 O 3 Of (b) is Cr 3+ Can occupy octahedral space to replace Mg 2+ Resulting in dissolution. Anorthite is a framework silicate mineral whose silica unit is [ SiO ] 4 ]Tetrahedral, partially aluminium oxide tetrahedron [ AlO 4 ]Instead, an excessive negative charge occurs. These excess negative charges must be neutralized by cations. There may be more octahedral spaces between the silica chains of anorthite due to isomorphic phenomena.
Therefore, as shown in FIG. 23, Cr in the chromium-containing solid waste 3+ Can occupy the octahedral space of the generated diopside and anorthite system to replace Mg 2+ And Al 3+ Resulting in dissolution. From SEM, with increasing chromium contentAdditionally, fine grains appeared gradually in the graph, possibly indicating free Mg as chromium ions entered 2+ And Al 3+ With unreacted SiO 2 Combine to form MgAlO 4 And Mg 2 Si 2 O 6 . And the intensity of the characteristic peak in XRD decreases because smaller and smaller grains may be one of the reasons as new phases are generated.
4.2.2MnO，Fe 2 O 3
MnO and Fe 2 O 3 Is a common component in stainless steel slag and MnO and Fe are analyzed and researched 2 O 3 On the basis of the above experiments, three groups of experiments shown in table 7 were designed for the influence of stainless steel slag on the preparation of microcrystalline glass.
As shown in fig. 24, the XRD detection results of the samples are shown, and table 8 shows the semi-quantitative analysis results of XRD. As can be seen from the figure, MnO and Fe 2 O 3 The doping of (A) has little influence on the main crystal phase, and the overall crystallization peak intensities are almost the same. Both reduced the content of anorthite. In addition, semi-quantitative analysis shows that Mg in the system 2 Si 2 O 6 The content of (B) is slightly reduced, while MgAl 2 O 4 The relative content of (a) is increased.
TABLE 7 MnO, Fe 2 O 3 Doped experimental project
Table 4-4 MnO,Fe 2 O 3 doping experimental project
Figure BDA0003673608830000181
TABLE 8 semi-quantitative analysis of XRD measurements
Figure BDA0003673608830000182
FIG. 25 shows MnO and Fe 2 O 3 MnO and Fe 2 O 3 SEM photograph of doping. Larger and collapsed particles can be seen in the picture of doped MnO. In Fe 2 O 3 In the picture of the doping, it is,we can see uniform and very fine particles. Two types of doped sample shapes and Fe 2 O 3 Similarly. MnO and Fe are observed from the scanning electron microscope test image of the sample 2 O 3 The crystal phase of the glass ceramic is more uniform.
4.3 Performance testing
4.3.1 chemical stability
The chemical stability and hardness of the material were tested as shown in fig. 26. The material has good stability in alkaline environment, and loss rate data measured in laboratory environment is almost zero, so the loss rate data is not listed in the figure. As can be seen from fig. 26, the temperature has a greater effect on the acid resistance of the material than the holding time and chromium content. Higher weight loss may result because the glass-ceramic is not sufficiently crystallized at lower temperatures. Within the error range of the test in the article, the chromium content has little influence on the acid resistance. MnO and Fe 2 O 3 The addition of (b) reduces acid resistance.
4.3.2 hardness
Fig. 27 shows the effect of heat treatment temperature, time and chromium content on the hardness of the microcrystalline glass. As shown in the figure, the hardness of the microcrystalline glass is gradually improved along with the increase of the heat treatment temperature and the heat preservation time. In FIG. 27(c), the sample with 1% by mass of chromium has a significantly higher chromium content than the other samples with chromium content, and the chromium content has little effect on the chromium content as the chromium content continues to increase. In several groups of doping experiments, Fe 2 O 3 The addition of (b) increases the hardness of the sample, while the MnO decreases the hardness.
4.4 kinetics of crystallization
For better analysis of MnO and Fe 2 O 3 The influence on the crystallization performance of the microcrystalline glass prepared from the chromium-containing stainless steel slag by the one-step method is analyzed and researched by utilizing a crystallization kinetics method in the section.
In the kinetics of crystallization, the activation energy (E) of crystallization and the crystal growth index (n) are two important indicators for analyzing glass. White et al combined with Augis-Bennett's formula investigated the crystal growth index with Cr 2 O 3 The amount of the compound is changed. They can useHas shown that Cr 2 O 3 The increase in the content contributes to an increase in the crystal growth index. Therefore, increasing the phase transformation ratio is advantageous to reduce the initial crystallization time. In addition, Cr 2 O 3 The addition of (2) also contributes to the reduction of the crystallization activation energy. The doping of MnO is beneficial to the growth of spinel crystals and the enrichment of chromium in spinel phase. The effect of MnO on the crystallization kinetics of this material needs further investigation.
The kinetics of phase transitions in glass can be expressed by the JMA equation:
-ln(1-x)＝(kt) n
wherein x is the volume fraction of precipitated phases in the glass when t is, n is the crystal growth index, k is the reaction constant in the crystallization process, and can be determined by an Arrhenius equation:
Figure BDA0003673608830000191
where T is the absolute temperature, upsilon is the frequency factor, E is the crystallization activation energy of the glass, and R is the gas constant. Combining these two equations, one can derive equations describing the crystallization kinetics of the glass in a non-isothermal state:
Figure BDA0003673608830000192
T P the temperature corresponding to the crystallization peak is denoted as a temperature increase rate. By testing the crystallization peak temperatures corresponding to the same glass sample at different heating rates, an ln ((T _ P ^2)/a) -1/T _ P coordinate graph can be drawn, and the crystallization activation energy of the glass sample can be calculated according to the slope of a fitted line. Meanwhile, the crystal growth index n can be calculated by the Augis-Bennett equation:
Figure BDA0003673608830000201
in the formula, Δ T is the full width at half maximum corresponding to the maximum crystallization exothermic peak in the curve.
Based on the above composition, is not dopedDoped with 3% MnO and 3% Fe 2 O 3 3% MnO and 3% Fe 2 O 3 The DSC results of the samples showed heating rates of 10, 15, and 20 ℃/min, respectively, and the chromium content at 5% is shown in FIG. 28.
As shown in FIG. 29, based on the results obtained in FIG. 28, the four types of crystallized glasses were plotted
Figure BDA0003673608830000202
And (5) a coordinate graph.
The crystallization activation energy (E) and the crystal growth index (n) of the glass ceramic were calculated, and the results are shown in FIG. 9. MnO and Fe 2 O 3 The doping of (a) results in an increase in the devitrification activation energy and both decrease the growth index of the system. Fe 2 O 3 And MnO is added to inhibit the crystallization of the system.
TABLE 9 Crystal activation energy and Crystal growth index of the samples
Figure BDA0003673608830000203
4.5 nubs
In this chapter, experimental research is carried out on microcrystalline glass prepared by pure substance simulation stainless steel slag-containing component one-step method, and the main research content comprises the preparation process conditions of the microcrystalline glass, including heat treatment temperature and heat preservation time. In addition, the influence of chromium element on crystallizing of the microcrystalline glass is researched by simulating the stainless steel slag component by using pure substances and adjusting the chromium content in the raw materials. Finally, MnO and Fe 2 O 3 As a common component in chromium-containing stainless steel slag, MnO and Fe were studied 2 O 3 The influence of doping on the crystallization and physical properties of the material. The conclusion of the research in this chapter can be summarized as follows:
(1) as the heat treatment temperature and holding time increased, the crystallization of the sample became more and more complete. The optimal heat treatment system is 1090 ℃ and 4 h;
(2) as the chromium content increased until 5%, almost no chromium-containing phase appeared in the sample, chromium ions entered diopside and calcium ions grewIn the crystal lattice of the stone, magnesium ions and aluminum ions enter the crystal lattices of diopside and anorthite. The original lattice combines to form a new phase. This indicates that the formulation has better chromium fixation properties. MnO and Fe 2 O 3 The doping may reduce magnesium spinel precipitation and increase aluminosilicate.
(3) Under the test conditions, the samples had good alkali resistance. The acid resistance is gradually increased along with the increase of the heat treatment temperature, and the heat preservation time and the chromium content have little influence on the acid resistance of the sample. The weight loss rate is the lowest and is 1.37 percent under the conditions that the heat treatment temperature is 1090 ℃ and the heat preservation is carried out for 2 hours. MnO and Fe 2 O 3 The doping of (2) has little effect on the chemical stability. With the increase of the heat preservation time and the heat treatment temperature, the Vickers hardness of the sample is gradually improved, and the influence of the chromium content on the hardness of the sample is small. The optimal hardness is 1447.1 when the heat treatment temperature is 1090 ℃ and the heat preservation time is 4 hours. MnO and Fe 2 O 3 The doping of (a) has little effect on the hardness.
(4) In the crystallization kinetic analysis, MnO and Fe were obtained by fitting DSC data 2 O 3 Influences on the crystallization activation energy of the microcrystalline glass prepared by simulating the chromium-containing stainless steel slag component on pure substances. The results showed that the undoped crystal activation energy was 126.5KJ and the crystal growth index was 4.21. MnO and Fe 2 O 3 The doping improves the crystallization activity of the glass ceramics and reduces the crystallization capacity of the glass.
Fifth, research on one-step method for preparing microcrystalline glass by actual steel slag
By researching the raw material proportion and the heat treatment system, in order to verify the feasibility of the formula in the actual steel slag, the microcrystalline glass is prepared by taking the actual electric furnace slag as the raw material. Several additives commonly used in the smelting of glass ceramics and steel, such as the flux Na, were studied 2 O、K 2 O、CaF 2 And mixed crystal nucleus agent TiO 2 And P 2 O 5 The influence of (c). On the basis of actual steel slag, the content of Cr element in the raw material is changed to analyze the influence of the Cr content. Finally, the microcrystalline glass of the part is subjected to physical property characterization and Cr leaching test.
5.1 Effect of fluxing agent on actual Steel slag melting Point
Stainless steel slag generally has a relatively high melting point. In order to reduce the energy consumption for preparing the microcrystalline glass, Na is added on the basis of actual steel slag in the experiment of the part 2 O+K 2 O and CaF 2 Two fluxes are mixed, microcrystalline glass is prepared, and the influence of the two fluxes on the actual steel slag melting point and the phase and microstructure of the microcrystalline glass is researched.
5.1.1 melting Point analysis
To study Na 2 O+K 2 The effect of O on melting point, a comparative experiment as in table 10 was designed. The actual steel slag and the formulated steel slag compositions are shown in Table 11. By adding analytically pure SiO to the actual steel slag 2 MgO and Al 2 O 3 To obtain prepared steel slag
TABLE 10-Na 2 O+K 2 Experimental project for influence of O on melting point
Figure BDA0003673608830000221
TABLE 11 actual and formulated Steel slag compositions
Figure BDA0003673608830000222
The melting points of the respective sets of samples are shown in FIG. 30. The melting point of the original steel slag is remarkably reduced after the configuration, which is probably because SiO is added in the configuration process 2 The result is. 1 wt% Na 2 O+K 2 O also caused a significant drop in the melting point of the sample, probably due to Na 2 O and K 2 O is a network external body, the content of the O and the content of the O are increased, the number of the provided free oxygen is increased, and the function of breaking the network is achieved, so that the glass structure becomes loose, the viscous flow and the mass transfer process are accelerated, and the sample can be sintered, crystallized and flattened at a lower temperature.
However, when the amount is too large, sintering is adversely affected. This may be due to excessive Na 2 O and K 2 O makes the crystal lowerPrecipitation at temperature, which adversely affects sintering. Thus 1 wt% Na was added 2 O+K 2 O is a preferred choice.
On the basis of the above experiments, CaF was continuously studied 2 Influence on the melting point. CaF 2 As a fluxing agent and a crystal nucleus agent commonly used in the process of smelting microcrystalline glass and steel, CaF is necessary to be subjected to process research 2 The effects of (a) were investigated. Several sets of experiments as shown in table 12 were designed.
TABLE 12 CaF 2 Experimental items on influence of melting point
Figure BDA0003673608830000223
Figure BDA0003673608830000231
The test results are shown in fig. 31. CaF 2 The influence on the melting point is not as good as that of Na 2 O+K 2 O is evident. A small amount slightly lowers the melting point of the system, but more CaF 2 So that the melting point of the system is instead higher. Thus 1 wt% CaF was added 2 Is a more ideal choice.
5.1.2 phase analysis
Based on the above experiment, the original steel slag, the steel slag after preparation and the steel slag are mixed with 1 wt% of Na 2 O+1wt％K 2 O+1wt％CaF 2 The sample of (2) is prepared into microcrystalline glass, and as shown in fig. 32, the XRD detection result of the sample is shown, and 5-4 is semi-quantitative analysis of the XRD result. The steel slag after being prepared has larger difference compared with the phase generated in the original steel slag system. The crystal phase in the steel slag system is gehlenite and Ca 2 SiO 4 Mainly calcium aluminum garnet, and the steel slag after preparation is similar to the calculation result, mainly anorthite and diopside, and in addition, a small amount of MgSiO is generated 3 . From fig. 33, it is understood that the system is more likely to form anorthite, and the relative content of anorthite is 52% and the relative content of diopside is 44% in the material without flux, which are relatively close to each other. Flux-added bodyThe content of anorthite in the system is slightly increased to 55 percent, and the relative content of diopside is reduced to 35 percent 3 From 4% to 4%. Different from the calculation result, calcium aluminum garnet is not seen in the detection result.
5.1.3 microstructural analysis
The set of samples was analyzed using a scanning electron microscope, and the results are shown in fig. 34. The microscopic morphology of the samples prepared entirely from steel slag is in the form of uniformly sized particles, which results in poor mechanical properties, low brittleness and low hardness of the actual samples. The configured sample has a layered microscopic appearance, and irregular holes are distributed on the sample. A particle phase of uniform size is visible in the pores.
The effect of the composite flux on the sample micro-topography is shown in fig. 35. The composite fluxing agent effectively reduces the melting point of the system, the microscopic appearance is in the form of particles with uniform size, the particles are distributed in clusters, and the whole body is compact.
5.2 influence of chromium content of steel slag on devitrification of microcrystalline glass prepared by one-step method of steel slag preparation
In the experiment, the influence of the chromium content in the steel slag on the crystallization performance of the microcrystalline glass prepared by the actual steel slag one-step method is researched by means of phase analysis, microstructure scanning and the like.
5.2.1 phase analysis
On the basis of the above-mentioned components, Cr was produced as shown in Table 13 2 O 3 Samples with mass fractions of 2, 3, 4 and 5. The XRD detection results are shown in fig. 36. FIG. 37 is a semi-quantitative analysis of the XRD detection results of the samples. The detection result is basically consistent with the calculation result. The chromium element is completely enriched in the spinel phase, and the chromium element is not detected in other phases. As the chromium content increased, the system appeared to have more spinel phase, and semi-quantitative analysis showed that the system was more prone to anorthite formation. The peak intensity of the system shows a downward trend, probably because the system generates more new phases as the chromium element increases, and the spinel containing the chromium element as a nucleating agent induces more homogeneous phenomena to appear. From semi-quantitative analysis of XRD, when the chromium content increasesAt 3 wt% addition, a more pronounced chromium-containing phase appeared in the system. The chromium-containing phase only exists in the spinel phase, so that the system has better chromium fixing performance.
TABLE 13 Experimental items for the influence of chromium content
Figure BDA0003673608830000241
5.2.2 microstructural analysis
The set of samples was analyzed using a scanning electron microscope, and the results are shown in fig. 38. The increase of the chromium content changes the shape of the crystal grains, so that the original granular crystal grains are changed into strips with irregular shapes, compared with a sample with less chromium content, the pores are slightly increased, and the density shows a descending trend.
5.3 influence of nucleating agent on crystallization of microcrystalline glass prepared by steel slag one-step method
5.3.1 phase analysis
As shown in Table 14, TiO was investigated on the basis of the above experiment 2 And P 2 O 5 The two nucleating agents have influence on crystallization of the microcrystalline glass prepared by the actual steel slag one-step method.
TABLE 14-TiO 2 And P 2 O 5 Experimental items of influence
Figure BDA0003673608830000242
FIG. 39 shows the addition of 3 wt% TiO 2 And P 2 O 5 XRD detection results of two crystal nucleating agents, and a semi-quantitative analysis of the XRD detection results of the sample is shown in figure 40. TiO 2 2 The main crystal phase of the doped sample has higher strength, while P 2 O 5 The doping of (2) reduces the crystallization peak intensity of the main crystal phase of the sample. It can be concluded that TiO 2 Doping is beneficial to the precipitation of anorthite and diopside phases. From semi-quantitative analysis of XRD results, TiO 2 The doped sample has the ratio of anorthite to diopside of 1:1, and basically no other components are detected. And TiO 2 2 And P 2 O 5 The relative content of anorthite precipitated from a system in which the two crystal nucleating agents are mixed reaches 70 percent. TiO 2 2 And P 2 O 5 Meanwhile, the precipitated phase in the doped sample is mainly anorthite phase.
5.3.2 microstructural analysis
As shown in FIG. 41, is undoped, TiO 2 ，P 2 O 5 With TiO 2 And P 2 O 5 The microstructure of the sample is doped. The doped TiO can be seen from the figure 2 The surface of the sample (A) shows the presence of particles of relatively uniform size, while P 2 O 5 The doped sample microstructure showed significant melting and larger and uniform grain size was also seen. TiO 2 2 And P 2 O 5 In addition to the microstructure of the sample used in the blend having grains of relatively uniform size, the lower right hand corner of the sample microstructure also showed a marked tendency to melt. Can infer P 2 O 5 May cause melting of the sample grains, which, as mentioned above, may lead to doping of P in the XRD results 2 O 5 The main crystallization peak intensity of the post sample is reduced.
5.4 physical Properties and chromium Leaching test
5.4.1 physical Properties
Table 15 shows the effect of the flux on the hardness and corrosion resistance of the anorthite-diopside microcrystalline glass. The addition of the fluxing agent obviously increases the hardness of the sample, and the corrosion resistance of the sample is also better improved. In combination with the micro-morphology of the sample, this is probably because the flux makes the sample grains more compact and the pores are reduced, thus improving the hardness and the acid and alkali corrosion resistance of the sample.
TABLE 15 influence of flux on sample hardness and Corrosion resistance
Figure BDA0003673608830000251
FIG. 42 shows the effect of chromium content on the hardness and corrosion resistance of the samples, and Table 16 shows the effect of the nucleating agent on the physical properties of the samples. In a hardness test, the increase of the chromium content reduces the microhardness of a sample, and the hardness of the sample added with the fluxing agent reaches about 3000 HV. In an acid and alkali resistance test, the result shows that the acid resistance of the sample is better than the alkali resistance of the sample, and the acid resistance and the alkali resistance do not show obvious trend under experimental conditions along with the increase of the chromium content. In combination with the micro-morphology, the increase in chromium content decreases the density of the sample and increases the porosity, which may lead to a decrease in the hardness and corrosion resistance of the microcrystalline glass material.
TABLE 16 Effect of the nucleating agent on the physical Properties of the samples
Figure BDA0003673608830000261
5.4.2 chromium Leaching test
As shown in Table 17, in the chromium leaching experiment, 0.311mg/L of chromium was detected in the sample completely prepared from the steel slag, and no chromium element was detected in any of the other samples. This is in contrast to the XRD detection result that the chromium-containing phase is only MgCr 2 O 4 The result of (b) corresponds to MgCr 2 O 4 As an insoluble phase, the microcrystalline glass of the system has better chromium fixing performance.
TABLE 17 results of ICP-OES testing of chromium leaching experiments
Figure BDA0003673608830000262
5.5 knots
Under the guidance of thermodynamic calculation and pure substance simulation of chromium-containing stainless steel slag components, the microcrystalline glass is prepared by utilizing actual steel slag, the influence of a fluxing agent on the melting point of an experimental raw material is researched, the influence of chromium content on the physical property and crystallization property of a material is researched by changing the chromium content in the material, and the influence of a crystal nucleating agent on the physical property and crystallization property of the material is researched.
(1) In the melting point test, the experimental results showed excessive addition of Na 2 O、K 2 O and CaF 2 The melting point of the raw materials is increased, so that the melting point of the raw materials is increased to reduce energy consumptionThe lower level is reached, and the more ideal adding amount of the fluxing agent is 1 wt% of Na obtained by research in experiments 2 O，1wt％K 2 O，1wt％CaF 2 ；
(2) Compared with the microcrystalline glass completely prepared from stainless steel slag, the microcrystalline glass prepared from the prepared steel slag has better chromium fixation performance because a spinel phase is generated, and the generated phase is basically consistent with the calculation result of thermodynamic software in the third chapter. In the experimental research of the influence of the chromium content on the crystallization performance of the microcrystalline glass prepared by the steel slag, Cr 2 O 3 The chromium-containing phase is only spinel when the mass fraction of the chromium-containing phase reaches 5%. Semi-quantitative analysis showed that the system was more prone to anorthite phase formation. The increase of the chromium content changes the micro-morphology of the sample, the whole sample is changed from granular to strip with irregular shape, and the porosity is increased, so that the density is reduced;
(3) the hardness of the sample is increased by adding the fluxing agent, the highest hardness reaches about 3000HV, and the hardness of the sample is reduced by increasing the chromium content. The acid resistance of the sample is better than the alkali resistance, and the chromium content has little influence on the corrosion resistance. All samples prepared from the steel slag after being configured have no chromium element detected in the chromium leaching experiment. This indicates that the microcrystalline glass sample prepared from the actual steel slag has better chromium fixation efficiency.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered as the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.

Claims (5)

1. A one-step method for preparing microcrystalline glass from chromium-containing stainless steel slag is characterized by comprising the following steps: the process takes chromium-containing stainless steel slag as a raw material, and generates diopside according to the theory: the anorthite is a crystal phase component with the ratio of 1:1, and pure substances are added, so that the ratio of CaO in the raw materials is as follows: SiO 2 2 ：Al 2 O 3 : MgO is 2:4:1: 1; and carrying out heat treatment on the prepared raw materials to obtain the microcrystalline glass.
2. The one-step process for preparing microcrystalline glass from chromium-containing stainless steel slag according to claim 1 is characterized in that: the heat treatment is to put the prepared raw materials into a furnace to heat up to 900-.
3. The one-step process for preparing microcrystalline glass from chromium-containing stainless steel slag according to claim 2 is characterized in that: and the heat treatment is to put the prepared raw materials into a furnace, raise the temperature to 1090 ℃ at the speed of 5 ℃/min, preserve the heat for 4h, then lower the temperature to 500 ℃, preserve the heat for 2h, anneal and cool to obtain the microcrystalline glass.
4. The one-step method for preparing microcrystalline glass from chromium-containing stainless steel slag according to claim 1, which is characterized in that: 0.5-2 wt% of Na is added into the stainless steel slag 2 O、0.5-2wt％K 2 O and 0.5-2 wt% CaF 2 。
5. The one-step method for preparing microcrystalline glass from chromium-containing stainless steel slag according to claim 4 is characterized in that: 1 wt% of Na is added into the stainless steel slag 2 O、1wt％K 2 O and 1 wt% CaF 2 。
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