Stable steel-manganese mixed slag-based cement ink material, preparation method and application

Abstract

The application discloses a stable steel-manganese mixed slag-based cement ink material, a preparation method and application. The refining slag contains free calcium oxide, the free calcium oxide (f-CaO) in the refining slag is an unstable component, is easy to react with water to generate calcium hydroxide, and causes volume expansion and material cracking. Through unit laboratory research, it is found that under the premise that no additional process is used to change the composition of the refining slag, the free calcium oxide in the refining slag is absorbed by introducing electrolytic manganese slag, the problem of poor stability of the refining slag is solved, and the problem of pollution existing in the building field of the electrolytic manganese slag is also solved. The refining slag and the electrolytic manganese slag are processed by a superfine tire roller mill, the specific surface area is large, and the hydration activity of the refining slag is more conducive to being excited, the hydration activity is excited, early strength is formed, and part of the double-quick cement can be replaced.

Description

Technical Field

[0001] This invention belongs to the field of 3D printing of buildings and resource utilization of solid waste, specifically a stabilized steel-manganese mixed slag-based cement ink material, its preparation method and application. Background Technology

[0002] With societal development, the drawbacks of traditional construction have become increasingly apparent. Traditional construction suffers from material waste, limitations imposed by formwork shape and fabrication, and the need for extensive manual labor in concrete construction, resulting in long construction cycles. These issues constrain the development of traditional construction. In recent years, 3D printing technology has rapidly advanced, and its application in the construction industry has become a current trend. 3D printing technology allows for precise control of material usage, effectively reducing waste. Furthermore, it enables the printing of complex architectural structures, expanding design freedom. Automated production further reduces labor costs and saves time. However, 3D printing places strict requirements on material properties.

[0003] With the development of my country's economy, its steelmaking technology is also rapidly advancing. As a major industrial country, my country generates a large amount of steelmaking slag annually. However, the utilization rate of refining slag in my country is low. Refining slag contains elements such as calcium, silicon, iron, aluminum, and sodium. It contains dicalcium silicate and tricalcium silicate, which exhibit hydration activity and can be used as an early-maturing material in the construction industry. However, the hydration activity of refining slag is not strong in the early stages, and it contains free calcium oxide, resulting in poor volume stability. These factors restrict the application of refining slag in the construction industry.

[0004] Currently, my country has become the world's largest producer of electrolytic manganese, and electrolytic manganese slag, as the waste residue from electrolytic manganese production, is also generated in large quantities every year. Currently, electrolytic manganese enterprises typically dispose of this slag by constructing slag dumps, which not only occupies a large amount of land, but also contains elements such as calcium, silicon, iron, nitrogen, cobalt, nickel, aluminum, chromium, and zinc, in addition to manganese, ammonia nitrogen, and sulfates. Under long-term weathering and leaching, these soluble ions and heavy metals have migrated and been released into the surrounding soil, surface water, and groundwater, causing serious pollution to the local environment and residents' drinking water. Summary of the Invention

[0005] The purpose of this invention is to overcome at least one defect in the existing technology by providing a stable steel-manganese mixed slag cement ink material, its preparation method, and its application. This invention blends refining slag and electrolytic manganese slag. The manganese slag absorbs free calcium oxide from the refining slag, improving the stability of the steel slag. Simultaneously, it stimulates the early hydration activity of the refining slag, resulting in early-strength mortar, which can replace fast-setting cement. Furthermore, after the electrolytic manganese slag absorbs free calcium oxide, the environmental impact of ammonium salts in the electrolytic manganese slag can be eliminated. The stable steel-manganese mixed slag cement ink material, its preparation method, and its application not only rationally utilize refining slag and electrolytic manganese slag, solving the problem of poor volume stability of steel slag, but also proposes using steel-manganese mixed slag to replace fast-setting cement in the 3D printing industry, improving the early strength of 3D printed cement-based materials.

[0006] To solve the above-mentioned technical problems, the inventors, through practice and summarization, derived the technical solution of this invention, which adopts the following technical solution:

[0007] A steel-manganese mixed slag cementitious material comprises a mixture of 500-700 mesh refined slag ultrafine powder obtained by ultrafine tire vertical mill and 500-700 mesh electrolytic manganese slag ultrafine powder obtained by ultrafine tire vertical mill from manganese slag produced by electrolysis, with a mass ratio of 1:1 to 3:1.

[0008] The steel slag is a refining slag, and its chemical composition and mass percentage are as follows: SiO2 4.98%–5.80%, crystalline CaO 44.06%–49.39%, f-CaO 3.07%–4.21%, MgO 7.25%–8.46%, Al2O3 27.21%–29.86%, FeO 0.40%–3.48%, MnO 0.19%–1.06%, TiO2 0.25%–0.39%, P2O5 0.04%–0.30%, with the balance being impurities;

[0009] The manganese slag is electrolytic manganese slag, and its chemical composition and mass percentage content are as follows: SiO2 39.94%~42.34%, Al2O3 9.17%~9.87%, CaO 12.51%~14.45%, SO3 20.9%~23.9%, Fe2O3 3.75%~4.25%, MgO 2.05%~2.48%, MnO 2.17~3.25%, with the balance being impurities;

[0010] The formula is calculated using C=M(SO3) / M(f-CaO), where M(SO3) is the mass percentage of SO3 in the steel-manganese mixed slag, and M(f-CaO) is the mass percentage of f-CaO in the steel-manganese mixed slag. The mass relationship satisfies 2.346≤C≤7.043.

[0011] In the steel-manganese mixed slag cementitious material, the steel slag is a refined slag, and its chemical composition and mass percentage content are as follows: SiO2 5.66%, crystalline CaO 44.08%, f-CaO 3.11%, MgO 7.61%, Al2O3 27.21%, FeO 3.06%, MnO 1.06%, TiO2 0.39%, P2O5 0.30%, with the balance being impurities;

[0012] The manganese slag is electrolytic manganese slag, and its chemical composition and mass percentage content are as follows: SiO2 40.84%, Al2O3 9.37%, CaO 13.54%, SO3 21.9%, Fe2O3 4.00%, MgO 2.45%, MnO 3.21%, with the balance being impurities;

[0013] The formula is calculated using C=M(SO3) / M(f-CaO), where M(SO3) is the mass percentage of SO3 in the steel-manganese mixed slag, and M(f-CaO) is the mass percentage of f-CaO in the steel-manganese mixed slag. The mass relationship satisfies 2.346≤C≤7.043.

[0014] A stabilized steel-manganese mixed slag-based cement ink material, comprising the following components in parts by weight: 50-60 parts ordinary cement, 100-110 parts sand, 10-20 parts steel-manganese mixed slag cementitious material, 4-10 parts silica fume, 0.6-1 part water-reducing agent, 4-10 parts expansion agent, and 20-30 parts water.

[0015] In the stabilized steel-manganese mixed slag-based cement ink material, the sand includes quartz sand and manufactured sand with a particle size of 0.075-0.5 mm;

[0016] The silica fume is micro silica powder (SiO2) with a content of 92%-98%.

[0017] The water-reducing agent is a polycarboxylate water-reducing agent, which is in powder form.

[0018] The ordinary cement is ordinary Portland cement with a strength of 42.5;

[0019] The expansive agent is a UEA-type concrete expansive agent, and its physical form is powder.

[0020] The water in question is tap water.

[0021] A method for preparing stabilized steel-manganese mixed slag-based cement ink material, the method comprising the following steps:

[0022] 1) Mix ordinary cement, silica fume, sand, expansion agent, and water-reducing agent to obtain mixture A:

[0023] 2) Thoroughly mix the refining slag and electrolytic manganese slag and add them to mixture A in batches to obtain mixture B;

[0024] 3) Add water in batches to mixture B and mix and stir to obtain stable steel-manganese mixed slag-based cement ink material.

[0025] In the preparation method of stable steel-manganese mixed slag-based cement ink material, the mixing and stirring speed in step 1) is 100-200 rpm and the time is 120-300 s.

[0026] In the preparation method of the stabilized steel-manganese mixed slag-based cement ink material, in step 2), when mixing the refining slag and electrolytic manganese slag, the stirring speed is 100-150 rpm and the stirring time is 120-180 s. Each addition is made at a stirring speed of 100-200 rpm and a stirring time of 180-420 s.

[0027] In the preparation method of stable steel-manganese mixed slag-based cement ink material, in step 3), 50% water is first added to mixture B and mixed and stirred at a speed of 100-200 rpm for 60-180 s.

[0028] In the preparation method of stable steel-manganese mixed slag-based cement ink material, in step 3), 50% water is added to mixture B for mixing and stirring at a speed of 300-500 rpm for 300-600 s.

[0029] Application of a stable steel-manganese mixed slag-based cement ink material, wherein the ink material is used in the 3D printing construction industry.

[0030] Compared with the prior art, the present invention has the following beneficial effects:

[0031] 1) This invention, applied to 3D printing scenarios, utilizes dual-fast cement in its components to achieve rapid setting of the ink material. Furthermore, the components incorporate refining slag and electrolytic manganese slag, both processed by an ultrafine tire vertical mill. Their large specific surface area facilitates the activation of the refining slag's hydration activity, resulting in early strength. This activated hydration activity also partially replaces the dual-fast cement, reducing the use of this energy-intensive product. Additionally, the ultrafine tire vertical mill produces smaller particle sizes, allowing for better dispersion within the cement material. Smaller particle sizes improve mortar fluidity and interlayer bonding strength, resulting in smoother material flow and higher strength printed components during 3D printing.

[0032] 2) The refining slag used in this invention contains free calcium oxide (f-CaO), which is an unstable component that readily reacts with water to form calcium hydroxide, leading to volume expansion and material cracking. Laboratory research has shown that, without altering the composition of the refining slag through additional processes, introducing electrolytic manganese slag to absorb the free calcium oxide in the refining slag can partially replace fast-acting cement, solve the problem of poor stability in the refining slag, and also address the pollution issues associated with using electrolytic manganese slag in the construction industry.

[0033] Furthermore, based on the formula C=M(SO3) / M(f-CaO), strict adjustments were made to ensure that the mass ratio of the mixed slag met the condition 2.346≤C≤7.043. When C is too low, the free calcium oxide in the refining slag cannot be fully absorbed, resulting in poor material stability; when the ratio is too high, the f-CaO content is too low, affecting the early hydration strength of the manganese slag and hindering the absorption of ammonium salts from the electrolytic manganese slag.

[0034] By reducing the potential environmental impact of refining slag and electrolytic manganese slag, this technology helps promote the development of the environmental protection industry. Furthermore, it can serve as a successful example of solid waste resource utilization, providing a reference for the treatment of other similar wastes.

[0035] 3) The steel slag used in this invention is refining slag, which has a high Al2O3 content and exhibits aluminosilicate characteristics. The sulfate content in the electrolytic manganese slag is strictly controlled within the range of 20.9% to 23.9%, which can accelerate the hydration of the refining slag, promote the formation of ettringite, and facilitate the activation of the hydration activity of the refining slag. Furthermore, when the free calcium oxide in the refining slag is absorbed by the electrolytic manganese slag, it stimulates the early release of alkalinity in the refining slag, further activating its hydration activity. The early hydration activity of the refining slag is doubly activated, resulting in an early and strong effect, thus solving the problem of slow activation of the hydration activity of the refining slag.

[0036] 4) The free calcium oxide content of the refining slag used in this invention is strictly controlled within the range of 3.07% to 4.21%, which is conducive to its absorption by electrolytic manganese slag, thereby reacting with the ammonium salt in the electrolytic manganese slag. This can solve the problem of poor stability and also solve the environmental impact of ammonium salt in electrolytic manganese slag.

[0037] 5) The water-reducing agent, expanding agent, and other materials (excluding water) used in this invention are all in powder form. Laboratory studies have found that when traditional liquid-based cement ink materials are mixed with the water-reducing agent and expanding agent (liquid components), homogenization cannot be achieved. Due to intermolecular forces, these materials (water-reducing agent, expanding agent, and other materials) are encapsulated by the cementitious powder, forming tiny monomers. This hinders thorough mixing and affects the strength performance of the printed components. Therefore, the powdered material used in this application, compared to traditional cement ink materials containing liquid components, effectively solves the problem of uneven material distribution affecting material performance. Furthermore, the powdered form facilitates transportation, production processing, and on-site mixing.

[0038] 6) This invention strictly blends refining slag and electrolytic manganese slag, partially replacing double-fast cement, and combines it with 3D printing intelligent building technology to prepare a steel-manganese mixed slag cement ink material that meets the requirements of 3D printing and has early strength. It makes full use of the resources of metallurgical solid waste and the advantages of on-site construction of 3D printing. It not only helps to solve the problem of the need for a large amount of manual labor in the traditional construction industry, but also helps to solve the problem of resource reuse of refining slag and electrolytic manganese slag, and has high environmental protection and economic benefits.

[0039] 7) This invention provides a method for preparing and applying a stable steel-manganese mixed slag cement ink material, which has better stability than ordinary ink materials containing refining slag; and its early strength is improved compared to ordinary cement ink materials. Detailed Implementation

[0040] Example 1:

[0041] A stable steel-manganese mixed slag-based cement ink material comprises the following components by weight: 55 parts ordinary cement, 105 parts sand, 15 parts steel-manganese mixed slag, 7 parts silica fume, 0.8 parts water-reducing agent, 7 parts expansion agent, and 25 parts water.

[0042] Among them, the ordinary cement is PO 42.5 ordinary Portland cement; the silica fume is microsilica powder with a SiO2 content of 94%; the quartz sand particle size is 0.075-0.5mm; the water-reducing agent is solid powder type polycarboxylate high-efficiency water-reducing agent with a water reduction efficiency of 20%; the water is ordinary tap water; and the expansion agent is UEA type concrete expansion agent (powder).

[0043] The steel-manganese mixed slag is a mixture of 500-mesh refined slag ultrafine powder obtained by ultrafine tire vertical mill and 500-mesh electrolytic manganese slag ultrafine powder obtained by ultrafine tire vertical mill from manganese slag produced by electrolysis, with a mass ratio of 2:1.

[0044] Furthermore, the steel slag is a refining slag, and its chemical composition and mass percentage content are as follows: SiO2 5.66%, crystalline CaO 44.08%, f-CaO 3.11%, MgO 7.61%, Al2O3 27.21%, FeO 3.06%, MnO 1.06%, TiO2 0.39%, P2O5 0.30%, with the balance being impurities;

[0045] The manganese slag is electrolytic manganese slag, and its chemical composition and mass percentage content are as follows: SiO2 40.84%, Al2O3 9.37%, CaO 13.54%, SO3 21.9%, Fe2O3 4.00%, MgO 2.45%, MnO 3.21%, with the balance being impurities.

[0046] The formula C = M(SO3) / M(f-CaO) is used for calculation, where M(SO3) is the mass percentage of SO3 in the steel-manganese mixed slag, and M(f-CaO) is the mass percentage of f-CaO in the steel-manganese mixed slag. The mass relationship satisfies C = 3.521 (rounded).

[0047] The specific steps for producing the above-mentioned steel-manganese mixed slag cement ink material are as follows:

[0048] 1) Take ordinary silicate cement, quartz sand, silica fume, expansion agent and water-reducing agent and mix them. The mixing speed is 150 rpm and the mixing time is 180 s to obtain mixture A.

[0049] 2) Thoroughly mix the refining slag and electrolytic manganese slag and add them to mixture A in batches, stirring to obtain mixture B. By weight percentage, add 30% the first time, 30% the second time, and 40% the third time, stirring at 150 rpm for 420 seconds each time.

[0050] 3) Add water to mixture B in batches and mix. When adding 50% of the water for the first time, the mixing time is 60 seconds and the mixing speed is 250 rpm. When adding the remaining water for the second time, the mixing time is 420 seconds and the mixing speed is 450 rpm. This will give you a stable steel-manganese mixed slag-based cement ink material.

[0051] Example 2:

[0052] A stable steel-manganese mixed slag-based cement ink material comprises the following components by weight: 55 parts ordinary cement, 105 parts sand, 15 parts steel-manganese mixed slag, 7 parts silica fume, 0.8 parts water-reducing agent, 7 parts expansion agent, and 25 parts water.

[0053] Among them, the ordinary cement is PO 42.5 ordinary Portland cement; the silica fume is microsilica powder with a SiO2 content of 94%; the quartz sand particle size is 0.075-0.5mm; the water-reducing agent is solid powder type polycarboxylate high-efficiency water-reducing agent with a water reduction efficiency of 20%; the water is ordinary tap water; and the expansion agent is UEA type concrete expansion agent (powder).

[0054] The steel-manganese mixed slag is a mixture of 600-mesh refined slag ultrafine powder obtained by ultrafine tire vertical mill and 600-mesh electrolytic manganese slag ultrafine powder obtained by ultrafine tire vertical mill from manganese slag produced by electrolysis, with a mass ratio of 2:1.

[0055] Furthermore, the steel slag is a refining slag, and its chemical composition and mass percentage content are as follows: SiO2 5.66%, crystalline CaO 44.08%, f-CaO 3.11%, MgO 7.61%, Al2O3 27.21%, FeO 3.06%, MnO 1.06%, TiO2 0.39%, P2O5 0.30%, with the balance being impurities;

[0056] The manganese slag is electrolytic manganese slag, and its chemical composition and mass percentage content are as follows: SiO2 40.84%, Al2O3 9.37%, CaO 13.54%, SO3 21.9%, Fe2O3 4.00%, MgO 2.45%, MnO 3.21%, with the balance being impurities.

[0057] The formula C = M(SO3) / M(f-CaO) is used for calculation, where M(SO3) is the mass percentage of SO3 in the steel-manganese mixed slag, and M(f-CaO) is the mass percentage of f-CaO in the steel-manganese mixed slag. The mass relationship satisfies C = 3.521 (rounded).

[0058] The specific steps for producing the above-mentioned steel-manganese mixed slag cement ink material are as follows:

[0059] 1) Take ordinary silicate cement, quartz sand, silica fume, expansion agent and water-reducing agent and mix them. The mixing speed is 150 rpm and the mixing time is 180 s to obtain mixture A.

[0060] 2) Thoroughly mix the refining slag and electrolytic manganese slag and add them to mixture A in batches, stirring to obtain mixture B. By weight percentage, add 30% the first time, 30% the second time, and 40% the third time, stirring at 150 rpm for 420 seconds each time.

[0061] 3) Add water to mixture B in batches and mix. When adding 50% of the water for the first time, the mixing time is 60 seconds and the mixing speed is 250 rpm. When adding the remaining water for the second time, the mixing time is 420 seconds and the mixing speed is 450 rpm. This will give you a stable steel-manganese mixed slag-based cement ink material.

[0062] Example 3:

[0063] A stable steel-manganese mixed slag-based cement ink material comprises the following components by weight: 55 parts ordinary cement, 105 parts sand, 15 parts steel-manganese mixed slag, 7 parts silica fume, 0.8 parts water-reducing agent, 7 parts expansion agent, and 25 parts water.

[0064] Among them, the ordinary cement is PO 42.5 ordinary Portland cement; the silica fume is microsilica powder with a SiO2 content of 94%; the quartz sand particle size is 0.075-0.5mm; the water-reducing agent is solid powder type polycarboxylate high-efficiency water-reducing agent with a water reduction efficiency of 20%; the water is ordinary tap water; and the expansion agent is UEA type concrete expansion agent (powder).

[0065] The steel-manganese mixed slag is a mixture of 700-mesh refined slag ultrafine powder obtained by ultrafine tire vertical mill and 700-mesh electrolytic manganese slag ultrafine powder obtained by ultrafine tire vertical mill of manganese slag produced by electrolysis, with a mass ratio of 2:1.

[0066] Furthermore, the steel slag is a refining slag, and its chemical composition and mass percentage content are as follows: SiO2 5.66%, crystalline CaO 44.08%, f-CaO 3.11%, MgO 7.61%, Al2O3 27.21%, FeO 3.06%, MnO 1.06%, TiO2 0.39%, P2O5 0.30%, with the balance being impurities;

[0067] The manganese slag is electrolytic manganese slag, and its chemical composition and mass percentage content are as follows: SiO2 40.84%, Al2O3 9.37%, CaO 13.54%, SO3 21.9%, Fe2O3 4.00%, MgO 2.45%, MnO 3.21%, with the balance being impurities.

[0068] The formula C = M(SO3) / M(f-CaO) is used for calculation, where M(SO3) is the mass percentage of SO3 in the steel-manganese mixed slag, and M(f-CaO) is the mass percentage of f-CaO in the steel-manganese mixed slag. The mass relationship satisfies C = 3.521 (rounded).

[0069] The specific steps for producing the above-mentioned steel-manganese mixed slag cement ink material are as follows:

[0070] 1) Take ordinary silicate cement, quartz sand, silica fume, expansion agent and water-reducing agent and mix them. The mixing speed is 150 rpm and the mixing time is 180 s to obtain mixture A.

[0071] 2) Thoroughly mix the refining slag and electrolytic manganese slag and add them to mixture A in batches, stirring to obtain mixture B. By weight percentage, add 30% the first time, 30% the second time, and 40% the third time, stirring at 150 rpm for 420 seconds each time.

[0072] 3) Add water to mixture B in batches and mix. When adding 50% of the water for the first time, the mixing time is 60 seconds and the mixing speed is 250 rpm. When adding the remaining water for the second time, the mixing time is 420 seconds and the mixing speed is 450 rpm. This will give you a stable steel-manganese mixed slag-based cement ink material.

[0073] Example 4:

[0074] A stable steel-manganese mixed slag-based cement ink material comprises the following components by weight: 55 parts ordinary cement, 105 parts sand, 15 parts steel-manganese mixed slag, 7 parts silica fume, 0.8 parts water-reducing agent, 7 parts expansion agent, and 25 parts water.

[0075] Among them, the ordinary cement is PO 42.5 ordinary Portland cement; the silica fume is microsilica powder with a SiO2 content of 94%; the quartz sand particle size is 0.075-0.5mm; the water-reducing agent is solid powder type polycarboxylate high-efficiency water-reducing agent with a water reduction efficiency of 20%; the water is ordinary tap water; and the expansion agent is UEA type concrete expansion agent (powder).

[0076] The steel-manganese mixed slag is a mixture of 600-mesh refined slag ultrafine powder obtained by ultrafine tire vertical mill and 600-mesh electrolytic manganese slag ultrafine powder obtained by ultrafine tire vertical mill from manganese slag produced by electrolysis, with a mass ratio of 1:1.

[0077] Furthermore, the steel slag is a refining slag, and its chemical composition and mass percentage content are as follows: SiO2 5.66%, crystalline CaO 44.08%, f-CaO 3.11%, MgO 7.61%, Al2O3 27.21%, FeO 3.06%, MnO 1.06%, TiO2 0.39%, P2O5 0.30%, with the balance being impurities;

[0078] The manganese slag is electrolytic manganese slag, and its chemical composition and mass percentage content are as follows: SiO2 40.84%, Al2O3 9.37%, CaO 13.54%, SO3 21.9%, Fe2O3 4.00%, MgO 2.45%, MnO 3.21%, with the balance being impurities.

[0079] The formula C = M(SO3) / M(f-CaO) is used for calculation, where M(SO3) is the mass percentage of SO3 in the steel-manganese mixed slag, and M(f-CaO) is the mass percentage of f-CaO in the steel-manganese mixed slag. The mass relationship satisfies C = 7.042 (rounded).

[0080] The specific steps for producing the above-mentioned steel-manganese mixed slag cement ink material are as follows:

[0081] 1) Take ordinary silicate cement, quartz sand, silica fume, expansion agent and water-reducing agent and mix them. The mixing speed is 150 rpm and the mixing time is 180 s to obtain mixture A.

[0082] 2) Thoroughly mix the refining slag and electrolytic manganese slag and add them to mixture A in batches, stirring to obtain mixture B. By weight percentage, add 30% the first time, 30% the second time, and 40% the third time, stirring at 150 rpm for 420 seconds each time.

[0083] 3) Add water to mixture B in batches and mix. When adding 50% of the water for the first time, the mixing time is 60 seconds and the mixing speed is 250 rpm. When adding the remaining water for the second time, the mixing time is 420 seconds and the mixing speed is 450 rpm. This will give you a stable steel-manganese mixed slag-based cement ink material.

[0084] Example 5:

[0085] A stable steel-manganese mixed slag-based cement ink material comprises the following components by weight: 55 parts ordinary cement, 105 parts sand, 15 parts steel-manganese mixed slag, 7 parts silica fume, 0.8 parts water-reducing agent, 7 parts expansion agent, and 25 parts water.

[0086] Among them, the ordinary cement is PO 42.5 ordinary Portland cement; the silica fume is microsilica powder with a SiO2 content of 94%; the quartz sand particle size is 0.075-0.5mm; the water-reducing agent is solid powder type polycarboxylate high-efficiency water-reducing agent with a water reduction efficiency of 20%; the water is ordinary tap water; and the expansion agent is UEA type concrete expansion agent (powder).

[0087] The steel-manganese mixed slag is a mixture of 600-mesh refined slag ultrafine powder obtained by ultrafine tire vertical mill and 600-mesh electrolytic manganese slag ultrafine powder obtained by ultrafine tire vertical mill from manganese slag produced by electrolysis, with a mass ratio of 3:1.

[0088] Furthermore, the steel slag is a refining slag, and its chemical composition and mass percentage content are as follows: SiO2 5.66%, crystalline CaO 44.08%, f-CaO 3.11%, MgO 7.61%, Al2O3 27.21%, FeO 3.06%, MnO 1.06%, TiO2 0.39%, P2O5 0.30%, with the balance being impurities;

[0089] The manganese slag is electrolytic manganese slag, and its chemical composition and mass percentage content are as follows: SiO2 40.84%, Al2O3 9.37%, CaO 13.54%, SO3 21.9%, Fe2O3 4.00%, MgO 2.45%, MnO 3.21%, with the balance being impurities.

[0090] The formula C = M(SO3) / M(f-CaO) is used for calculation, where M(SO3) is the mass percentage of SO3 in the steel-manganese mixed slag, and M(f-CaO) is the mass percentage of f-CaO in the steel-manganese mixed slag. The mass relationship satisfies C = 2.347 (rounded).

[0091] The specific steps for producing the above-mentioned steel-manganese mixed slag cement ink material are as follows:

[0092] 1) Take ordinary silicate cement, quartz sand, silica fume, expansion agent and water-reducing agent and mix them. The mixing speed is 150 rpm and the mixing time is 180 s to obtain mixture A.

[0093] 2) Thoroughly mix the refining slag and electrolytic manganese slag and add them to mixture A in batches, stirring to obtain mixture B. By weight percentage, add 30% the first time, 30% the second time, and 40% the third time, stirring at 150 rpm for 420 seconds each time.

[0094] 3) Add water to mixture B in batches and mix. When adding 50% of the water for the first time, the mixing time is 60 seconds and the mixing speed is 250 rpm. When adding the remaining water for the second time, the mixing time is 420 seconds and the mixing speed is 450 rpm. This will give you a stable steel-manganese mixed slag-based cement ink material.

[0095] Example 6:

[0096] A stable steel-manganese mixed slag-based cement ink material comprises the following components by weight: 50 parts ordinary cement, 100 parts sand, 20 parts steel-manganese mixed slag, 4 parts silica fume, 0.6 parts water-reducing agent, 4 parts expansion agent, and 20 parts water.

[0097] Among them, the ordinary cement is PO 42.5 ordinary Portland cement; the silica fume is microsilica powder with a SiO2 content of 94%; the quartz sand particle size is 0.075-0.5mm; the water-reducing agent is solid powder type polycarboxylate high-efficiency water-reducing agent with a water reduction efficiency of 20%; the water is ordinary tap water; and the expansion agent is UEA type concrete expansion agent (powder).

[0098] The steel-manganese mixed slag is a mixture of 600-mesh refined slag ultrafine powder obtained by ultrafine tire vertical mill and 600-mesh electrolytic manganese slag ultrafine powder obtained by ultrafine tire vertical mill from manganese slag produced by electrolysis, with a mass ratio of 2:1.

[0099] Furthermore, the steel slag is a refining slag, and its chemical composition and mass percentage content are as follows: SiO2 5.15%, crystalline CaO 46.11%, f-CaO 3.22%, MgO 7.64%, Al2O3 28.14%, FeO 3.11%, MnO 1.05%, TiO2 0.33%, P2O5 0.23%, with the balance being impurities;

[0100] The manganese slag is electrolytic manganese slag, and its chemical composition and mass percentage content are as follows: SiO2 41.25%, Al2O3 9.68%, CaO 13.87%, SO3 22.32%, Fe2O3 4.25%, MgO 2.43%, MnO 3.12%, with the balance being impurities.

[0101] The formula is calculated using C = M(SO3) / M(f-CaO), where M(SO3) is the mass percentage of SO3 in the steel-manganese mixed slag, and M(f-CaO) is the mass percentage of f-CaO in the steel-manganese mixed slag. The mass relationship satisfies C = 3.466 (rounded).

[0102] The specific steps for producing the above-mentioned steel-manganese mixed slag cement ink material are as follows:

[0103] 1) Take ordinary silicate cement, quartz sand, silica fume, expansion agent and water-reducing agent and mix them. The mixing speed is 150 rpm and the mixing time is 180 s to obtain mixture A.

[0104] 2) Thoroughly mix the refining slag and electrolytic manganese slag and add them to mixture A in batches, stirring to obtain mixture B. By weight percentage, add 30% the first time, 30% the second time, and 40% the third time, stirring at 150 rpm for 420 seconds each time.

[0105] 3) Add water to mixture B in batches and mix. When adding 50% of the water for the first time, the mixing time is 60 seconds and the mixing speed is 250 rpm. When adding the remaining water for the second time, the mixing time is 420 seconds and the mixing speed is 450 rpm. This will give you a stable steel-manganese mixed slag-based cement ink material.

[0106] Example 7:

[0107] A stable steel-manganese mixed slag-based cement ink material, comprising the following components by weight: 60 parts ordinary cement, 110 parts sand, 10 parts steel-manganese mixed slag, 10 parts silica fume, 1 part water-reducing agent, 10 parts expansion agent, and 30 parts water.

[0108] Among them, the ordinary cement is PO 42.5 ordinary Portland cement; the silica fume is microsilica powder with a SiO2 content of 94%; the quartz sand particle size is 0.075-0.5mm; the water-reducing agent is solid powder type polycarboxylate high-efficiency water-reducing agent with a water reduction efficiency of 20%; the water is ordinary tap water; and the expansion agent is UEA type concrete expansion agent (powder).

[0109] The steel-manganese mixed slag is a mixture of 600-mesh refined slag ultrafine powder obtained by ultrafine tire vertical mill and 600-mesh electrolytic manganese slag ultrafine powder obtained by ultrafine tire vertical mill from manganese slag produced by electrolysis, with a mass ratio of 2:1.

[0110] Furthermore, the steel slag is a refining slag, and its chemical composition and mass percentage content are as follows: SiO2 5.66%, crystalline CaO 44.08%, f-CaO 3.11%, MgO 7.61%, Al2O3 27.21%, FeO 3.06%, MnO 1.06%, TiO2 0.39%, P2O5 0.30%, with the balance being impurities;

[0111] The manganese slag is electrolytic manganese slag, and its chemical composition and mass percentage content are as follows: SiO2 40.84%, Al2O3 9.37%, CaO 13.54%, SO3 21.9%, Fe2O3 4.00%, MgO 2.45%, MnO 3.21%, with the balance being impurities.

[0112] The formula C = M(SO3) / M(f-CaO) is used for calculation, where M(SO3) is the mass percentage of SO3 in the steel-manganese mixed slag, and M(f-CaO) is the mass percentage of f-CaO in the steel-manganese mixed slag. The mass relationship satisfies C = 3.521 (rounded).

[0113] The specific steps for producing the above-mentioned steel-manganese mixed slag cement ink material are as follows:

[0114] 1) Take ordinary silicate cement, quartz sand, silica fume, expansion agent and water-reducing agent and mix them. The mixing speed is 150 rpm and the mixing time is 180 s to obtain mixture A.

[0115] 2) Thoroughly mix the refining slag and electrolytic manganese slag and add them to mixture A in batches, stirring to obtain mixture B. By weight percentage, add 30% the first time, 30% the second time, and 40% the third time, stirring at 150 rpm for 420 seconds each time.

[0116] 3) Add water to mixture B in batches and mix. When adding 50% of the water for the first time, the mixing time is 60 seconds and the mixing speed is 250 rpm. When adding the remaining water for the second time, the mixing time is 420 seconds and the mixing speed is 450 rpm. This will give you a stable steel-manganese mixed slag-based cement ink material.

[0117] Comparative Example 1:

[0118] A manganese slag cement ink material comprises the following components by weight: 55 parts ordinary cement, 105 parts sand, 15 parts manganese slag, 7 parts silica fume, 0.8 parts water-reducing agent, 9 parts expansion agent, and 25 parts water.

[0119] Among them, the ordinary cement is PO 42.5 ordinary Portland cement; the silica fume is microsilica powder with a SiO2 content of 94%; the quartz sand particle size is 0.075-0.5mm; the water-reducing agent is solid powder type polycarboxylate high-efficiency water-reducing agent with a water reduction efficiency of 20%; the water is ordinary tap water; and the expansion agent is UEA type concrete expansion agent (powder).

[0120] The manganese slag is 600-mesh electrolytic manganese slag ultrafine powder obtained by electrolytic manganese slag produced by an ultrafine tire vertical mill. Its chemical composition and mass percentage content are as follows: SiO2 40.84%, Al2O3 9.37%, CaO 13.54%, SO3 21.9%, Fe2O3 4.00%, MgO 2.45%, MnO 3.21%, with the balance being impurities.

[0121] The specific implementation steps for the above-mentioned manganese slag cement ink material are as follows:

[0122] 1) Take ordinary silicate cement, quartz sand, silica fume, expansion agent and water-reducing agent and mix them. The mixing speed is 150 rpm and the mixing time is 180 s to obtain mixture A.

[0123] 2) Add the electrolytic manganese slag to mixture A in batches and stir to obtain mixture B. By weight percentage, add 30% the first time, 30% the second time, and 40% the third time. Each addition is stirred at 150 rpm for 420 seconds.

[0124] 3) After mixing water and water-reducing agent in batches, add them to mixture B for mixing and stirring. The first time 50% of the water is added, the stirring time is 60s and the stirring speed is 250rpm. The second time the remaining water is added, the stirring time is 420s and the stirring speed is 450rpm, to obtain manganese slag cement ink material.

[0125] Comparative Example 2:

[0126] A stable steel-manganese mixed slag-based cement ink material, comprising the following components by weight: 60 parts ordinary cement, 110 parts sand, 10 parts steel-manganese mixed slag, 10 parts silica fume, 1 part water-reducing agent, 10 parts expansion agent, and 30 parts water.

[0127] Among them, the ordinary cement is PO 42.5 ordinary Portland cement; the silica fume is microsilica powder with a SiO2 content of 94%; the quartz sand particle size is 0.075-0.5mm; the water-reducing agent is solid powder type polycarboxylate high-efficiency water-reducing agent with a water reduction efficiency of 20%; the water is ordinary tap water; and the expansion agent is UEA type concrete expansion agent (powder).

[0128] The steel-manganese mixed slag is a mixture of 600-mesh refined slag ultrafine powder obtained by ultrafine tire vertical mill and 600-mesh electrolytic manganese slag ultrafine powder obtained by ultrafine tire vertical mill from manganese slag produced by electrolysis, with a mass ratio of 4:1.

[0129] Furthermore, the steel slag is a refining slag, and its chemical composition and mass percentage content are as follows: SiO2 5.66%, crystalline CaO 44.08%, f-CaO 3.11%, MgO 7.61%, Al2O3 27.21%, FeO 3.06%, MnO 1.06%, TiO2 0.39%, P2O5 0.30%, with the balance being impurities;

[0130] The manganese slag is electrolytic manganese slag, and its chemical composition and mass percentage content are as follows: SiO2 40.84%, Al2O3 9.37%, CaO 13.54%, SO3 21.9%, Fe2O3 4.00%, MgO 2.45%, MnO 3.21%, with the balance being impurities.

[0131] The formula C = M(SO3) / M(f-CaO) is used for calculation, where M(SO3) is the mass percentage of SO3 in the steel-manganese mixed slag, and M(f-CaO) is the mass percentage of f-CaO in the steel-manganese mixed slag. The mass relationship satisfies C = 1.760.

[0132] The specific steps for producing the above-mentioned steel-manganese mixed slag cement ink material are as follows:

[0133] 1) Take ordinary silicate cement, quartz sand, silica fume, expansion agent and water-reducing agent and mix them. The mixing speed is 150 rpm and the mixing time is 180 s to obtain mixture A.

[0134] 2) Thoroughly mix the refining slag and electrolytic manganese slag and add them to mixture A in batches, stirring to obtain mixture B. By weight percentage, add 30% the first time, 30% the second time, and 40% the third time, stirring at 150 rpm for 420 seconds each time.

[0135] 3) Add water to mixture B in batches and mix. When adding 50% of the water for the first time, the mixing time is 60 seconds and the mixing speed is 250 rpm. When adding the remaining water for the second time, the mixing time is 420 seconds and the mixing speed is 450 rpm. This will give you a stable steel-manganese mixed slag-based cement ink material.

[0136] Comparative Example 3:

[0137] A fast-acting cement ink material comprising the following components by weight: 55 parts ordinary cement, 105 parts sand, 15 parts fast-acting cement, 7 parts silica fume, 0.8 parts water-reducing agent, 9 parts expansion agent, and 25 parts water.

[0138] The ordinary cement is PO 42.5 ordinary Portland cement; the quick-setting cement is sulfoaluminate cement; the silica fume is microsilica with a SiO2 content of 94%; the quartz sand particle size is 0.075-0.5mm; the water-reducing agent is solid powder type polycarboxylate high-efficiency water-reducing agent with a water reduction efficiency of 20%; the water is ordinary tap water; the expansion agent is UEA type concrete expansion agent (powder).

[0139] The specific steps for producing the above-mentioned fast-acting cement ink material are as follows:

[0140] 1) Take ordinary Portland cement, quick-setting cement, quartz sand, silica fume and expansion agent and mix them. The mixing speed is 150 rpm and the mixing time is 180 s to obtain mixture A.

[0141] 2) Add water to mixture A in batches and mix. When adding 50% of the water for the first time, the mixing time is 60 seconds and the mixing speed is 250 rpm. When adding the remaining water for the second time, the mixing time is 420 seconds and the mixing speed is 450 rpm to obtain the double-fast cement ink material.

[0142] The stabilized steel-manganese mixed slag-based cement ink materials prepared in Examples 1-7 and other cement ink materials prepared in Comparative Examples 1-3 were mixed separately, and their extrudability was measured using a printing glue gun; their stability was measured using the test cake method; after being cast into standard test blocks of 70.7mm×70.7mm×70.7mm, they were cured in a standard curing room for 3 days and 28 days, and then cubic compressive strength tests were conducted. All test specimens were tested under completely identical conditions. The test results are shown in the table.

[0143] Results of experiments in Examples 1 to 7 and Comparative Examples 1 to 3:

[0144]

[0145] As shown in the table, the early-strength steel-manganese mixed slag-based cement ink material proposed in this invention has good extrudability and stability. After standard curing, the 3-day compressive strength of the cubic specimen is greater than that of ordinary cement ink material, and the 28-day cubic compressive strength does not change much.

[0146] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be easily made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

[0147] The above description is merely a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. The substitutions may be replacements of some structures, devices, or method steps, or they may be complete technical solutions. Equivalent substitutions or modifications made to the technical solutions and inventive concepts of the present invention should all be covered within the scope of protection of the present invention.

Claims

1. A steel-manganese mixed slag cementitious material, characterized in that, The mixture comprises 500-700 mesh refining slag ultrafine powder obtained by ultrafine tire vertical mill and 500-700 mesh electrolytic manganese slag ultrafine powder obtained by ultrafine tire vertical mill from manganese slag produced by electrolysis, with a mass ratio of 1:1 to 3:

1. The steel slag is a refining slag, and its chemical composition and mass percentage are as follows: SiO2 4.98%~5.80%, crystalline CaO 44.06%~49.39%, f-CaO 3.07%~4.21%, MgO 7.25%~8.46%, Al2O3 27.21%~29.86%, FeO 0.40%~3.48%, MnO 0.19%~1.06%, TiO2 0.25%~0.39%, P2O5 0.04%~0.30%, with the balance being impurities; The manganese slag is electrolytic manganese slag, and its chemical composition and mass percentage content are as follows: SiO2 39.94%~42.34%, Al2O3 9.17%~9.87%, CaO 12.51%~14.45%, SO3 20.9%~23.9%, Fe2O3 3.75%~4.25%, MgO 2.05%~2.48%, MnO 2.17~3.25%, with the balance being impurities; The formula is calculated using C=M(SO3) / M(f-CaO), where M(SO3) is the mass percentage of SO3 in the steel-manganese mixed slag, and M(f-CaO) is the mass percentage of f-CaO in the steel-manganese mixed slag. The mass relationship satisfies 2.346≤C≤7.

043.

2. The steel-manganese mixed slag cementitious material according to claim 1, characterized in that, The steel slag is a refining slag, and its chemical composition and mass percentage are as follows: SiO2 5.66%, crystalline CaO 44.08%, f-CaO 3.11%, MgO 7.61%, Al2O3 27.21%, FeO 3.06%, MnO 1.06%, TiO2 0.39%, P2O5 0.30%, with the balance being impurities; The manganese slag is electrolytic manganese slag, and its chemical composition and mass percentage content are as follows: SiO2 40.84%, Al2O3 9.37%, CaO 13.54%, SO3 21.9%, Fe2O3 4.00%, MgO 2.45%, MnO 3.21%, with the balance being impurities; The formula is calculated using C=M(SO3) / M(f-CaO), where M(SO3) is the mass percentage of SO3 in the steel-manganese mixed slag, and M(f-CaO) is the mass percentage of f-CaO in the steel-manganese mixed slag. The mass relationship satisfies 2.346≤C≤7.

043.

3. A stabilized steel-manganese mixed slag-based cement ink material, characterized in that, The ink material comprises the following components by weight: 50-60 parts of ordinary cement, 100-110 parts of sand, 10-20 parts of the steel-manganese mixed slag cementitious material as described in claim 1, 4-10 parts of silica fume, 0.6-1 parts of water-reducing agent, 4-10 parts of expansion agent, and 20-30 parts of water.

4. The stabilized steel-manganese mixed slag-based cement ink material according to claim 3, characterized in that, The sand includes quartz sand and manufactured sand, with a particle size of 0.075-0.5 mm; The ordinary cement is ordinary Portland cement with a strength of 42.5; The silica fume is micro silica powder (SiO2) with a content of 92%-98%. The water-reducing agent is a polycarboxylate water-reducing agent, which is in powder form. The expansive agent is a UEA-type concrete expansive agent, and its physical form is powder. The water in question is tap water.

5. A method for preparing a stabilized steel-manganese mixed slag-based cement ink material as described in claim 3 or 4, characterized in that, The method includes the following steps: 1) Mix ordinary cement, silica fume, sand, expansion agent, and water-reducing agent to obtain mixture A: 2) Thoroughly mix the refining slag and electrolytic manganese slag and add them to mixture A in batches to obtain mixture B; 3) Add water in batches to mixture B and mix and stir to obtain stable steel-manganese mixed slag-based cement ink material.

6. The method for preparing a stabilized steel-manganese mixed slag-based cement ink material according to claim 5, characterized in that, In step 1), the mixing speed is 100-200 rpm and the time is 120-300 s.

7. The method for preparing a stabilized steel-manganese mixed slag-based cement ink material according to claim 6, characterized in that, In step 2), when mixing the refining slag and electrolytic manganese slag, the stirring speed is 100-150 rpm and the stirring time is 120-180 s. Each addition is made at a stirring speed of 100-200 rpm and a stirring time of 180-420 s.

8. The method for preparing a stabilized steel-manganese mixed slag-based cement ink material according to claim 7, characterized in that, In step 3), first add 50% water to mixture B and mix and stir at a speed of 100-200 rpm for 60-180 seconds.

9. The method for preparing a stabilized steel-manganese mixed slag-based cement ink material according to claim 8, characterized in that, In step 3), add 50% water to mixture B and mix and stir at a speed of 300-500 rpm for 300-600 seconds.

10. The application of a stabilized steel-manganese mixed slag-based cement ink material as described in claim 3 or 4, characterized in that, The ink material is used in the 3D printing construction industry.

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