A mold-proof and antibacterial material for phosphogypsum building materials and a preparation method thereof
By using solid-phase sintered ZnO-TiO2 composite antibacterial agent in phosphogypsum building materials, the problem of mold growth in phosphogypsum building materials under humid and hot conditions has been solved, achieving stronger antibacterial performance and bacteriostatic effect, and improving the health level of the living environment.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- GUIZHOU UNIV
- Filing Date
- 2023-09-27
- Publication Date
- 2026-07-07
Smart Images
Figure SMS_1 
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Abstract
Description
Technical Field
[0001] This invention relates to the field of anti-mildew phosphogypsum materials, specifically to an anti-mildew and antibacterial phosphogypsum building material and its preparation method. Background Technology
[0002] Prolonged exposure to hot and humid climates can lead to mold growth on phosphogypsum building materials, providing an ideal environment for microbial growth. Fungi are a significant factor contributing to adverse changes in phosphogypsum building materials and the bio-erosion and bio-weathering of the phosphogypsum matrix. Mold causes severe damage to phosphogypsum buildings, affecting their appearance, with mold rates reaching almost 100%. Furthermore, microbial contamination in indoor buildings constructed with phosphogypsum is becoming a major route for the spread of infectious diseases, reducing air quality and causing health problems such as allergies, poisoning, and respiratory illnesses, resulting in significant economic losses and deaths. Currently, research on mold prevention for phosphogypsum building materials is still in its early stages both domestically and internationally, with most studies focusing on mold prevention measures for easily mold-prone materials such as food, wood, leather, and textiles. Therefore, this paper proposes an anti-mold and antibacterial material for phosphogypsum building materials, its preparation method, and its application method. Summary of the Invention
[0003] To address the shortcomings of existing technologies, this invention proposes a mildew-resistant and antibacterial phosphogypsum building material and its preparation method.
[0004] The objective of this invention can be achieved through the following technical solutions:
[0005] A method for preparing phosphogypsum building materials includes the following steps:
[0006] 800-1000 parts by weight of phosphogypsum powder are mixed with deionized water and then cast into phosphogypsum blocks.
[0007] An antibacterial agent is obtained by mixing 10-50 parts by weight of solid-state sintered ZnO powder and 1-5 parts by weight of TiO2 powder.
[0008] The antibacterial agent is mixed into 800-1000 parts by weight of phosphogypsum powder and deionized water before casting, or it is applied to the surface of the phosphogypsum block after 800-1000 parts by weight of phosphogypsum powder and deionized water have been mixed, cast, and shaped.
[0009] Optionally, the sintering process includes the following steps:
[0010] Weigh 10-50 parts by weight of ZnO powder and 1-5 parts by weight of TiO2 powder, mix and grind them in a mortar, and place the ground powder into a crucible and place it in a lifting furnace for solid-phase sintering.
[0011] After the powder is cooled in the lifting furnace, the sample is ground, and the finely ground sample is sintered at a constant temperature in the lifting furnace.
[0012] After sintering, the sample is cooled in the furnace, ground, and sieved.
[0013] Optionally, the sintering time is 2 hours.
[0014] Optionally, the sintering temperature is 300°C.
[0015] Optionally, the coating may be applied multiple times.
[0016] A building material for use with phosphogypsum comprises the following raw materials in parts by weight:
[0017] 800-1000 parts of phosphogypsum powder;
[0018] 10-50 parts ZnO powder and 1-5 parts TiO2 powder.
[0019] The beneficial effects of this invention are:
[0020] This invention first selects pure ZnO and pure TiO2 as composite antibacterial materials, overcoming the shortcomings of using either material alone, and obtaining an antibacterial material with superior antibacterial properties. Through solid-state sintering, photocatalytic antibacterial material titanium dioxide and inorganic antibacterial material zinc oxide are composited, enabling photocatalytic antibacterial activity under strong light and antibacterial activity under dark conditions using zinc oxide, thus achieving a synergistic antibacterial effect of the inorganic antibacterial materials. In summary, the solid-state sintered ZnO-TiO2 composite powder exhibits stronger antibacterial properties than pure ZnO and pure TiO2. The high surface defect content plays an important role in the antibacterial efficiency mechanism of metal oxides. The TiO2 and ZnO inorganic antibacterial agents show strong antibacterial capabilities against various bacterial groups, including Gram-positive, Gram-negative bacteria, and Bacillus, demonstrating excellent antibacterial performance. Compared with similar inorganic antibacterial agents from Japan, they exhibit better antibacterial performance and are expected to be widely used. To rapidly improve the quality of human living environments, controlling bacterial growth on or within wall materials is essential. Traditional methods for preventing mold on phosphogypsum, food, and wood mostly involve soaking or applying antibacterial agents and waterproof and moisture-proof materials, while a few methods use internal mixing of antibacterial agents to achieve the purpose of antibacterial and mold prevention. Detailed Implementation
[0021] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0022] Implementation Case 1
[0023] 800 parts of phosphogypsum powder were dried in a constant temperature drying oven at 50°C for 2 hours, sealed and stored for later use to obtain component A;
[0024] Weigh 10 parts ZnO powder and 1 part TiO2 powder, transfer the weighed powders to a mortar, mix evenly and grind for 2 hours. Place the ground powder in a crucible and place it in a lifting furnace for solid-state sintering for 2 hours at a temperature of 300℃. After the powder cools in the lifting furnace, grind the sample for 2 hours. Continue to sinter the finely ground sample in the lifting furnace at a constant temperature for 2 hours at a temperature of 300℃. After sintering, cool the sample in the furnace, grind it through a 200-mesh (75μm) sieve, seal it for later use, and obtain component B.
[0025] 1. Weigh 800 parts of component A and 10 parts of component B and put them into a beaker. Mix them evenly with a stirrer at a speed of 1600 r / min. After mixing evenly, mix the powder with deionized water and pour it into a mold. After solidification, remove the mold to obtain an antibacterial phosphogypsum test block.
[0026] 2. Weigh 800 parts of component A, mix component A with deionized water until homogeneous, then pour into a mold for casting. After solidification, remove the mold to obtain a phosphogypsum test block. Take 10 parts of the prepared component B and mix it with deionized water to prepare an antibacterial agent. Apply the antibacterial agent to the surface of the phosphogypsum test block with a coating thickness of 0.5 mm. After 2 hours, apply another layer of antibacterial agent with a coating thickness of 0.5 mm. After 24 hours, apply the antibacterial agent to the surface of the test block with a coating thickness of 1 mm. After air drying for 1 week, apply another layer of antibacterial agent with a coating thickness of 1 mm. After air drying for 24 hours, a composite antibacterial phosphogypsum test block coated with antibacterial material is obtained.
[0027] 3. Weigh 800 parts of component A and 10 parts of component B and place them in a beaker. Mix them thoroughly with a stirrer at 1600 rpm. After mixing, combine the powder with deionized water and pour the mixture into a mold. After solidification, remove the mold to obtain an antibacterial phosphogypsum block. Apply an antibacterial agent to the surface of the antibacterial phosphogypsum block with a coating thickness of 0.5 mm. After 2 hours, apply another layer of antibacterial agent with a coating thickness of 0.5 mm. After 24 hours, apply another layer of antibacterial agent to the surface of the block with a coating thickness of 1 mm. After air drying for 1 week, apply another layer of antibacterial agent with a coating thickness of 1 mm. After air drying for 24 hours, a composite antibacterial phosphogypsum block coated with antibacterial material is obtained.
[0028] Implementation Case 2
[0029] 850 parts of phosphogypsum powder were dried in a constant temperature drying oven at 50°C for 3 hours, sealed and stored for later use to obtain component A;
[0030] Weigh 20 parts ZnO powder and 2 parts TiO2 powder, transfer the weighed powders to a mortar, mix evenly and grind for 2 hours. Place the ground powder in a crucible and place it in a lifting furnace for solid-state sintering for 2 hours at a temperature of 300℃. After the powder cools in the lifting furnace, grind the sample for 2 hours. Continue to sinter the finely ground sample in the lifting furnace at a constant temperature for 2 hours at a temperature of 300℃. After sintering, cool the sample in the furnace, grind it through a 200-mesh (75μm) sieve, seal it for later use, and obtain component B.
[0031] 1. Weigh 850 parts of component A and 20 parts of component B and put them into a beaker. Mix them evenly with a stirrer at a speed of 1700 r / min. After mixing evenly, mix the powder with deionized water and pour it into a mold. After solidification, remove the mold to obtain an antibacterial phosphogypsum test block.
[0032] 2. Weigh 850 parts of component A, mix component A with deionized water until homogeneous, then pour into a mold for casting. After solidification, remove the mold to obtain a phosphogypsum test block. Take 20 parts of the prepared component B and mix it with deionized water to prepare an antibacterial agent. Apply the antibacterial agent to the surface of the phosphogypsum test block with a coating thickness of 0.5 mm. After 2 hours, apply another layer of antibacterial agent with a coating thickness of 0.5 mm. After 24 hours, apply the antibacterial agent to the surface of the test block with a coating thickness of 1 mm. After air drying for 1 week, apply another layer of antibacterial agent with a coating thickness of 1 mm. After air drying for 24 hours, a composite antibacterial phosphogypsum test block coated with antibacterial material is obtained.
[0033] 3. Weigh 850 parts of component A and 20 parts of component B and place them in a beaker. Mix them thoroughly with a stirrer at 1700 rpm. After mixing, combine the powder with deionized water and pour the mixture into a mold. After solidification, remove the mold to obtain an antibacterial phosphogypsum block. Apply an antibacterial agent to the surface of the antibacterial phosphogypsum block with a coating thickness of 0.5 mm. After 2 hours, apply another layer of antibacterial agent with a coating thickness of 0.5 mm. After 24 hours, apply another layer of antibacterial agent to the surface of the block with a coating thickness of 1 mm. After air drying for 1 week, apply another layer of antibacterial agent with a coating thickness of 1 mm. After air drying for 24 hours, a composite antibacterial phosphogypsum block coated with antibacterial material is obtained.
[0034] Implementation Case 3
[0035] 900 parts of phosphogypsum powder were dried in a constant temperature drying oven at 50°C for 4 hours, sealed and stored for later use to obtain component A;
[0036] Weigh 30 parts ZnO powder and 3 parts TiO2 powder, transfer the weighed powders to a mortar, mix evenly and grind for 2 hours. Place the ground powder in a crucible and place it in a lifting furnace for solid-state sintering for 2 hours at a temperature of 300℃. After the powder cools in the lifting furnace, grind the sample for 2 hours. Continue to sinter the finely ground sample in the lifting furnace at a constant temperature for 2 hours at a temperature of 300℃. After sintering, cool the sample in the furnace, grind it through a 200-mesh (75μm) sieve, seal it for later use, and obtain component B.
[0037] 1. Weigh 900 parts of component A and 30 parts of component B and put them into a beaker. Mix them evenly with a stirrer at a speed of 1800 r / min. After mixing evenly, mix the powder with deionized water and pour it into a mold. After solidification, remove the mold. The resulting antibacterial phosphogypsum test block can be obtained.
[0038] 2. Weigh 900 parts of component A, mix component A with deionized water until homogeneous, then pour into a mold for casting. After solidification, remove the mold to obtain a phosphogypsum test block. Take 30 parts of the prepared component B and mix it with deionized water to prepare an antibacterial agent. Apply the antibacterial agent to the surface of the phosphogypsum test block with a coating thickness of 0.5 mm. After 2 hours, apply another layer of antibacterial agent with a coating thickness of 0.5 mm. After 24 hours, apply the antibacterial agent to the surface of the test block with a coating thickness of 1 mm. After air drying for 1 week, apply another layer of antibacterial agent with a coating thickness of 1 mm. After air drying for 24 hours, a composite antibacterial phosphogypsum test block coated with antibacterial material is obtained.
[0039] 3. Weigh 900 parts of component A and 30 parts of component B and place them in a beaker. Mix them thoroughly with a stirrer at 1800 rpm. After mixing, combine the powder with deionized water and pour the mixture into a mold. After solidification, remove the mold to obtain an antibacterial phosphogypsum block. Apply an antibacterial agent to the surface of the antibacterial phosphogypsum block with a coating thickness of 0.5 mm. After 2 hours, apply another layer of antibacterial agent with a coating thickness of 0.5 mm. After 24 hours, apply another layer of antibacterial agent to the surface of the block with a coating thickness of 1 mm. After air drying for 1 week, apply another layer of antibacterial agent with a coating thickness of 1 mm. After air drying for 24 hours, a composite antibacterial phosphogypsum block coated with antibacterial material is obtained.
[0040] Implementation Case 4
[0041] 950 parts of phosphogypsum powder were dried in a constant temperature drying oven at 50°C for 5 hours, sealed and stored for later use to obtain component A;
[0042] Weigh 40 parts of ZnO powder and 4 parts of TiO2 powder, transfer the weighed powders to a mortar, mix them evenly, and grind for 2 hours. Place the ground powder in a crucible and sinter it in a lifting furnace for 2 hours at a temperature of 300℃. After the powder cools in the lifting furnace, grind the sample for 2 hours. Continue to sinter the finely ground sample in the lifting furnace at a constant temperature for 2 hours at a temperature of 300℃. After sintering, cool the sample in the furnace, grind it through a 200-mesh (75μm) sieve, seal it for later use, and obtain component B.
[0043] 1. Weigh 950 parts of component A and 40 parts of component B and put them into a beaker. Mix them evenly with a stirrer at a speed of 1900 r / min. After mixing evenly, mix the powder with deionized water and pour it into a mold. After solidification, remove the mold to obtain an antibacterial phosphogypsum test block.
[0044] 2. Weigh 950 parts of component A, mix component A with deionized water until homogeneous, then pour into a mold for casting. After solidification, remove the mold to obtain a phosphogypsum test block. Take 40 parts of the prepared component B and mix it with deionized water to prepare an antibacterial agent. Apply the antibacterial agent to the surface of the phosphogypsum test block with a coating thickness of 0.5 mm. After 2 hours, apply another layer of antibacterial agent with a coating thickness of 0.5 mm. After 24 hours, apply the antibacterial agent to the surface of the test block with a coating thickness of 1 mm. After air drying for 1 week, apply another layer of antibacterial agent with a coating thickness of 1 mm. After air drying for 24 hours, a composite antibacterial phosphogypsum test block coated with antibacterial material is obtained.
[0045] 3. Weigh 950 parts of component A and 40 parts of component B and place them in a beaker. Mix them thoroughly with a stirrer at 1900 rpm. After mixing, combine the powder with deionized water and pour the mixture into a mold. After solidification, remove the mold to obtain an antibacterial phosphogypsum block. Apply an antibacterial agent to the surface of the antibacterial phosphogypsum block with a coating thickness of 0.5 mm. After 2 hours, apply another layer of antibacterial agent with a coating thickness of 0.5 mm. After 24 hours, apply another layer of antibacterial agent to the surface of the block with a coating thickness of 1 mm. After air drying for 1 week, apply another layer of antibacterial agent with a coating thickness of 1 mm. After air drying for 24 hours, a composite antibacterial phosphogypsum block coated with antibacterial material is obtained.
[0046] Implementation Case 5
[0047] 1000 parts of phosphogypsum powder were dried in a constant temperature drying oven at 50°C for 6 hours, sealed and stored for later use to obtain component A;
[0048] Weigh 50 parts of ZnO powder and 5 parts of TiO2 powder, transfer the weighed powders to a mortar, mix them evenly, and grind for 2 hours. Place the ground powder in a crucible and sinter it in a lifting furnace for 2 hours at a temperature of 300℃. After the powder cools in the lifting furnace, grind the sample for 2 hours. Continue to sinter the finely ground sample in the lifting furnace at a constant temperature for 2 hours at a temperature of 300℃. After sintering, cool the sample in the furnace, grind it through a 200-mesh (75μm) sieve, seal it for later use, and obtain component B.
[0049] 1. Weigh 1000 parts of component A and 50 parts of component B and put them into a beaker. Mix them evenly with a stirrer at a speed of 2000 r / min. After mixing evenly, mix the powder with deionized water and pour it into a mold. After solidification, remove the mold to obtain an antibacterial phosphogypsum test block.
[0050] 2. Weigh 1000 parts of component A, mix component A with deionized water until homogeneous, then pour into a mold for casting. After solidification, remove the mold to obtain a phosphogypsum test block. Take 50 parts of the prepared component B and mix it with deionized water to prepare an antibacterial agent. Apply the antibacterial agent to the surface of the phosphogypsum test block with a coating thickness of 0.5 mm. After 2 hours, apply another layer of antibacterial agent with a coating thickness of 0.5 mm. After 24 hours, apply the antibacterial agent to the surface of the test block with a coating thickness of 1 mm. After air drying for 1 week, apply another layer of antibacterial agent with a coating thickness of 1 mm. After air drying for 24 hours, a composite antibacterial phosphogypsum test block coated with antibacterial material is obtained.
[0051] 3. Weigh 1000 parts of component A and 50 parts of component B and place them in a beaker. Mix them thoroughly with a stirrer at 2000 rpm. After mixing, combine the powder with deionized water and pour the mixture into a mold. After solidification, remove the mold to obtain an antibacterial phosphogypsum block. Apply an antibacterial agent to the surface of the antibacterial phosphogypsum block with a coating thickness of 0.5 mm. After 2 hours, apply another layer of antibacterial agent with a coating thickness of 0.5 mm. After 24 hours, apply another layer of antibacterial agent to the surface of the block with a coating thickness of 1 mm. After air drying for 1 week, apply another layer of antibacterial agent with a coating thickness of 1 mm. After air drying for 24 hours, a composite antibacterial phosphogypsum block coated with antibacterial material is obtained.
[0052] Comparative Example
[0053] Comparative Example 1
[0054] The difference between Comparative Example 1 and Example 1 is that Component B was not added to the raw materials of Comparative Example 1 and Component B was not applied to the surface of the phosphogypsum test block. All other aspects are consistent with Example 1.
[0055] Comparative Example 2
[0056] The difference between Comparative Example 2 and Example 2 is that component B in Comparative Example 2 did not contain TiO2, while all other components remained the same as in Example 2.
[0057] Comparative Example 3
[0058] The difference between Comparative Example 3 and Example 3 is that ZnO was not added to component B in Comparative Example 3, while all other components were the same as in Example 3.
[0059] Comparative Example 4
[0060] The difference between Comparative Example 4 and Example 1 is that component B in Comparative Example 4 was not subjected to sintering in a lifting furnace, while all other components were the same as in Example 1.
[0061] Performance testing
[0062] 1. Compressive strength: Referring to the test method published in GB / T17669.3-1999 "Determination of mechanical properties of building gypsum", specimens with a size of 40mm*40mm*160mm were prepared. The compressive strength of antibacterial phosphogypsum specimens in Examples 1-5 and Comparative Examples 1-4 was tested for 28 days using a pressure testing machine. The results are shown in Table 1.
[0063] 2. Flexural strength: Referring to the test method published in GB / T17669.3-1999 "Determination of Mechanical Properties of Building Gypsum", specimens with a size of 40mm*40mm*160mm were prepared. The flexural strength of antibacterial phosphogypsum specimens in Examples 1-5 and Comparative Examples 1-4 was tested for 28 days using a pressure testing machine. The results are shown in Table 1.
[0064] 3. Inhibition zone: Following the method for detecting inhibition zones, 20mm diameter inhibition discs were prepared and tested on Examples 1-5 and Comparative Examples 1-4. The diameter of the inhibition zone was measured and the inhibition rate was calculated. The results are shown in Table 1.
[0065] Table 1. Performance Comparison of Antibacterial Phosphogypsum Products in Different Examples and Comparative Examples
[0066]
[0067]
[0068] Comparing the results of Comparative Example 1 and Example 1, it can be seen that when preparing antibacterial phosphogypsum, the compressive strength and flexural strength of the phosphogypsum specimens prepared by adding component B and applying component B in Example 1 are lower than those of the compressive strength and flexural strength obtained in Comparative Example 1, but the antibacterial rate is higher than that of Comparative Example 1. It can be seen that adding antibacterial materials to phosphogypsum and applying antibacterial materials can effectively improve the antibacterial rate and the strength level meets the standard requirements.
[0069] Comparing the results of Comparative Example 2 and Example 2, it can be seen that when preparing antibacterial phosphogypsum, the compressive strength, flexural strength, and antibacterial rate of the phosphogypsum specimen of Example 2 are all higher than those of Comparative Example 2. This shows that adding antibacterial materials to phosphogypsum and applying antibacterial materials can effectively improve the antibacterial rate. Moreover, the antibacterial effect of the composite antibacterial material with added TiO2 is stronger than that of pure ZnO, and the strength grade meets the standard requirements.
[0070] Comparing the results of Comparative Example 3 and Example 3, it can be seen that when preparing antibacterial phosphogypsum, the compressive strength and flexural strength of the phosphogypsum specimen in Example 3 are higher than those in Comparative Example 3, while the antibacterial rate is lower than that in Comparative Example 3. This shows that adding antibacterial materials to phosphogypsum and applying antibacterial materials can effectively improve the antibacterial rate. Furthermore, the antibacterial effect of the composite antibacterial material of pure TiO2 is lower than that of pure ZnO, and the strength grade meets the standard requirements.
[0071] Comparing the results of Comparative Example 4 and Example 4, it can be seen that when preparing antibacterial phosphogypsum, the compressive strength and flexural strength of the phosphogypsum specimens prepared by adding component B and applying component B in Example 1 are not much different from those of the compressive strength and flexural strength obtained in Comparative Example 1, but the antibacterial rate is higher than that of Comparative Example 4. It can be seen that the antibacterial material after solid-phase sintering can effectively improve the antibacterial rate and the strength level meets the standard requirements.
[0072] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.
[0073] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the claimed invention.
Claims
1. A method for preparing phosphogypsum building materials, comprising the following steps: 800-1000 parts by weight of phosphogypsum powder are mixed with deionized water and then cast into phosphogypsum blocks. An antibacterial agent is obtained by sintering a component containing 10-50 parts by weight of ZnO powder and 1-5 parts by weight of TiO2 powder. The antibacterial agent is mixed in with 800-1000 parts by weight of phosphogypsum powder and deionized water before casting and molding, or it is applied to the surface of the phosphogypsum block after 800-1000 parts by weight of phosphogypsum powder and deionized water have been cast and molded. The sintering process includes the following steps: Weigh 10-50 parts by weight of ZnO powder and 1-5 parts by weight of TiO2 powder, mix and grind them in a mortar, and place the ground powder into a crucible and place it in a lifting furnace for solid-phase sintering. After the powder is cooled in the lifting furnace, the sample is ground, and the finely ground sample is sintered at a constant temperature in the lifting furnace. After sintering, the sample is cooled in the furnace, ground, and sieved. The sintering time is 2 hours and the sintering temperature is 300℃.
2. The method for preparing a phosphogypsum building material according to claim 1, characterized in that, The coating process is repeated multiple times.
3. The phosphogypsum building material prepared according to the method of claim 1 or 2, characterized in that, Including the following parts by weight of raw materials: 800-1000 parts of phosphogypsum powder; A composite antibacterial agent consisting of 10-50 parts of solid-state sintered ZnO powder and 1-5 parts of TiO2 powder.