Degradable basalt fiber and preparation method thereof

Abstract

According to the degradable basalt fiber and the preparation method thereof, by modifying fiber components, controlling the content of P2O5 and CaO and by means of the unsaturated metastable state of phosphorus-oxygen double bonds in a phosphorus-oxygen tetrahedron, the solubility is increased, the degradation capacity of the fiber is improved, however, the larger the mass ratio of a phosphorus-containing compound is, the larger the mechanical influence on the fiber is, and the mechanical property of the fiber is improved. Therefore, the mass ratio of P2O5 is controlled not to exceed 8%, CaO does not belong to a glass network forming body structure, degradation performance can be improved to a certain extent after introduction of the mass ratio is improved, but mechanical performance of the fiber can be reduced after excessive introduction, so that the mass ratio of calcium oxide is controlled to be between 8% and 17%, and the degradation performance of the fiber is improved. The degradation capability is enhanced while the mechanical property of the basalt fiber is ensured, the harm to a human body is reduced, the waste fiber is promoted to be degraded more quickly, and the basalt fiber has the characteristics of greenness, environmental protection and high biological safety.

Description

Technical Field

[0001] The present application relates to the field of fiber modification, and in particular to a degradable basalt fiber and a preparation method thereof. Background Art

[0002] Basalt fiber is a continuous fiber made by drawing natural basalt ore after melting at temperatures between 1350°C and 1500°C. It possesses excellent physical and mechanical properties, including high strength, high modulus, excellent high and low temperature resistance, acid and alkali resistance, oxidation resistance, radiation resistance, thermal insulation, sound insulation, fire retardancy, good filterability, high compressive and shear strength, and suitability for use in various environments. The fiber-forming process does not emit alkaline oxides or harmful gases into the atmosphere, and it naturally degrades into soil parent material after use. The energy consumption of the manufacturing process is 1 / 33 to 1 / 16 of that of carbon fiber production. It ranks alongside carbon fiber, aramid fiber, and ultra-high molecular weight fiber as one of the four major fiber materials being developed in my country. Basalt fiber has a structural composition similar to glass fiber. While not inherently harmful to the human body, direct contact with the fiber can cause severe irritation to the skin and eyes, and inhalation of dust particles containing glass fiber may irritate the nasal cavity, trachea, and throat. Symptoms of irritation are generally nonspecific and temporary, and may include itching, coughing, or wheezing. Large amounts of fibers exposed to the air may aggravate existing asthma or bronchitis-like diseases, especially when rock wool boards are widely used in building insulation.

[0003] Therefore, improving the biodegradability of basalt fiber is of great significance to reducing harm to the human body and promoting faster degradation of waste fibers and returning them to the soil. Summary of the Invention

[0004] The present application provides a degradable basalt fiber and a preparation method thereof, which can enhance the degradation ability while ensuring the mechanical properties of the basalt fiber, reduce harm to the human body and promote faster degradation of waste fibers, and has the characteristics of being green, environmentally friendly and highly biosafe.

[0005] The embodiment of the present application is implemented as follows:

[0006] In a first aspect, the present invention provides a degradable basalt fiber, wherein the components of the degradable basalt fiber include: 50-55% SiO2, 10-15% Al2O3, 8-17% CaO, 9-13% FeO and Fe2O3, 4-6% MgO, 0-1% K2O, 1-2% TiO2, 3-10% Na2O, and 0-8% P2O5.

[0007] In an optional embodiment, the mass proportion of P2O5 is 6-8%.

[0008] In an optional embodiment, the mass proportion of CaO is 12-16.5%.

[0009] In a second aspect, the present invention provides a method for preparing degradable basalt fiber, which is used to prepare the degradable basalt fiber according to any of the aforementioned embodiments, and the method comprises the following steps:

[0010] S1, adding CaO to the basalt raw material or adding a phosphorus-containing compound and CaO and mixing them uniformly;

[0011] S2, heating the uniformly mixed powder into a melt;

[0012] S3, drawing the melt to form degradable basalt fibers.

[0013] In alternative embodiments, the phosphorus-containing compound comprises sodium pyrophosphate, ammonium phosphate, or calcium pyrophosphate.

[0014] In an optional embodiment, in step S1, nano-silicon dioxide is further added so that the mass proportion of SiO2 in the degradable basalt fiber is 50-55%.

[0015] In an optional embodiment, in step S1, a star-shaped ball mill is used for mixing for 30-60 minutes.

[0016] In an optional embodiment, the uniformly mixed powder is sieved through a 800-100 mesh sieve.

[0017] In an optional embodiment, step S2 includes:

[0018] S21, placing the uniformly mixed powder into a corundum crucible, heating in a muffle furnace, controlling the heating rate from room temperature to 300°C to be 5°C / min, the heating rate from 300°C to 1000°C to be 7.5°C / min, and the heating rate from 1000°C to 1500°C to be 3°C / min, and maintaining the temperature for 2-4 hours;

[0019] S22, pouring the melt into water and quenching it to 25°C to obtain black glass;

[0020] S23, placing the black glass into a platinum crucible and heating it in a drawing furnace at a heating rate of 10°C / min and controlling the temperature at 1450-1550°C;

[0021] S24, the fiber is drawn and wound onto a reel.

[0022] In an optional embodiment, in step S24, the diameter of the degradable basalt fiber can be controlled to be 10-20 μm by changing the rotation speed of the reel to 100-600 m / min.

[0023] By modifying the fiber composition and controlling the content of P2O5 and CaO, the solubility is increased by taking advantage of the unsaturated metastable state of the phosphorus-oxygen double bond in the phosphorus-oxygen tetrahedron, thereby increasing the degradation ability of the fiber. However, the greater the mass proportion of the phosphorus-containing compound, the greater the mechanical impact on the fiber. Therefore, the mass proportion of P2O5 is controlled to be no more than 8%. CaO does not belong to the glass network molding structure. When the mass proportion is increased, the degradation performance will be improved to a certain extent. However, excessive introduction will reduce the mechanical properties of the fiber. Therefore, the mass proportion of calcium oxide is controlled between 8-17%. This ensures the mechanical properties of basalt fiber while enhancing the degradation ability, reducing harm to the human body and promoting faster degradation of waste fibers. It has the characteristics of being green, environmentally friendly and highly biosafe. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following is a brief introduction to the drawings required for use in the embodiments. It should be understood that the following drawings only show certain embodiments of the present application and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other relevant drawings can be obtained based on these drawings without creative work.

[0025] Figure 1 This is a flowchart of the method for preparing degradable basalt fiber according to an embodiment of the present application. DETAILED DESCRIPTION

[0026] As used herein:

[0027] "Prepared from" is synonymous with "comprising." As used herein, the terms "comprising," "including," "having," "containing," or any other variations thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises the listed elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

[0028] When an amount, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper preferred values and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pairing of any range upper limit or preferred value with any range lower limit or preferred value, regardless of whether the range is disclosed alone. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted as including the range "1 to 4", "1 to 3", "1 to 2", "1 to 2 and 4 to 5", "1 to 3 and 5", etc. When a numerical range is described herein, unless otherwise stated, the range is intended to include its end values and all integers and fractions within the range.

[0029] In these examples, parts and usage ratios are based on mass unless otherwise specified.

[0030] The embodiments of the present application will be described in detail below with reference to the examples, but it will be understood by those skilled in the art that the following examples are merely illustrative of the present application and should not be considered as limiting the scope of the present application. In the examples, if specific conditions are not specified, the conditions are carried out according to conventional conditions or manufacturer recommendations. The reagents or instruments used are not specified by the manufacturer and are conventional products that can be purchased commercially.

[0031] An embodiment of the present application discloses a degradable basalt fiber, the components of which include: 50-55% SiO2, 10-15% Al2O3, 8-17% CaO, 9-13% FeO and Fe2O3, 4-6% MgO, 0-1% K2O, 1-2% TiO2, 3-10% Na2O, and 0-8% P2O5.

[0032] In this embodiment, by modifying the fiber composition and controlling the contents of P2O5 and CaO, the solubility is increased by means of the unsaturated metastable state of the phosphorus-oxygen double bond in the phosphorus-oxygen tetrahedron, thereby increasing the degradation ability of the fiber. However, the greater the mass proportion of the phosphorus-containing compound, the greater the mechanical influence on the fiber. Therefore, the mass proportion of P2O5 is controlled to be no more than 8%. CaO does not belong to the glass network molded body structure. When the mass proportion is increased, the degradation performance will be improved to a certain extent. However, excessive introduction will reduce the mechanical properties of the fiber. Therefore, the mass proportion of calcium oxide is controlled to be between 8-17%, so as to enhance the degradation ability while ensuring the mechanical properties of basalt fiber, reduce harm to the human body, and promote faster degradation of waste fibers. It has the characteristics of being green, environmentally friendly, and highly biosafe.

[0033] In order to better ensure the mechanical properties and degradation performance of basalt fiber, the mass proportion of P2O5 is controlled at 6-8%, and the mass proportion of CaO is controlled at 12-16.5%, further improving the comprehensive performance of degradable basalt fiber.

[0034] Combine Figure 1 The present application also discloses a method for preparing degradable basalt fiber, which is used to prepare the above-mentioned degradable basalt fiber. The method includes the following steps S to S3:

[0035] Step S1, adding CaO or adding a phosphorus-containing compound and CaO to the basalt raw material and mixing them uniformly;

[0036] Step S2, heating the uniformly mixed powder into a melt;

[0037] Step S3: Drawing the melt into degradable basalt fibers.

[0038] In this way, by adding phosphorus-containing compounds and CaO or only CaO to the existing basalt raw materials, the evenly mixed powder is heated, and the phosphorus-containing compound is decomposed at high temperature to form P2O5. The addition of CaO powder can increase the CaO content in the melt, and then increase the CaO content in the fiber formed by the final drawing, thereby obtaining the above-mentioned degradable basalt fiber, ensuring mechanical properties while enhancing degradation ability.

[0039] The phosphorus-containing compound includes sodium pyrophosphate, ammonium phosphate or calcium pyrophosphate, etc., as long as it is a material that can decompose at high temperature to form P2O5.

[0040] In step S1, nano-silica is also added to make the mass proportion of SiO2 in the degradable basalt fiber be 50-55%. Nano-silica can significantly increase the roughness and chemical reaction activity of the fiber surface, improve the surface activity and interfacial bonding strength of the fiber, and the dispersibility of nano-SiO2 can be optimized through the melt blending process. Moreover, the introduction of nano-SiO2 can enhance the tensile strength and elastic modulus of the fiber. Increasing the mass proportion of SiO2 in the fiber can accelerate the hydrolysis of the fiber under specific pH conditions, while maintaining the mechanical properties of the overall material until degradation is complete.

[0041] In step S1, a star-shaped ball mill is used for mixing for 30-60 minutes. The uniformly mixed powder is sieved through an 800-100 mesh sieve to control the powder particle size for better fusion in the molten state.

[0042] In detail, step S2 includes the following steps S21 to S24:

[0043] Step S21: Place the mixed powder into a corundum crucible and heat it in a muffle furnace. Control the heating rate from room temperature to 300°C at 5°C / min, the heating rate from 300°C to 1000°C at 7.5°C / min, and the heating rate from 1000°C to 1500°C at 3°C / min, and keep the temperature for 2-4 hours.

[0044] Specifically, slowly heating from room temperature to 300°C (5°C / min) can reduce the thermal stress between powder particles and avoid pores or microcracks caused by rapid expansion. 300°C to 1000°C (7.5°C / min) accelerates the early densification process. At this stage, powder particles gradually eliminate pores through surface diffusion and grain boundary sliding, thereby increasing the density of the green body. Slowing down the heating in the high temperature section from 1000°C to 1500°C (3°C / min) can promote grain growth and pore closure, and sintering densification. During the holding stage, Ostwald ripening is used to further optimize the grain size distribution and improve the mechanical properties of the material.

[0045] Step S22: pouring the melt into water and quenching it to 25°C to obtain black glass; the melt (at high temperature is a liquid disordered structure, and rapid cooling (>103°C / s) prevents the atoms / molecules from being orderly arranged into crystals, forming amorphous glass.

[0046] Step S23: Place the black glass into a platinum crucible and heat it in a drawing furnace at a heating rate of 10°C / min. The temperature is controlled at 1450-1550°C to keep the melt in a drawable state.

[0047] In step S24, the fiber is drawn and wound onto a reel.

[0048] In step S24, the diameter of the degradable basalt fiber can be controlled to be 10-20 μm by changing the rotation speed of the reel to 100-600 m / min.

[0049] In summary, the present application discloses a degradable basalt fiber and a preparation method thereof. The method has a simple process, low cost, and can be regulated during the basalt preparation process without affecting the normal process of fiber preparation. The prepared fiber is green, environmentally friendly, and has high biosafety. It has a great comparative advantage, especially in products related to human food health in agriculture, fisheries, and other fields. In addition to its green and safe characteristics, the economic efficiency of the material after large-scale production also has significant advantages compared with other materials.

[0050] The following is a further detailed description of the method for preparing the degradable basalt fiber according to the embodiment of the present application in combination with Table 1 and Table 2, and the performance and degradation ability of the fibers in each embodiment are tested:

[0051] Blank group

[0052] The composition of ordinary basalt fiber is: 52.94% SiO2, 14% Al2O3, 8.59% CaO, 12.53% FeO+Fe2O3, 5.78% MgO, 1.68% TiO2, 0.46% K2O, 3.06% Na2O.

[0053] Example 1

[0054] 1. According to the requirement of 90-90.5g basalt powder and 7-7.5g sodium pyrophosphate per 100g melt, the proportion of P2O5 is controlled to 4%. At the same time, 2-2.5g nano-silicon dioxide is introduced to control the mass percentage of SiO2 in the ingredients to about 50%.

[0055] 2. Mix in a planetary ball mill for 60 minutes, and sieve the uniformly mixed powder through a 100-mesh sieve. 500 g of each mixture.

[0056] 3. Place the evenly mixed ingredients into a corundum crucible and heat in a high-temperature muffle furnace. The heating rate is 5°C / min from room temperature to 300°C, 7.5°C / min from 300 to 1000°C, and 3°C / min from 1000 to 1500°C. Keep warm for 4 hours.

[0057] 4. Quickly pour the melt into water to quench the block glass to 25°C to obtain black glass.

[0058] 5. Take 25±1g of the melted glass block and add it to a platinum crucible. Use a drawing furnace to heat it at a rate of 10℃ / min. The temperature is controlled between 1450℃ until the melt is in a drawable state.

[0059] 6. Pull the fiber and wind it onto a reel. By varying the reel's rotational speed to 509 m / min, the fiber diameter is controlled to range from 14 to 16 μm. The fiber composition is: 50% SiO2, 13.24% Al2O3, 7.76% CaO, 11.32% FeO+Fe2O3, 5.22% MgO, 1.52% TiO2, 0.42% K2O, 6.26% Na2O, and 4% P2O5.

[0060] 7. Referring to GB / T 16886.14-2003 and ISO 10933-14:2001, the fiber was tested for weight loss in 1 mol / L HCl and 1 mol / L NaOH solutions at 60°C for 32 hours, and in pH 3 citric acid buffer at 37°C for 5 days. The test results show that the mechanical properties of the fiber are slightly reduced, but the degradation performance in acidic environment is better than that of the blank group.

[0061] Example 2

[0062] 1. According to the requirement of 82-82.5g basalt powder and 11-11.5g sodium pyrophosphate per 100g melt, the proportion of P2O5 is controlled at 6%. At the same time, 6-6.5g nano-silicon dioxide is introduced to control the mass percentage of SiO2 in the ingredients to about 50%.

[0063] 2. Mix in a planetary ball mill for 60 minutes, and sieve the uniformly mixed powder through a 100-mesh sieve. 500 g of each mixture.

[0064] 3. Place the evenly mixed ingredients into a corundum crucible and heat in a high-temperature muffle furnace. The heating rate is 5°C / min from room temperature to 300°C, 7.5°C / min from 300 to 1000°C, and 3°C / min from 1000 to 1500°C. Keep warm for 4 hours.

[0065] 4. Quickly pour the melt into water to quench the block glass to 25°C to obtain black glass.

[0066] 5. Take 25±1g of the melted glass block and add it to a platinum crucible. Use a drawing furnace to heat it at a rate of 10℃ / min. The temperature is controlled between 1430℃ to achieve a drawable state.

[0067] 6. Pull the fiber and wind it onto a reel. By changing the reel's rotation speed to 509 m / min, the fiber diameter is controlled to range from 14 to 15 μm. The fiber composition ratio is: 50% SiO2, 12.07% Al2O3, 7.07% CaO, 10.32% FeO + Fe2O3, 4.76% MgO, 1.38% TiO2, 0.38% K2O, 7.76% Na2O, and 6% P2O5.

[0068] 7. Referring to GB / T 16886.14-2003 and ISO 10933-14:2001 standards, the fiber was tested for weight loss in 1 mol / L HCl and 1 mol / L NaOH solutions at 60°C for 32 hours, and in pH 3 citric acid buffer at 37°C for 5 days. The experimental results showed that the fiber modulus decreased, while the strength retention rate was above 95%, and the degradation performance under acidic conditions was better than that of the blank control.

[0069] Example 3

[0070] 1. For every 100g of melt, 98g of basalt powder and 5.5-6g of ammonium phosphate are required, with the P2O5 ratio controlled at 2%. At the same time, an appropriate amount of nano-silicon dioxide is introduced to control the mass percentage of SiO2 in the ingredients to around 50%.

[0071] 2. Use a planetary ball mill to mix for 120 minutes, and observe every 15 minutes to see if there are any lumps. Sieve the evenly mixed powder through a 100-mesh sieve. 500g of each mixture.

[0072] 3. Place the evenly mixed ingredients into a corundum crucible and heat in a high-temperature muffle furnace. The heating rate is 5°C / min from room temperature to 300°C, 7.5°C / min from 300 to 1000°C, and 3°C / min from 1000 to 1500°C. Keep warm for 4 hours.

[0073] 4. Quickly pour the melt into water to quench the block glass to 25°C to obtain black glass.

[0074] 5. Take 25±1g of the melted glass block and add it to a platinum crucible. Use a drawing furnace to heat it at a rate of 10℃ / min. The temperature is controlled at 1500℃ until the melt is in a drawable state.

[0075] 6. Pull the fiber and wind it onto a reel. By varying the reel's rotational speed to 407 m / min, the fiber diameter is controlled to approximately 15 μm. The fiber composition is: 51.88% SiO2, 14.37% Al2O3, 8.42% CaO, 12.28% FeO+Fe2O3, 5.66% MgO, 1.65% TiO2, 0.45% K2O, 3.00% Na2O, and 2% P2O5.

[0076] 7. Referring to GB / T 16886.14-2003 and ISO 10933-14:2001, the fiber was tested for weight loss in 1 mol / L HCl and 1 mol / L NaOH solutions at 60°C for 32 hours, and in pH 3 citric acid buffer at 37°C for 5 days. The results showed that the mechanical properties and degradation performance of the fiber in acidic conditions were superior to those of the blank control.

[0077] Example 4

[0078] 1. For every 100g of melt, 96g of basalt powder and 11-11.5g of ammonium phosphate are required, with the P2O5 ratio controlled at 4%. At the same time, an appropriate amount of nano-silicon dioxide is introduced to control the mass percentage of SiO2 in the ingredients to around 50%.

[0079] 2. Use a planetary ball mill to mix for 120 minutes, and observe every 15 minutes to see if there are any lumps. Sieve the evenly mixed powder through a 100-mesh sieve. 500g of each mixture.

[0080] 3. Place the evenly mixed ingredients into a corundum crucible and heat in a high-temperature muffle furnace. The heating rate is 5°C / min from room temperature to 300°C, 7.5°C / min from 300 to 1000°C, and 3°C / min from 1000 to 1500°C. Keep warm for 4 hours.

[0081] 4. Quickly pour the melt into water to quench the block glass to 25°C to obtain black glass.

[0082] 5. Take 25±1g of the melted glass block and add it to a platinum crucible. Use a drawing furnace to heat it at a rate of 10℃ / min. The temperature is controlled at 1500℃ until the melt is in a drawable state.

[0083] 6. Pull the fiber and wind it onto a reel. By varying the reel's rotational speed to 407 m / min, the fiber diameter is controlled to approximately 15 μm. The fiber composition is: 50.82% SiO2, 14.07% Al2O3, 8.25% CaO, 12.03% FeO+Fe2O3, 5.55% MgO, 1.61% TiO2, 0.44% K2O, 2.94% Na2O, and 4% P2O5.

[0084] 7. Referring to GB / T 16886.14-2003 and ISO 10933-14:2001, the fiber was tested for weight loss in 1 mol / L HCl and 1 mol / L NaOH solutions at 60°C for 32 hours, and in pH 3 citric acid buffer at 37°C for 5 days. The results showed that the mechanical properties and degradation performance of the fiber in acidic conditions were superior to those of the blank control.

[0085] Example 5

[0086] 1. According to the requirement of 93.5g basalt powder and 17-17.5g ammonium phosphate per 100g melt, the proportion of P2O5 is controlled at 6%. At the same time, 0-0.6g nano-silicon dioxide is introduced to control the mass percentage of SiO2 in the ingredients to about 50%.

[0087] 2. Use a planetary ball mill to mix for 120 minutes, and observe every 15 minutes to see if there are any lumps. Sieve the evenly mixed powder through a 100-mesh sieve. 500g of each mixture.

[0088] 3. Place the evenly mixed ingredients into a corundum crucible and heat in a high-temperature muffle furnace. The heating rate is 5°C / min from room temperature to 300°C, 7.5°C / min from 300 to 1000°C, and 3°C / min from 1000 to 1500°C. Keep warm for 4 hours.

[0089] 4. Quickly pour the melt into water to quench the block glass to 25°C to obtain black glass.

[0090] 5. Take 25±1g of the melted glass block and add it to a platinum crucible. Use a drawing furnace to heat it at a rate of 10℃ / min. The temperature is controlled between 1450℃ and 1500℃ so that the melt can be drawn.

[0091] 6. Pull the fiber and wind it onto a reel. By varying the reel's rotational speed to 407 m / min, the fiber diameter is controlled to 15-16 μm. The fiber composition is: 50.00% SiO2, 13.70% Al2O3, 8.03% CaO, 11.71% FeO+Fe2O3, 5.40% MgO, 1.57% TiO2, 0.43% K2O, 2.86% Na2O, and 6% P2O5.

[0092] 7. Referring to GB / T 16886.14-2003 and ISO 10933-14:2001 standards, the fiber was tested for weight loss in 1 mol / L HCl and 1 mol / L NaOH solutions at 60°C for 32 hours, and in a pH 3 citric acid buffer solution at 37°C for 5 days. The experimental results showed that the mechanical properties of the fiber decreased, but the breaking strength retention rate was over 90%. The degradation performance under acidic conditions was greatly improved, and the dissolution rate was 10-20 times that of the blank group.

[0093] Example 6

[0094] 1. According to the requirement of 89-89.5g basalt powder and 22.5-23g ammonium phosphate per 100g melt, the proportion of P2O5 is controlled at 8%. At the same time, 2.5-3g nano-silicon dioxide is introduced to control the mass percentage of SiO2 in the ingredients to about 50%.

[0095] 2. Use a planetary ball mill to mix for 120 minutes, and observe every 15 minutes to see if there are any lumps. Sieve the evenly mixed powder through a 100-mesh sieve. 500g of each mixture.

[0096] 3. Place the evenly mixed ingredients into a corundum crucible and heat in a high-temperature muffle furnace. The heating rate is 5°C / min from room temperature to 300°C, 7.5°C / min from 300 to 1000°C, and 3°C / min from 1000 to 1500°C. Keep warm for 4 hours.

[0097] 4. Quickly pour the melt into water to quench the block glass to 25°C to obtain black glass.

[0098] 5. Take 25±1g of the melted glass block and add it to a platinum crucible. Use a drawing furnace to heat it at a rate of 10℃ / min. The temperature is controlled between 1450℃ and 1500℃ so that the melt can be drawn.

[0099] 6. Pull the fiber and wind it onto a reel. By changing the reel's rotation speed to 305 m / min, the fiber diameter is controlled to be around 15 μm. The fiber composition ratio is: 50.00% SiO2, 13.08% Al2O3, 7.67% CaO, 11.18% FeO+Fe2O3, 5.16% MgO, 1.50% TiO2, 0.41% K2O, 2.73% Na2O, and 8% P2O5.

[0100] 7. Fiber weight loss was tested in 1 mol / L HCl and 1 mol / L NaOH solutions at 60°C for 32 hours, and in pH 3 citric acid buffer at 37°C for 5 days, referring to GB / T 16886.14-2003 and ISO 10933-14:2001. The results showed that the fiber's mechanical properties declined, but its breaking strength retention rate exceeded 95%. Its degradation performance in both acidic and alkaline conditions was superior to that of the blank group. The dissolution rate in acidic conditions was over 50 times that of the blank group, and its initial dissolution rate was 235 times that of the blank group.

[0101] Example 7

[0102] 1. According to the requirement of about 91g basalt powder and 7-7.5g calcium pyrophosphate per 100g melt, the proportion of P2O5 is controlled at 4%. At the same time, 1.5-2g nano-silicon dioxide is introduced to control the mass percentage of SiO2 in the ingredients to about 50%.

[0103] 2. Mix in a planetary ball mill for 60 minutes, and sieve the uniformly mixed powder through a 100-mesh sieve. 500 g of each mixture.

[0104] 3. Place the evenly mixed ingredients into a corundum crucible and heat in a high-temperature muffle furnace. The heating rate is 5°C / min from room temperature to 300°C, 7.5°C / min from 300 to 1000°C, and 3°C / min from 1000 to 1500°C. Keep warm for 4 hours.

[0105] 4. Quickly pour the melt into water to quench the block glass to 25°C to obtain black glass.

[0106] 5. Take 25±1g of the melted glass block and add it to a platinum crucible. Use a drawing furnace to heat it at a rate of 10℃ / min. The temperature is controlled between 1450℃ until the melt is in a drawable state.

[0107] 6. Pull the fiber and wind it onto a reel. By changing the reel's rotation speed to 509 m / min, the fiber diameter is controlled to range from 14 to 15 μm. The fiber composition ratio is: 50.00% SiO2, 13.35% Al2O3, 10.97% CaO, 11.41% FeO + Fe2O3, 5.26% MgO, 1.53% TiO2, 0.42% K2O, 2.79% Na2O, and 4% P2O5.

[0108] 7. Fiber weight loss was tested in 1 mol / L HCl and 1 mol / L NaOH solutions at 60°C for 32 hours, and in pH 3 citric acid buffer at 37°C for 5 days, according to GB / T 16886.14-2003 and ISO 10933-14:2001 standards. The results showed that the mechanical properties of the fiber decreased, but the degradation performance under acidic conditions was better than that of the blank control.

[0109] Example 8

[0110] 1. According to the requirement of 83-83.5g basalt powder and 10.5-11g calcium pyrophosphate per 100g melt, the proportion of P2O5 is controlled at 6%, and 5.5-6g nano-silicon dioxide is introduced to control the mass percentage of SiO2 in the ingredients to about 50%.

[0111] 2. Mix in a planetary ball mill for 60 minutes, and sieve the uniformly mixed powder through a 100-mesh sieve. 500 g of each mixture.

[0112] 3. Place the evenly mixed ingredients into a corundum crucible and heat in a high-temperature muffle furnace. The heating rate is 5°C / min from room temperature to 300°C, 7.5°C / min from 300 to 1000°C, and 3°C / min from 1000 to 1500°C. Keep warm for 4 hours.

[0113] 4. Quickly pour the melt into water to quench the block glass to 25°C to obtain black glass.

[0114] 5. Take 25±1g of the melted glass block and add it to a platinum crucible. Use a drawing furnace to heat it at a rate of 10℃ / min. The temperature is controlled between 1450℃ until the melt is in a drawable state.

[0115] 6. Pull the fiber and wind it onto a reel. By changing the reel's rotation speed to 509 m / min, the fiber diameter is controlled to range from 14 to 15 μm. The fiber composition ratio is: 50.00% SiO2, 12.23% Al2O3, 11.90% CaO, 10.45% FeO + Fe2O3, 4.82% MgO, 1.40% TiO2, 0.38% K2O, 2.55% Na2O, and 6% P2O5.

[0116] 7. Fiber weight loss was tested in 1 mol / L HCl and 1 mol / L NaOH solutions at 60°C for 32 hours, and in pH 3 citric acid buffer at 37°C for 5 days, according to GB / T 16886.14-2003 and ISO 10933-14:2001. The results showed that the mechanical properties and degradation performance of the fiber under acidic conditions were superior to those of the blank control.

[0117] Embodiment 9

[0118] 1. Introduce calcium oxide into basalt powder at a mass ratio of 2.4-2.5%, control the proportion of CaO at about 11%, and introduce an appropriate amount of nano-silicon dioxide to control the mass percentage of SiO2 in the ingredients to about 50%.

[0119] 2. Mix in a planetary ball mill for 60 minutes, and sieve the uniformly mixed powder through a 100-mesh sieve. 500 g of each mixture.

[0120] 3. Place the evenly mixed ingredients into a corundum crucible and heat in a high-temperature muffle furnace. The heating rate is 5°C / min from room temperature to 300°C, 7.5°C / min from 300 to 1000°C, and 3°C / min from 1000 to 1500°C. Keep warm for 4 hours.

[0121] 4. Quickly pour the melt into water to quench the block glass to 25°C to obtain black glass.

[0122] 5. Take 25±1g of the melted glass block and add it to a platinum crucible. Use a drawing furnace to heat it at a rate of 10℃ / min. The temperature is controlled between 1450℃ until the melt is in a drawable state.

[0123] 6. Pull the fiber and wind it onto a reel. By varying the reel's rotation speed between 900 rpm and 509 m / min, the fiber diameter is controlled to approximately 15 μm. The fiber composition is: 51.65% SiO2, 14.30% Al2O3, 10.82% CaO, 12.22% FeO+Fe2O3, 5.64% MgO, 1.64% TiO2, 0.45% K2O, and 2.99% Na2O.

[0124] 7. Fiber weight loss was tested in 1 mol / L HCl and 1 mol / L NaOH solutions at 60°C for 32 hours, and in pH 3 citric acid buffer at 37°C for 5 days, referring to GB / T 16886.14-2003 and ISO 10933-14:2001. The results showed improved mechanical properties and better degradation performance under acidic conditions than the blank control.

[0125] Example 10

[0126] 1. Introduce calcium oxide into basalt powder at a mass ratio of 4-4.5%, control the proportion of CaO to about 12.5%, and introduce an appropriate amount of nano-silicon dioxide to control the mass percentage of SiO2 in the ingredients to about 50%.

[0127] 2. Mix in a planetary ball mill for 60 minutes, and sieve the uniformly mixed powder through a 100-mesh sieve. 500 g of each mixture.

[0128] 3. Place the evenly mixed ingredients into a corundum crucible and heat in a high-temperature muffle furnace. The heating rate is 5°C / min from room temperature to 300°C, 7.5°C / min from 300 to 1000°C, and 3°C / min from 1000 to 1500°C. Keep warm for 4 hours.

[0129] 4. Quickly pour the melt into water to quench the block glass to 25°C to obtain black glass.

[0130] 5. Take 25±1g of the melted glass block and add it to a platinum crucible. Use a drawing furnace to heat it at a rate of 10℃ / min. The temperature is controlled between 1450℃ until the melt is in a drawable state.

[0131] 6. Pull the fiber and wind it onto a reel. By varying the reel's rotation speed between 900 rpm and 509 m / min, the fiber diameter is controlled to approximately 15 μm. The fiber composition is: 50.56% SiO2, 14.00% Al2O3, 12.70% CaO, 11.97% FeO+Fe2O3, 5.52% MgO, 1.60% TiO2, 0.44% K2O, and 2.92% Na2O.

[0132] 7. Fiber weight loss was tested in 1 mol / L HCl and 1 mol / L NaOH solutions at 60°C for 32 hours, and in pH 3 citric acid buffer at 37°C for 5 days, referring to GB / T 16886.14-2003 and ISO 10933-14:2001. The results showed improved mechanical properties, with breaking strength increasing by approximately 10%. The degradation performance under acidic conditions was superior to that of the blank control, with a dissolution rate 10-20 times that of the blank control.

[0133] Example 11

[0134] 1. Introduce calcium oxide into basalt powder at a mass ratio of 6.5-7%, control the CaO ratio at around 14.5%, and introduce an appropriate amount of nano-silicon dioxide to control the mass percentage of SiO2 in the ingredients to around 50%.

[0135] 2. Mix in a planetary ball mill for 60 minutes, and sieve the uniformly mixed powder through a 100-mesh sieve. 500 g of each mixture.

[0136] 3. Place the evenly mixed ingredients into a corundum crucible and heat in a high-temperature muffle furnace. The heating rate is 5°C / min from room temperature to 300°C, 7.5°C / min from 300 to 1000°C, and 3°C / min from 1000 to 1500°C. Keep warm for 4 hours.

[0137] 4. Quickly pour the melt into water to quench the block glass to 25°C to obtain black glass.

[0138] 5. Take 25±1g of the melted glass block and add it to a platinum crucible. Use a drawing furnace to heat it at a rate of 10℃ / min. The temperature is controlled between 1450℃ until the melt is in a drawable state.

[0139] 6. Pull the fiber and wind it onto a reel. By varying the reel's rotation speed between 900 rpm and 509 m / min, the fiber diameter is controlled to approximately 15 μm. The fiber composition is: 50.00% SiO2, 13.53% Al2O3, 14.48% CaO, 11.57% FeO+Fe2O3, 5.34% MgO, 1.55% TiO2, 0.42% K2O, and 2.88% Na2O.

[0140] 7. Fiber weight loss was tested in 1 mol / L HCl and 1 mol / L NaOH solutions at 60°C for 32 hours, and in pH 3 citric acid buffer at 37°C for 5 days, referring to GB / T 16886.14-2003 and ISO 10933-14:2001. The results showed improved mechanical properties, better degradation performance under acidic conditions, and a dissolution rate 40-50 times that of the blank.

[0141] Example 12

[0142] 1. Introduce calcium oxide into basalt powder at a mass ratio of 8.5-9%, control the CaO ratio to about 16%, and introduce 3.5-4% nano-silicon dioxide to control the mass percentage of SiO2 in the ingredients to about 50%.

[0143] 2. Mix in a planetary ball mill for 60 minutes, and sieve the uniformly mixed powder through a 100-mesh sieve. 500 g of each mixture.

[0144] 3. Place the evenly mixed ingredients into a corundum crucible and heat in a high-temperature muffle furnace. The heating rate is 5°C / min from room temperature to 300°C, 7.5°C / min from 300 to 1000°C, and 3°C / min from 1000 to 1500°C. Keep warm for 4 hours.

[0145] 4. Quickly pour the melt into water to quench the block glass to 25°C to obtain black glass.

[0146] 5. Take 25±1g of the melted glass block and add it to a platinum crucible. Use a drawing furnace to heat it at a rate of 10℃ / min. The temperature is controlled between 1450℃ until the melt is in a drawable state.

[0147] 6. Pull the fiber and wind it onto a reel. By varying the reel's rotation speed between 900 rpm and 509 m / min, the fiber diameter is controlled to 15-16 μm. The fiber composition is: 50.00% SiO2, 12.85% Al2O3, 16.26% CaO, 10.99% FeO+Fe2O3, 5.07% MgO, 1.47% TiO2, 0.40% K2O, and 2.68% Na2O.

[0148] 7. Referring to GB / T 16886.14-2003 and ISO 10933-14:2001 standards, the fiber was tested for weight loss in 1 mol / L HCl and 1 mol / L NaOH solutions at 60°C for 32 hours, and in a pH 3 citric acid buffer solution at 37°C for 5 days. The experimental results show that the mechanical properties of the fiber are improved, with the breaking strength increased by approximately 5%. The degradation performance under acidic conditions is better than that of the blank group, with a dissolution rate over 40 times that of the blank group, and an initial dissolution rate 85 times that of the blank group.

[0149] Example 13

[0150] 1. Introduce calcium oxide into basalt powder at a mass ratio of 13-13.5%, control the proportion of CaO at about 20%, and introduce 8.5-9% nano-silicon dioxide to control the mass percentage of SiO2 in the ingredients to about 50%.

[0151] 2. Mix in a planetary ball mill for 60 minutes, and sieve the uniformly mixed powder through a 100-mesh sieve. 500 g of each mixture.

[0152] 3. Place the evenly mixed ingredients into a corundum crucible and heat in a high-temperature muffle furnace. The heating rate is 5°C / min from room temperature to 300°C, 7.5°C / min from 300 to 1000°C, and 3°C / min from 1000 to 1500°C. Keep warm for 4 hours.

[0153] 4. Quickly pour the melt into water to quench the block glass to 25°C to obtain black glass.

[0154] 5. Take 25±1g of the melted glass block and add it to a platinum crucible. Use a drawing furnace to heat it at a rate of 10℃ / min. The temperature is controlled between 1450℃ until the melt is in a drawable state.

[0155] 6. Pull the fiber and wind it onto a reel. By varying the reel's rotation speed between 900 rpm and 509 m / min, the fiber diameter is controlled to range from 15 to 16 μm. The fiber composition is: 50.00% SiO2, 11.43% Al2O3, 20% CaO, 9.77% FeO + Fe2O3, 4.51% MgO, 1.31% TiO2, 0.36% K2O, and 2.38% Na2O.

[0156] 7. Referring to GB / T 16886.14-2003 and ISO 10933-14:2001, the fiber was tested for weight loss in 1 mol / L HCl and 1 mol / L NaOH solutions at 60°C for 32 hours, and in pH 3 citric acid buffer at 37°C for 5 days. The experimental results showed that the fiber showed better degradation resistance, but the mechanical properties decreased by 20-25%.

[0157] The composition ratios of the blank group and Examples 1 to 13 are shown in Table 1 below:

[0158] Table 1: Fiber composition

[0159]

[0160]

[0161] Table 2: Fiber performance test data

[0162]

[0163]

[0164] As shown in Tables 1 and 2, the degradation of fibers in formulations with a P2O5 content of 2-8% showed more significant changes compared to the blank group, but had a significant impact on the mechanical properties of the fibers, with higher P2O5 content indicating a greater impact. Based on the experimental results, the 6-8% P2O5 content showed the best degradation performance, while also retaining a higher proportion of mechanical properties. CaO does not form part of the glass network structure, and increasing its introduction will improve degradation performance to a certain extent, but excessive introduction will reduce the mechanical properties of the fibers. The CaO content of the formulation should be controlled between 12 and 16.5%, and the appropriate ratio can be selected based on actual conditions.

[0165] In summary, this application introduces the P element into the traditional basalt fiber process, and uses the unsaturated metastable state of the phosphorus-oxygen double bond in the phosphorus-oxygen tetrahedron to increase solubility and increase the degradation ability of the fiber, or expand the ratio of sodium, potassium, and calcium elements in the mineral material to an appropriate range, thereby enhancing the degradation ability of the fiber while ensuring the mechanical properties of the fiber. By regulating the composition ratio of phosphorus-containing compounds in the basalt raw material, the mechanical properties and degradation properties of the basalt fiber can be regulated. By adjusting the composition ratio of alkali metal elements in the basalt mineral material, the mechanical properties and degradation properties of the basalt fiber can be improved.

[0166] The above are merely specific embodiments of the present application and are not intended to limit the present application. Those skilled in the art will readily appreciate that various modifications and variations are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present application shall be included within the scope of protection of the present application.

Claims

1. A degradable basalt fiber, characterized in that: The components of the degradable basalt fiber include: 50-55% SiO2, 10-15% Al2O3, 8-17% CaO, 9-13% FeO and Fe2O3, 4-6% MgO, 0-1% K2O, 1-2% TiO2, 3-10% Na2O, and 0-8% P2O5.

2. The degradable basalt fiber according to claim 1, characterized in that: The mass proportion of P2O5 is 6-8%.

3. The degradable basalt fiber according to claim 1, characterized in that: The mass proportion of CaO is 12-16.5%.

4. A method for preparing degradable basalt fiber, for preparing the degradable basalt fiber according to any one of claims 1 to 3, characterized in that: The method comprises the following steps: S1, adding CaO to the basalt raw material or adding a phosphorus-containing compound and CaO and mixing them uniformly; S2, heating the uniformly mixed powder into a melt; S3, drawing the melt to form degradable basalt fibers.

5. The method for preparing degradable basalt fiber according to claim 4, characterized in that: Phosphorus-containing compounds include sodium pyrophosphate, ammonium phosphate, or calcium pyrophosphate.

6. The method for preparing degradable basalt fiber according to claim 4, characterized in that: In step S1, nano-silicon dioxide is also added so that the mass proportion of SiO2 in the degradable basalt fiber is 50-55%.

7. The method for preparing degradable basalt fiber according to claim 4, characterized in that: In step S1, a star-shaped ball mill is used for mixing for 30-60 minutes.

8. The method for preparing degradable basalt fiber according to claim 7, characterized in that: The mixed powder was sieved through a 800-100 mesh sieve.

9. The method for preparing degradable basalt fiber according to claim 4, characterized in that: Step S2 includes: S21, placing the uniformly mixed powder into a corundum crucible, heating in a muffle furnace, controlling the heating rate from room temperature to 300°C to be 5°C / min, the heating rate from 300°C to 1000°C to be 7.5°C / min, and the heating rate from 1000°C to 1500°C to be 3°C / min, and maintaining the temperature for 2-4 hours; S22, pouring the melt into water and quenching it to 25°C to obtain black glass; S23, placing the black glass into a platinum crucible and heating it in a drawing furnace at a heating rate of 10°C / min and controlling the temperature at 1450-1550°C; S24, the fiber is drawn and wound onto a reel.

10. The method for preparing degradable basalt fiber according to claim 9, characterized in that: In step S24, the diameter of the degradable basalt fiber can be controlled to be 10-20 μm by changing the rotation speed of the reel to 100-600 m / min.

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