Preparation method of composite phase change fiber, composite phase change fiber and application of composite phase change fiber
Composite phase change fibers were prepared by combining sodium alginate, octadecane microcapsules, and graphene nanosheets using physical crosslinking and wet spinning techniques. This solved the problems of easy microcapsule detachment and low energy storage density, and achieved efficient thermal management.
Patent Information
- Application Number
- CN202411580470.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-06
- Publication Date
- 2026-05-08
AI Technical Summary
Existing microcapsule-based phase change fibers suffer from problems such as easy microcapsule detachment and low energy storage density, making it difficult to meet the requirements of efficient and intelligent thermal management.
Composite phase change fibers were prepared using sodium alginate, octadecane microcapsules, and graphene nanosheets as raw materials through physical crosslinking and wet spinning techniques. The self-crosslinking properties of sodium alginate and the reinforcing properties of graphene were utilized to form a stable fiber structure.
The prepared composite phase change fiber has high shape stability, no leakage, good flexibility, high heat storage density, and enthalpy value of 30-110 J g-1, making it suitable for the field of human body thermal management.
Smart Images
Figure CN121992530A_ABST
Abstract
Description
Technical Field
[0001] This application relates to a method for preparing composite phase change fibers, composite phase change fibers and their applications, belonging to the field of thermal storage technology. Background Technology
[0002] Rapid technological advancements and rising living standards have led to a significant increase in energy demand and consumption. Specifically, this demand is primarily driven by the need to maintain comfortable indoor temperatures, resulting in a heavy reliance on fossil fuels and electricity, putting pressure on the environment. To reduce energy consumption, there is an increasingly urgent need to focus on managing the temperature of the local environment surrounding the human body rather than controlling the temperature of the entire indoor space. Smart textiles, capable of effectively controlling the temperature of the human body's microenvironment, have attracted attention due to their ability to improve human comfort and significantly reduce energy consumption. Currently, smart temperature-regulating fabrics primarily achieve thermal management functions through infrared reflective materials, phase change materials, and thermal insulation materials. Among these, temperature-regulating fabrics based on organic phase change materials (PCMs) have received extensive research and attention due to their isothermal properties during the phase change process.
[0003] In addition, organic PCMs have other advantages, such as non-toxicity, high thermal energy storage density, and excellent biocompatibility. However, most organic PCMs undergo solid-liquid phase transitions, thus exhibiting some inherent drawbacks, such as liquid leakage during the phase transition and high rigidity in the solid state, making them difficult to use directly. Microencapsulation is currently an effective method for encapsulating solid-liquid phase change materials, which involves encapsulating the solid-liquid phase change material core with a shell made of polymer or inorganic material. The shell helps prevent leakage and shape changes of the phase change material during the phase transition. Therefore, microcapsule-based phase change fibers (PCFs) are a promising preparation strategy that can prevent solid-liquid leakage problems. However, existing microcapsule-based PCFs still have some problems to be solved. For example, the commercially available Outlast thermoregulatory fiber is made by blending microcapsules with fabrics such as polyester, where the microcapsules are located on the surface of the polyester fibers and are easily detached. Furthermore, Zhu et al. prepared a polyamide 6 and microcapsule composite PCF by melt spinning with a phase transition enthalpy of only 9.4 J / g. However, the low energy storage density of these PCFs makes it difficult to meet the requirements of efficient and intelligent thermal management. Based on these conditions, there is an urgent need to develop high-performance PCFs with high energy storage density, in which the microcapsules can remain stable. Summary of the Invention
[0004] This application presents a simple and efficient preparation method using a mixed solution of sodium alginate and octadecane microcapsules as the spinning solution to prepare phase change fibers with ultra-flexibility, high shape stability, and high enthalpy. The resulting flexible PCM fibers exhibit relatively high latent heat (up to 110 J g). -1Furthermore, the fiber prepared in this application has important applications in the field of human body thermal management due to its heat absorption platform of approximately 25°C.
[0005] One aspect of this application provides a method for preparing composite phase change fibers, which constructs composite phase change fibers through physical cross-linking strategies and wet spinning technology. Sodium alginate, octadecane microcapsules, and graphene nanosheets are used as raw materials. A uniform spinning precursor solution is prepared by stirring. Subsequently, composite phase change fibers are prepared by wet spinning, and finally, the fibers are obtained by multiple washings with deionized water.
[0006] Optionally, the method for preparing the composite phase change fiber includes:
[0007] (1) Add sodium alginate to deionized water and stir until solution I is obtained;
[0008] (2) Add the octadecane microcapsules to an aqueous solution containing sodium alginate, stir II, and obtain solution II;
[0009] (3) Add graphene nanosheets to solution I obtained in step (1), stir III to obtain spinning solution III, and let stand;
[0010] (4) Use metal salt and water to prepare coagulation bath, stir IV, and obtain spinning solution IV;
[0011] (5) The spinning solution obtained in step (3) is left to stand, and then placed in a wet spinning device for wet spinning and drying to obtain the composite phase change fiber.
[0012] In the wet spinning apparatus, the end outlet of the spinning head is placed in a coagulation bath.
[0013] Optionally, sodium alginate is used as a phase change material raw material for constructing phase change fibers, wherein the molecular weight of sodium alginate is 10,000 to 600,000.
[0014] Optionally, the molecular weight of the sodium alginate is independently selected from any value of 10,000, 100,000, 200,000, 300,000, 600,000 or a range between any two of the above.
[0015] Optionally, in the aqueous solution containing sodium alginate, the concentration of sodium alginate is 0.01–0.03 g sodium alginate / 1 mL water;
[0016] Optionally, the concentration of sodium alginate is independently selected from any value among 0.01 g sodium alginate / 1 mL water, 0.015 g sodium alginate / 1 mL water, 0.02 g sodium alginate / 1 mL water, 0.025 g sodium alginate / 1 mL water, 0.03 g sodium alginate / 1 mL water, or a range between any two of the above.
[0017] Optionally, the method for preparing the aqueous solution containing sodium alginate includes: dispersing sodium alginate in water and stirring (III) to form an aqueous solution containing sodium alginate;
[0018] The temperature of stirring III is 20–60°C, and the stirring time is 30–120 min.
[0019] Optionally, in solution I, the concentration of octadecane microcapsules is 0.005–0.06 g of octadecane microcapsules per 1 mL of water;
[0020] The temperature of stirring I is 20–60°C, and the stirring time is 30–120 min.
[0021] Optionally, in solution II, the concentration of octadecane microcapsules is independently selected from any value among 0.005 g octadecane microcapsules / 1 mL water, 0.01 g octadecane microcapsules / 1 mL water, 0.015 g octadecane microcapsules / 1 mL water, 0.02 g octadecane microcapsules / 1 mL water, 0.025 g octadecane microcapsules / 1 mL water, 0.03 g octadecane microcapsules / 1 mL water, 0.04 g octadecane microcapsules / 1 mL water, 0.045 g octadecane microcapsules / 1 mL water, 0.05 g octadecane microcapsules / 1 mL water, 0.06 g octadecane microcapsules / 1 mL water, or a range between any two of the above.
[0022] Optionally, the concentration of graphene nanosheets in the spinning solution is 0.005–0.01 g graphene nanosheets / 1 mL water;
[0023] The graphene nanosheets have a diameter of 0.5–3 μm;
[0024] The temperature of stirring III is 20–60°C, and the stirring time is 30–120 min.
[0025] Optionally, the concentration of graphene nanosheets in the spinning solution is independently selected from any value among 0.005 g graphene nanosheets / 1 mL water, 0.006 g graphene nanosheets / 1 mL water, 0.008 g graphene nanosheets / 1 mL water, 0.01 g graphene nanosheets / 1 mL water, or a range between any two of the above.
[0026] Optionally, the temperature for the settling period is 20–30°C;
[0027] The settling time is 8 hours to 24 hours;
[0028] The settling process is carried out in a vacuum environment with a vacuum level of 0 to 0.1 kPa.
[0029] The metal salt is selected from at least one of CaCl2, ZnCl2, FeCl3, and AlCl3;
[0030] In the coagulation bath, the mass ratio of metal salt to water is 3 to 6:100.
[0031] Optionally, in the coagulation bath, the mass ratio of metal salt to water is independently selected from any value of 3:100, 3.5:100, 4:100, 4.5:100, 5:100, 6:100 or a range between any two of the above.
[0032] Optionally, during the wet spinning process,
[0033] The temperature of the spinning solution is 20℃~60℃;
[0034] The temperature of the coagulation bath is 20℃~60℃.
[0035] Optionally, the drying temperature is 20–70°C;
[0036] The drying time is 2 to 24 hours.
[0037] As a specific implementation method, the synthesis of this composite phase change fiber mainly includes the following steps:
[0038] (1) Disperse sodium alginate in water and stir to form a homogeneous solution;
[0039] (2) Add 18-carbohydrate microcapsules to the original solution obtained in (1) and stir to form a homogeneous solution;
[0040] (3) Add different masses of graphene nanosheets to the original solution obtained in (2) and stir to form a uniform solution;
[0041] (4) Place the original solution obtained in (3) in a vacuum environment at room temperature to remove bubbles;
[0042] (5) Use an aqueous solution of a metal salt as a coagulation bath solution;
[0043] (6) Place the spinning solution obtained in (4) into a syringe and place it in a wet spinning instrument. Place the outlet in the coagulation bath prepared in (5) to obtain composite phase change fiber.
[0044] (7) Wash the composite phase change fiber obtained in (6) with deionized water multiple times.
[0045] (8) The washed phase change fiber obtained in (7) is dried to obtain the final composite phase change fiber.
[0046] The fiber prepared in step (6) needs to be kept at an ambient temperature below 60°C during the preparation process.
[0047] The deionized water used in step (7) during the fiber preparation process is below 60°C. Specifically, after spinning, the deionized water used for washing the fibers needs to be between 20°C and 60°C.
[0048] In another aspect of this application, a composite phase change fiber obtained by the above-described preparation method is provided, wherein the composite phase change fiber has a macroscopic morphology of linear.
[0049] The enthalpy value of the composite phase change fiber is 30–110 J g. -1 .
[0050] Another aspect of this application provides the application of the composite phase change fiber obtained by the above preparation method in human body thermal management temperature-regulating phase change fibers.
[0051] This application discloses a simple preparation method for constructing functional phase change fibers through physical blending. Sodium alginate, 18-decane microcapsules, and graphene nanosheets are used as raw materials. These materials undergo hydrogen bonding self-crosslinking, followed by mixing with the 18-decane microcapsules to obtain a homogeneous mixture. The composite phase change fiber is then obtained through wet spinning, ionic crosslinking, and subsequent processing. Furthermore, it demonstrates good performance in intelligent thermal management for the human body.
[0052] The beneficial effects that this application can produce include:
[0053] The process requirements of this application are low, and the prepared phase change fiber is linear, with features such as no leakage, high heat storage density, non-toxicity, good flexibility, and excellent light absorption performance. Moreover, the enthalpy value can be adjusted, making it very promising in the field of human body thermal management. Attached Figure Description
[0054] Figure 1 This is a photograph of the composite phase change fiber obtained in Example 1.
[0055] Figure 2 The differential scanning calorimetry curve of the composite phase change fiber obtained in Example 1 is shown.
[0056] Figure 3 The differential scanning calorimetry curve of the composite phase change fiber obtained in Example 2 is shown.
[0057] Figure 4 The differential scanning calorimetry curve of the composite phase change fiber obtained in Example 3 is shown. Detailed Implementation
[0058] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.
[0059] Unless otherwise specified, the raw materials and catalysts used in the embodiments of this application were all purchased commercially.
[0060] The analysis method in the embodiments of this application is as follows:
[0061] Differential scanning calorimetry (DSC) curves of phase change fibers were obtained under nitrogen conditions using a differential scanning calorimeter.
[0062] Example 1
[0063] (1) Dissolve 0.4g of sodium alginate with a molecular weight of 60W in 20mL of deionized water and heat and stir at 60℃ for 30min to obtain a homogeneous solution.
[0064] (2) Take 0.4g of octadecane microcapsules and add them to the homogeneous solution obtained in (1). Heat and stir at 60°C for 30 minutes to obtain a homogeneous solution.
[0065] (3) Take 0g of graphene nanosheets and add them to the homogeneous solution obtained in (2). Heat and stir at 50°C for 4 hours to obtain the spinning solution.
[0066] (4) Place the spinning solution obtained in (3) under vacuum (0.1Kpa) and 20℃ and let it stand for 8 hours.
[0067] (5) Dissolve 6g CaCl2 in 200mL of anhydrous ethanol and mix well to prepare a coagulation bath.
[0068] (6) Place the spinning solution obtained in (4) into the spinning instrument and inject it into the coagulation bath in (5) and keep the temperature at 40℃.
[0069] (7) The phase change fiber obtained in (6) is washed with deionized water at 40°C.
[0070] (8) Dry the phase change fiber obtained in (7) and keep it at 20°C for about 48 hours.
[0071] The phase change fiber obtained in this embodiment is a white fiber, such as... Figure 1 Furthermore, its enthalpy is 80 J / g. -1 The differential scanning calorimetry curve is as follows: Figure 2 As shown.
[0072] Example 2
[0073] (1) Dissolve 0.6g of sodium alginate with a molecular weight of 1W in 20mL of deionized water and stir at 20℃ for 1h to obtain a homogeneous solution.
[0074] (2) Take 1.2g of octadecane microcapsules and add them to the homogeneous solution obtained in (1). Heat and stir at 60°C for 1 min to obtain a homogeneous solution.
[0075] (3) Take 0.1g of graphene nanosheets and add them to the homogeneous solution obtained in (2). Heat and stir at 20°C for 30 minutes to obtain the spinning solution.
[0076] (4) Place the spinning solution obtained in (3) under vacuum (0.1 kPa) and 30°C and let it stand for 10 h.
[0077] (5) Dissolve 10g ZnCl2 in 200mL of anhydrous ethanol and mix well to prepare a coagulation bath.
[0078] (6) Place the spinning solution obtained in (4) into the spinning instrument and inject it into the coagulation bath in (5) and keep the temperature at 60°C.
[0079] (7) The phase change fiber obtained in (6) is washed with deionized water at 40°C.
[0080] (8) Dry the phase change fiber obtained in (7) and keep it at 60°C for about 2 hours.
[0081] The phase change fiber obtained in this embodiment has an enthalpy value of 110 J / g. -1 The differential scanning calorimetry curve is as follows: Figure 3 As shown.
[0082] Example 3
[0083] (1) Dissolve 0.3g of sodium alginate with a molecular weight of 30W in 20mL of deionized water and heat and stir at 40℃ for 2h to obtain a homogeneous solution.
[0084] (2) Take 0.1g of octadecane microcapsules and add them to the homogeneous solution obtained in (1). Heat and stir at 60°C for 5 hours to obtain a homogeneous solution.
[0085] (3) Take 0.2g of graphene nanosheets and add them to the homogeneous solution obtained in (2). Heat and stir at 30°C for 4 hours to obtain the spinning solution.
[0086] (4) Place the spinning solution obtained in (3) under vacuum (0.1Kpa) and 20℃ and let it stand for 8 hours.
[0087] (5) Dissolve 7g AlCl3 in 200mL of anhydrous ethanol and mix well to prepare a coagulation bath.
[0088] (6) Place the spinning solution obtained in (4) into the spinning instrument and inject it into the coagulation bath in (5) and keep the temperature at 20°C.
[0089] (7) The phase change fiber obtained in (6) is washed with deionized water at 50°C.
[0090] (8) Dry the phase change fiber obtained in (7) and keep it at 30°C for about 12 hours.
[0091] The phase change fiber obtained in this embodiment has an enthalpy value of 30 J / g. -1 The differential scanning calorimetry curve is as follows: Figure 4 As shown.
[0092] Example 4
[0093] (1) Dissolve 0.5g of sodium alginate with a molecular weight of 20W in 20mL of deionized water and heat and stir at 30℃ for 4h to obtain a homogeneous solution.
[0094] (2) Take 0.8g of octadecane microcapsules and add them to the homogeneous solution obtained in (1). Heat and stir at 20°C for 6 hours to obtain a homogeneous solution.
[0095] (3) Take 0.1g of graphene nanosheets and add them to the homogeneous solution obtained in (2). Heat and stir at 20°C for 8 hours to obtain the spinning solution.
[0096] (4) Place the spinning solution obtained in (3) under vacuum (0.1Kpa) and 20℃ and let it stand for 8 hours.
[0097] (5) Dissolve 9g FeCl3 in 200mL of anhydrous ethanol and mix well to prepare a coagulation bath.
[0098] (6) Place the spinning solution obtained in (4) into the spinning instrument and inject it into the coagulation bath in (5) and keep the temperature at 30°C.
[0099] (7) The phase change fiber obtained in (6) is washed with deionized water at 60°C.
[0100] (8) Dry the phase change fiber obtained in (7) and keep it at 70°C for about 3 hours.
[0101] Example 5
[0102] (1) Dissolve 0.4g of sodium alginate with a molecular weight of 10W in 20mL of deionized water and heat and stir at 20℃ for 2h to obtain a homogeneous solution.
[0103] (2) Take 0.9g of octadecane microcapsules and add them to the homogeneous solution obtained in (1). Heat and stir at 30°C for 5 hours to obtain a homogeneous solution.
[0104] (3) Take 0.2g of graphene nanosheets and add them to the homogeneous solution obtained in (2). Heat and stir at 30°C for 6 hours to obtain the spinning solution.
[0105] (4) Place the spinning solution obtained in (3) under vacuum (0.1Kpa) and 20℃ and let it stand for 8 hours.
[0106] (5) Dissolve 6g CaCl2 in 200mL of anhydrous ethanol and mix well to prepare a coagulation bath.
[0107] (6) Place the spinning solution obtained in (4) into the spinning instrument and inject it into the coagulation bath in (5) and keep the temperature at 50°C.
[0108] (7) The phase change fiber obtained in (6) is washed with deionized water at 40°C.
[0109] (8) Dry the phase change fiber obtained in (7) and keep it at 55°C for about 6 hours.
[0110] Example 6
[0111] (1) Dissolve 0.3g of sodium alginate with a molecular weight of 20W in 20mL of deionized water and heat and stir at 60℃ for 3h to obtain a homogeneous solution.
[0112] (2) Take 0.6g of octadecane microcapsules and add them to the homogeneous solution obtained in (1). Heat and stir at 40°C for 2 hours to obtain a homogeneous solution.
[0113] (3) Take 0.2g of graphene nanosheets and add them to the homogeneous solution obtained in (2). Heat and stir at 20°C for 4 hours to obtain the spinning solution.
[0114] (4) Place the spinning solution obtained in (3) under vacuum (0.1Kpa) and 20℃ and let it stand for 8 hours.
[0115] (5) Dissolve 9g ZnCl2 in 200mL of anhydrous ethanol and mix well to prepare a coagulation bath.
[0116] (6) Place the spinning solution obtained in (4) into the spinning instrument and inject it into the coagulation bath in (5) and keep the temperature at 60°C.
[0117] (7) The phase change fiber obtained in (6) is washed with deionized water at 50°C.
[0118] (8) Dry the phase change fiber obtained in (7) and keep it at 35°C for about 10 hours.
[0119] Example 7
[0120] (1) Dissolve 0.2g of sodium alginate with a molecular weight of 60W in 20mL of deionized water and heat and stir at 60℃ for 1h to obtain a homogeneous solution.
[0121] (2) Take 0.5g of octadecane microcapsules and add them to the homogeneous solution obtained in (1). Heat and stir at 50°C for 50 minutes to obtain a homogeneous solution.
[0122] (3) Take 0.1g of graphene nanosheets and add them to the homogeneous solution obtained in (2). Heat and stir at 50°C for 4 hours to obtain the spinning solution.
[0123] (4) Place the spinning solution obtained in (3) under vacuum (0.1Kpa) and 20℃ and let it stand for 8 hours.
[0124] (5) Dissolve 10g AlCl3 in 200mL of anhydrous ethanol and mix well to prepare a coagulation bath.
[0125] (6) Place the spinning solution obtained in (4) into the spinning instrument and inject it into the coagulation bath in (5) and keep the temperature at 20°C.
[0126] (7) The phase change fiber obtained in (6) is washed with deionized water at 30°C.
[0127] (8) Dry the phase change fiber obtained in (7) and keep it at 25°C for about 48 hours.
[0128] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.
Claims
1. A method for preparing composite phase change fibers, characterized in that, The preparation method includes: (1) Add sodium alginate to deionized water and stir until solution I is obtained; (2) Add the octadecane microcapsules to an aqueous solution containing sodium alginate, stir II, and obtain solution II; (3) Add graphene nanosheets to solution I obtained in step (1), stir III to obtain spinning solution III, and let stand; (4) Use metal salt and water to prepare coagulation bath, stir IV, and obtain spinning solution IV; (5) The spinning solution obtained in step (3) is left to stand, and then placed in a wet spinning device for wet spinning and drying to obtain the composite phase change fiber. In the wet spinning apparatus, the end outlet of the spinning head is placed in a coagulation bath.
2. The preparation method according to claim 1, characterized in that, The molecular weight of the sodium alginate is 10,000 to 600,000; The concentration of sodium alginate in the aqueous solution is 0.01–0.03 g sodium alginate / 1 mL water; The method for preparing the aqueous solution containing sodium alginate includes: dispersing sodium alginate in water and stirring to form an aqueous solution containing sodium alginate; The temperature of stirring I is 20-60℃, and the stirring time is 30-120 min.
3. The preparation method according to claim 1, characterized in that, In solution I, the concentration of octadecane microcapsules is 0.005–0.06 g of octadecane microcapsules per 1 mL of water; The temperature of stirring II is 20–60°C, and the stirring time is 30–120 min.
4. The preparation method according to claim 1, characterized in that, The concentration of graphene nanosheets in the spinning solution is 0–0.01 g graphene nanosheets / 1 mL water; The graphene nanosheets have a diameter of 0.5–3 μm; The temperature of stirring III is 20–60°C, and the stirring time is 30–120 min.
5. The preparation method according to claim 1, characterized in that, The temperature for static setting is 10–40°C; The settling time is 8 hours to 24 hours; The settling process is carried out in a vacuum environment with a vacuum level of 0 to 0.1 kPa.
6. The preparation method according to claim 1, characterized in that, The metal salt is selected from at least one of CaCl2, ZnCl2, FeCl3, and AlCl3; In the coagulation bath, the mass ratio of metal salt to water is 3 to 6:
100.
7. The preparation method according to claim 1, characterized in that, During the wet spinning process The temperature of the spinning solution is 20℃~60℃; The temperature of the coagulation bath is 20℃~60℃.
8. The preparation method according to claim 1, characterized in that, The drying temperature is 20–70°C; The drying time is 2 to 24 hours.
9. A composite phase change fiber obtained by the preparation method according to any one of claims 1 to 8, characterized in that, The composite phase change fiber has a linear macroscopic morphology. The enthalpy value of the composite phase change fiber is 30–110 J g. -1 .
10. The application of a composite phase change fiber obtained by the preparation method according to any one of claims 1 to 8 in human body thermal management temperature-regulating phase change fibers.