CN117448980B - Nano multi-metal doped tungsten bronze heat storage fiber and preparation method thereof - Google Patents
Nano multi-metal doped tungsten bronze heat storage fiber and preparation method thereof Download PDFInfo
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Abstract
The invention provides a nano multi-metal doped tungsten bronze heat storage fiber and a preparation method thereof, wherein the fiber is prepared from 10-60 parts by mass of heat storage slurry and 40-70 parts by mass of high polymer material, and the heat storage slurry is prepared from nano multi-metal doped tungsten bronze, a dispersion medium, a dispersing agent and a defoaming agent. The fiber has simple raw materials, is doped with the multi-ion tungsten bronze, realizes excellent near infrared band absorptivity under the condition of not introducing other materials, avoids the compatibility problem of various compounds in the compounding process, and the gelation phenomenon caused by the selection of different dispersing agents in the subsequent sanding treatment, improves the preparation efficiency of the heat storage fiber, and saves the production cost.
Description
Technical Field
The invention belongs to the field of functional fibers, and particularly relates to a nano multi-metal doped tungsten bronze heat storage fiber and a preparation method thereof.
Background
In winter, the temperature is low, and in order to maintain the body temperature stable, the warm clothing is necessary. The clothes woven by the functional fibers with heat accumulation and heat preservation are gradually increased, and compared with thick down jackets and cotton clothes, the requirements of people on lightness, thinness, warmth preservation and comfort can be met. Tungsten bronze has been used as a material for shielding near infrared light in master batches and fibers to provide heat absorption and heat storage functions. The cesium tungsten bronze has wider application, but the ion radius of the cesium ions is slightly larger than the diameter of a tungsten bronze crystal channel, and cesium ions can be separated out from the fiber due to aging, cleaning abrasion and the like in practical application, so that the near infrared shielding performance is reduced. Meanwhile, the absorptivity of the single metal doped tungsten bronze in the near infrared band often needs to be supplemented by other materials, and the advantage of the structural diversity of the tungsten bronze is not fully developed. For example, patent CN114541138B adopts cesium tungsten bronze, lanthanum hexaboride, rare earth oxide and the like to prepare thermal yarn, wherein the rare earth compound can play a role in anchoring cesium tungsten bronze to improve stability of cesium tungsten bronze, but nano-scale rare earth compound is difficult to prepare, is compounded by a plurality of compounds, and has a problem of gelation due to compatibility of materials after sanding, thereby influencing preparation efficiency.
Disclosure of Invention
In view of the above, the invention aims to provide a nano multi-metal doped tungsten bronze heat storage fiber and a preparation method thereof, wherein the nano multi-metal doped tungsten bronze heat storage fiber starts from a tungsten bronze crystal structure, and improves the near infrared absorptivity and absorption breadth while enhancing the structural stability of tungsten bronze by adjusting the proportion of doped elements and controlling the crystal form so as to achieve the functions of active heat absorption, heat storage and heat preservation.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
the nano multi-metal doped tungsten bronze heat accumulating fiber is prepared from 10-60 parts by mass of heat accumulating slurry and 40-70 parts by mass of high polymer material, wherein the heat accumulating slurry is prepared from nano multi-metal doped tungsten bronze, a dispersing medium, a dispersing agent and a defoaming agent, and the chemical formula of the nano multi-metal doped tungsten bronze is A x B y Re (0.33-x-2y)/3 WO 3 ，0<x<0.4、0<y<0.1、0<x+2y is less than or equal to 0.33, A is an alkali metal element, B is an alkaline earth metal element, and Re is a rare earth element.
Further, the heat storage slurry comprises the following raw materials in parts by weight: 10-40 parts of nano multi-metal doped tungsten bronze, 50-80 parts of dispersion medium, 5-20 parts of dispersing agent and 0.5-5 parts of defoaming agent, wherein the particle size of the nano multi-metal doped tungsten bronze is 70-500nm.
Further, the nano multi-metal doped tungsten bronze is prepared by the following method:
(1) Weighing raw materials of an alkali metal source, an alkaline earth metal source, a rare earth source and a tungsten source according to a proportion, and ball-milling all the raw materials in a ball-milling tank with a dispersion medium at a rotating speed of 200-600 r/min for 8-16h;
(2) Drying the ball-milled powder at 90-120 ℃ for 16-24 hours, and crushing the dried raw materials into powder by a crusher;
(3) And (3) charging the crushed raw materials into a rotary furnace, and calcining the raw materials in a crystal water removal stage, a first heat preservation stage, a reduction stage, a second heat preservation stage, a reaction water removal stage and a cooling protection stage, and performing ultrasonic treatment to obtain the nano multi-metal doped tungsten bronze powder with different crystal forms.
Wherein, in the step (3), 5% hydrogen-nitrogen mixed gas with the flow rate of 200ml/min is initially introduced into the rotary furnace, and the temperature is raised after 2 min; and (3) a crystallization water removal stage: heating from room temperature to 270 ℃ at a speed of 5 ℃/min, wherein the ventilation speed of the rotary furnace is 50ml/min, and the rotation speed is 5rpm; a first heat preservation stage: preserving heat for 30min, wherein the inclination angle of the rotary furnace is 15 degrees; reduction stage: heating to 500-900 ℃ at a speed of 3 ℃/min, wherein the ventilation speed of the rotary furnace is 100ml/min, the rotation speed is 50rpm, and the inclination angle of the rotary furnace is 10 degrees; and a second heat preservation stage: preserving heat for 4 hours, wherein the ventilation rate of the rotary furnace is 200ml/min, and the inclination angle of the rotary furnace is 0 degree; in the reaction water removal stage, the temperature is reduced to 450 ℃ at 10 ℃/min, the ventilation rate of the rotary furnace is 50ml/min, and the inclination angle of the rotary furnace is 10 degrees; and (3) a cooling protection stage: cooling to room temperature at 5 ℃ per minute, and enabling the ventilation rate of the rotary furnace to be 4ml/min.
Further, the alkali metal element is one of potassium, sodium and cesium, the alkali metal source is one or more of alkali metal carbonate, alkali metal chloride and alkali metal oxide, the alkaline earth metal is one of calcium and barium, the alkaline earth metal source is one or more of alkaline earth metal carbonate, alkaline earth metal chloride and alkaline earth metal oxide, the rare earth element is one of lanthanum, yttrium and europium, the rare earth source is one or more of rare earth carbonate, rare earth chloride, rare earth boride and rare earth nitrate, and the tungsten source is one or more of tungstic acid, ammonium tungstate and tungsten oxide.
Further, the alkali metal element, the alkaline earth metal element and the rare earth element are Cs, ca and La respectively, and the molar ratio of Cs to Ca to La in the nano multi-metal doped tungsten bronze is (0.22-0.25): 0.01: (0.01-0.03).
Further, the crystal structure of the nano multi-metal doped tungsten bronze is one of cubic crystals, tetragonal crystals and hexagonal crystals.
Further, the polymer material is one or more of ethylene terephthalate, polyurethane, polybutylene terephthalate and polystyrene; the dispersing agent is one or more of silane coupling agent KH550, silane coupling agent KH560, silane coupling agent KH570, polyethylene glycol, polyvinyl alcohol and polyvinylpyrrolidone; the dispersion medium is one or more of deionized water, diisobutyl ketone, ethyl acetate and propylene glycol methyl ether acetate; the defoamer is one or two of Foamex 810 and FoamStar A10.
The invention also provides a preparation method of the nano multi-metal doped tungsten bronze heat storage fiber, which comprises the following steps:
(1) Mixing nano multi-metal doped tungsten bronze powder, a dispersing agent, a dispersing medium and a defoaming agent according to a proportion, uniformly dispersing by using a dispersing machine, and performing ultrasonic treatment to 70-500nm to obtain heat storage slurry;
(2) Uniformly mixing 10-60 parts by mass of heat storage slurry and 40-70 parts by mass of high polymer material in a high-speed mixer;
(3) Drying the material obtained in the step (2) until the water content is not higher than 200ppm, then putting the material into a double-screw granulator, and performing high-temperature melt extrusion granulation to obtain heat-storage functional master batch;
(4) And (3) putting the obtained master batch into a melt spinning machine, melting the master batch at high temperature to obtain a beam-shaped high polymer melt, and winding and collecting filaments which are formed by air-cooling condensation of the high polymer melt pressed out of a spinning nozzle to obtain the nano multi-metal doped tungsten bronze heat storage fiber.
Further, the ultrasonic power in the step (1) is 400-600W;
further, the rotating speed of the high-speed mixer in the step (2) is 500-1200r/min, and the interval between every two stirring steps is 5-10min when each stirring step is 10-20min, so that the high-speed mixer is prevented from being excessively high due to continuous operation temperature;
the temperature of the drying in the step (3) is 80-120 ℃, the duration time is 12-24h, the rotating speed of the double-screw granulator is 50-250r/min, and the temperature is 220-280 ℃;
the spinning temperature in the step (4) is 220-320 ℃.
The invention also provides application of the nano multi-metal doped tungsten bronze heat storage fiber in the field of home textile and clothing fabric textile.
Compared with the prior art, the nano multi-metal doped tungsten bronze heat storage fiber and the preparation method thereof have the following advantages:
(1) The nano multi-metal doped tungsten bronze heat storage fiber disclosed by the invention is simple in raw material, and the multi-ion doped tungsten bronze is adopted, so that excellent near infrared band absorptivity is realized under the condition that other materials are not introduced, the compatibility problem of various compounds in the compounding process is avoided, the gelation phenomenon caused by the selection of different dispersing agents in the subsequent sanding treatment is avoided, the preparation efficiency of the heat storage fiber is improved, and the production cost is saved.
(2) According to the invention, the rotating speed and the reaction conditions of the rotary furnace are adjusted by utilizing abundant structures and properties of the tungsten bronze according to actual demands, the nanoscale tungsten bronze powder with different crystal structures (cubic crystals, tetragonal crystals and hexagonal crystals) is synthesized, and the near infrared light absorptivity of the tungsten bronze can be improved by adjusting the preparation process, so that the heat absorption and heat accumulation capacity of the fiber can be enhanced.
(3) The nano multi-metal doped tungsten bronze adopts a solid phase reaction method, the prepared nano-level powder is in a soft aggregation state, and can be dispersed through ultrasonic treatment without additional sanding treatment, so that the process flow is shortened, and the nano multi-metal doped tungsten bronze is a process capable of being produced in a large scale and can be produced in a large scale.
(4) The mass ratio of the heat storage slurry to the high polymer material in the heat storage fiber is (20-40): and 40, the surface of the master batch is smooth and flat, so that the next step of spinning is facilitated, nano particles in the fiber cannot be aggregated, the breaking strength of the fiber can be kept, and the temperature rise effect of the heat storage fiber woven fabric sample can be improved by 6 ℃ compared with a blank fabric sample under the condition of sunlight.
(5) According to the invention, repeated experiments and screening are carried out for many times, when the alkali metal, alkaline earth metal and rare earth elements in the nano multi-metal doped tungsten bronze are Cs, ca and La, the prepared multi-metal doped tungsten bronze has the best absorption capacity on near infrared light, wherein the molar ratio Cs is Ca: la= (0.22-0.25): 0.01: the near infrared spectrum absorption and sunlight irradiation temperature rise performance in the process of (0.01-0.03) are better than those of other proportions. The reason for the performance improvement is probably that the ion radius of cesium ions is large, the tungsten bronze with a rod-shaped hexagonal structure is formed in the synthesis process of tungsten bronze, the absorption of the tungsten bronze with the rod-shaped structure in a near-infrared long wave band is obviously improved, the near-infrared light absorption capacity of the 800-1100nm wave band can be improved by adding lanthanum ions, gaps in a tungsten bronze tunnel structure can be fully filled with the smaller ion radius of calcium ions, the carrier concentration is improved, the absorption of near-infrared light is enhanced, the defect that the near-infrared absorption capacity is rapidly reduced due to the precipitation of tungsten bronze metal ions in practical application is overcome, and the durability of the heat storage fiber is enhanced.
(6) The heat accumulating fiber can improve the heat accumulating and heat insulating performance of the fabric through various modes such as printing, dipping coating and melt spinning, and has wide application range.
Drawings
FIG. 1 is a graph comparing spectral absorptivity at 250-2500nm for nano-scale multi-metal doped tungsten bronzes of examples 1-2 and comparative examples 1-4;
FIG. 2 is an electron microscope image of the heat accumulating master batch prepared in example 3;
fig. 3 is a cross-sectional view of the heat accumulating fiber prepared in example 3.
Detailed Description
It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other. The following examples are all conventional biochemical reagents unless otherwise specified; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to examples.
EXAMPLE 1 preparation of nanocrystalline form Cs 0.22 Ca 0.01 La 0.03 WO 3 ：
(1) Cs produced 0.22 Ca 0.01 La 0.03 WO 3 In terms of mole ratio Cs: ca: la: w=0.22: 0.01: 36 parts by mass of cesium carbonate, 1 part by mass of calcium carbonate, 7 parts by mass of lanthanum carbonate, 232 parts by mass of tungsten oxide and 552 parts by mass of deionized water are weighed in a ratio of 0.03:1.
(2) Mixing the raw materials, and then putting the mixture into a ball mill to ball mill for 16 hours at 300 r/min;
(3) The ball-milled raw materials are kept in an oven at 105 ℃ for 12 hours;
(4) Crushing the dried raw materials by a crusher and then placing the crushed raw materials into a rotary furnace;
(5) The rotary furnace is initially charged with 5% hydrogen-nitrogen mixed gas with the flow rate of 200ml/min, and the temperature is raised after 2 min; and (3) a crystallization water removal stage: heating from room temperature to 270 ℃ at a speed of 5 ℃/min, wherein the ventilation speed of the rotary furnace is 50ml/min, and the rotation speed is 5rpm; a first heat preservation stage: preserving heat for 30min, wherein the inclination angle of the rotary furnace is 15 degrees; reduction stage: heating to 600 ℃ at a speed of 3 ℃/min, wherein the ventilation speed of the rotary furnace is 100ml/min, the rotation speed is 50rpm, and the inclination angle of the rotary furnace is 10 degrees; and a second heat preservation stage: preserving heat for 4 hours, wherein the ventilation rate of the rotary furnace is 200ml/min, and the inclination angle of the rotary furnace is 0 degree; in the reaction water removal stage, the temperature is reduced to 450 ℃ at 10 ℃/min, the ventilation rate of the rotary furnace is 50ml/min, and the inclination angle of the rotary furnace is 10 degrees; and (3) a cooling protection stage: cooling to room temperature at 5 ℃/min, and performing ultrasonic treatment for 1h at a rotary furnace ventilation rate of 4ml/min and 600W to obtain hexagonal nanometer multi-metal doped tungsten bronze Cs with powder particle size of 70-500nm 0.22 Ca 0.01 La 0.03 WO 3 The absorption rate is shown in figure 1, and the average particle size is 100-200nm.
EXAMPLE 2 preparation of nanocrystalline form of Cs 0.25 Ca 0.01 La 0.02 WO 3 ：
(1) Cs produced 0.25 Ca 0.01 La 0.02 WO 3 In terms of molar ratio Cs: ca: la: w=0.25: 0.01: weighing 41 parts by weight of cesium carbonate, 1 part by weight of calcium carbonate, 5 parts by weight of lanthanum carbonate, 232 parts by weight of tungsten oxide and 558 parts by weight of deionized water according to a ratio of 0.02:1; rest stepsThe procedure is as in example 1.
Comparative example 1 preparation of nano hexagonal form Cs 0.15 Ca 0.06 La 0.04 WO 3 ：
(1) Cs produced 0.15 Ca 0.06 La 0.04 WO 3 In terms of mole ratio Cs: ca: la: w=0.15: 0.06: weighing 24 parts by weight of cesium carbonate, 6 parts by weight of calcium carbonate, 9 parts by weight of lanthanum carbonate, 232 parts by weight of tungsten oxide and 542 parts by weight of deionized water according to a ratio of 0.04:1; the remaining steps are the same as in example 1.
Comparative example 2 preparation of nano hexagonal form Cs 0.28 Ca 0.02 La 0.01 WO 3 ：
(1) Cs produced 0.28 Ca 0.02 La 0.01 WO 3 In terms of mole ratio Cs: ca: la: w=0.28: 0.02: weighing 46 parts by mass of cesium carbonate, 1 part by mass of calcium carbonate, 2 parts by mass of lanthanum carbonate, 232 parts by mass of tungsten oxide and 562 parts by mass of deionized water according to a ratio of 0.01:1; the remaining steps are the same as in example 1.
Comparative example 3 preparation of nanocrystalline tetragonal form of Cs 0.22 Ca 0.01 La 0.03 WO 3 ：
(1) Cs produced 0.22 Ca 0.01 La 0.03 WO 3 In terms of mole ratio Cs: ca: la: w=0.22: 0.01: 36 parts by mass of cesium carbonate, 1 part by mass of calcium carbonate, 7 parts by mass of lanthanum carbonate, 232 parts by mass of tungsten oxide and 552 parts by mass of deionized water are weighed in a ratio of 0.03:1.
(2) Mixing the raw materials, and then putting the mixture into a ball mill to ball mill for 16 hours at 300 r/min;
(3) The ball-milled raw materials are kept in an oven at 105 ℃ for 12 hours;
(4) Crushing the dried raw materials by a crusher and then placing the crushed raw materials into a rotary furnace;
(5) The rotary furnace is initially charged with 5% hydrogen-nitrogen mixed gas with the flow rate of 200ml/min, and the temperature is raised after 2 min; and (3) a crystallization water removal stage: heating from room temperature to 270 ℃ at a speed of 5 ℃/min, wherein the ventilation speed of the rotary furnace is 50ml/min, and the rotation speed is 5rpm; a first heat preservation stage: preserving heat for 30min, wherein the inclination angle of the rotary furnace is 15 degrees; reduction stage: at a rate of 3 ℃/minThe temperature is raised to 800 ℃, the ventilation rate of the rotary furnace is 100ml/min, the rotation rate is 50rpm, and the inclination angle of the rotary furnace is 10 degrees; and a second heat preservation stage: preserving heat for 4 hours, wherein the ventilation rate of the rotary furnace is 200ml/min, and the inclination angle of the rotary furnace is 0 degree; in the reaction water removal stage, the temperature is reduced to 450 ℃ at 10 ℃/min, the ventilation rate of the rotary furnace is 50ml/min, and the inclination angle of the rotary furnace is 10 degrees; and (3) a cooling protection stage: cooling to room temperature at 5 ℃ per minute, and enabling the ventilation rate of the rotary furnace to be 4ml/min. After ultrasonic treatment, tetragonal crystal nanometer multi-metal doped tungsten bronze Cs can be obtained 0.22 Ca 0.01 La 0.03 WO 3 。
Comparative example 4 preparation of nanocube type Cs 0.22 Ca 0.01 La 0.03 WO 3 ：
(1) Cs produced 0.22 Ca 0.01 La 0.03 WO 3 In terms of mole ratio Cs: ca: la: w=0.22: 0.01: 36 parts by mass of cesium carbonate, 1 part by mass of calcium carbonate, 7 parts by mass of lanthanum carbonate, 232 parts by mass of tungsten oxide and 552 parts by mass of deionized water are weighed in a ratio of 0.03:1.
(2) Mixing the raw materials, and then putting the mixture into a ball mill to ball mill for 16 hours at 300 r/min;
(3) The ball-milled raw materials are kept in an oven at 105 ℃ for 12 hours;
(4) Crushing the dried raw materials by a crusher and then placing the crushed raw materials into a rotary furnace;
(5) The rotary furnace is initially charged with 5% hydrogen-nitrogen mixed gas with the flow rate of 200ml/min, and the temperature is raised after 2 min; and (3) a crystallization water removal stage: heating from room temperature to 270 ℃ at a speed of 5 ℃/min, wherein the ventilation speed of the rotary furnace is 50ml/min, and the rotation speed is 5rpm; a first heat preservation stage: preserving heat for 30min, wherein the inclination angle of the rotary furnace is 15 degrees; reduction stage: heating to 900 ℃ at a speed of 3 ℃/min, wherein the ventilation speed of the rotary furnace is 100ml/min, the rotation speed is 50rpm, and the inclination angle of the rotary furnace is 10 degrees; and a second heat preservation stage: preserving heat for 4-8 hours, wherein the ventilation rate of the rotary furnace is 200ml/min, and the inclination angle of the rotary furnace is 0 degree; in the reaction water removal stage, the temperature is reduced to 450 ℃ at 10 ℃/min, the ventilation rate of the rotary furnace is 50ml/min, and the inclination angle of the rotary furnace is 10 degrees; and (3) a cooling protection stage: cooling to room temperature at 5 deg.c/min and ventilating the rotary furnaceThe rate was 4ml/min. After ultrasonic treatment, the cubic crystal type nano multi-metal doped tungsten bronze Cs can be obtained 0.22 Ca 0.01 La 0.03 WO 3 。
The nano-multi-metal doped tungsten bronze obtained in the above examples 1-2 and comparative examples 1-4 was tested for spectral absorptivity in the wavelength band of 250-2500nm using an ultraviolet-visible-near infrared spectrophotometer, as shown in fig. 1, it was found that when Cs: ca: la= (0.22-0.25): 0.01: (0.01-0.03), i.e., the spectral absorptance of examples 1-2 is higher than that of comparative examples 1-2; under the same conditions, the hexagonal tungsten bronze (example 1) obtained by reduction at 600 ℃ has better performance than the tetragonal tungsten bronze (comparative example 3) obtained by reduction at 800 ℃ and the cubic tungsten bronze (comparative example 4) obtained by reduction at 900 ℃.
Example 3 preparation of nano-multimetal doped tungsten bronze thermal storage fiber
(1) Taking Cs prepared in example 1 0.22 Ca 0.01 La 0.03 WO 3 30 parts by mass of powder, 10 parts by mass of a silane coupling agent (KH 560), 60 parts by mass of deionized water and 0.5 part by mass of a foam killer Foamex 810, dispersing for 1h by a dispersing machine, and mixing in an environment with ultrasonic power of 600W to obtain heat storage slurry;
(2) Putting 20 parts by mass of heat storage slurry and 40 parts by mass of PET into a high-speed mixer, wherein the rotating speed is 1000r/min, the mixing time is 10min, the interval time is 5min, and the circulation is performed for three times;
(3) Drying the mixed materials at 80 ℃ for 20 hours to ensure that the water content is not higher than 200ppm, then placing the materials into a double-screw granulator, and melting, cooling and cutting the materials at 270 ℃ and 220r/min to obtain heat-accumulating master batches, wherein the structure of the heat-accumulating master batches is shown in figure 2;
(4) Putting the master batch into a melt spinning machine, melting the master batch into a bundle-shaped high polymer melt at high temperature, feeding filaments formed by cooling and condensing the high polymer melt extruded from a spinning nozzle into a rotary collector to obtain rare earth heat storage fibers, monitoring the pressure at the tail end of a spinning assembly to be 4.5Mpa at the spinning temperature of 280 ℃ for keeping the stability of spinning, and collecting the heat storage fibers at the winding speed of 2400m/min, wherein the cross section of the heat storage fibers is shown in figure 3;
(5) Dividing the collected 80D heat storage fibers into warp yarns and weft yarns, weaving plain weave fabric with the width of 50cm and the length of 5 meters on a loom to obtain the heat storage fabric, and testing the sunlight heat storage performance and the breaking strength of the fibers by using a near infrared lamp irradiation.
Example 4 preparation of nano-multimetal doped tungsten bronze thermal storage fiber
(1) Taking Cs prepared in example 1 0.22 Ca 0.01 La 0.03 WO 3 30 parts by mass of powder, 10 parts by mass of a silane coupling agent (KH 560), 60 parts by mass of deionized water and 0.5 part by mass of a foam killer Foamex 810, dispersing for 1h by using a dispersing machine, and mixing in an environment with ultrasonic power of 600W to obtain heat storage slurry;
(2) 30 parts by mass of heat storage slurry and 40 parts by mass of PET are put into a high-speed mixer, the rotating speed is 1000r/min, the mixing time is 10min, the interval time is 5min, and the circulation is performed for three times;
(3) Drying the mixed material at 80 ℃ for 20 hours to ensure that the water content is not higher than 200ppm, then placing the mixed material into a double-screw granulator, and melting, cooling and cutting the mixed material at 270 ℃ and 220r/min to obtain heat storage functional master batch;
(4) Putting the master batch into a melt spinning machine, melting the master batch into a bundle-shaped high polymer melt at high temperature, feeding filaments formed by cooling and condensing the high polymer melt extruded from a spinning nozzle into a rotary collector to obtain rare earth heat accumulating fibers, monitoring the pressure at the tail end of a spinning component to be 4.5Mpa at the spinning temperature of 280 ℃ for keeping the spinning stable, and collecting the heat accumulating fibers at the winding speed of 2400 m/min;
(5) Dividing the collected 80D heat storage fibers into warp yarns and weft yarns, weaving plain weave fabric with the width of 50cm and the length of 5 meters on a loom to obtain the heat storage fabric, and testing the sunlight heat storage performance and the breaking strength of the fibers by using a near infrared lamp irradiation.
Example 5 preparation of nano-multimetal doped tungsten bronze thermal storage fiber
(1) Example 1 preparationPrepared Cs 0.22 Ca 0.01 La 0.03 WO 3 30 parts by mass of powder, 10 parts by mass of a silane coupling agent (KH 560), 60 parts by mass of deionized water and 0.5 part by mass of a foam killer Foamex 810, dispersing for 1h by using a dispersing machine, and mixing in an environment with ultrasonic power of 600W to obtain heat storage slurry;
(2) Putting 40 parts by mass of heat storage slurry and 40 parts by mass of PET into a high-speed mixer, wherein the rotating speed is 1000r/min, the mixing time is 10min, the interval time is 5min, and the circulation is performed for three times;
(3) Drying the mixed material at 80 ℃ for 20 hours to ensure that the water content is not higher than 200ppm, then placing the mixed material into a double-screw granulator, and melting, cooling and cutting the mixed material at 270 ℃ and 220r/min to obtain heat storage functional master batch;
(4) Putting the master batch into a melt spinning machine, melting the master batch into a bundle-shaped high polymer melt at high temperature, feeding filaments formed by cooling and condensing the high polymer melt extruded from a spinning nozzle into a rotary collector to obtain rare earth heat accumulating fibers, monitoring the pressure at the tail end of a spinning component to be 4.5Mpa at the spinning temperature of 280 ℃ for keeping the spinning stable, and collecting the heat accumulating fibers at the winding speed of 2400 m/min;
(5) Dividing the collected 80D heat storage fibers into warp yarns and weft yarns, weaving plain weave fabric with the width of 50cm and the length of 5 meters on a loom to obtain the heat storage fabric, and testing the sunlight heat storage performance and the breaking strength of the fibers by using a near infrared lamp irradiation.
Example 6 preparation of nano-multimetal doped tungsten bronze thermal storage fiber
(1) Taking Cs prepared in example 1 0.22 Ca 0.01 La 0.03 WO 3 30 parts by mass of powder, 10 parts by mass of a silane coupling agent (KH 560), 60 parts by mass of deionized water and 0.5 part by mass of a foam killer Foamex 810, dispersing for 1h by using a dispersing machine, and mixing in an environment with ultrasonic power of 600W to obtain heat storage slurry;
(2) Putting 20 parts by mass of heat storage slurry and 50 parts by mass of PET into a high-speed mixer, wherein the rotating speed is 1000r/min, the mixing time is 10min, the interval time is 5min, and the circulation is performed for three times;
(3) Drying the mixed material at 80 ℃ for 20 hours to ensure that the water content is not higher than 200ppm, then placing the mixed material into a double-screw granulator, and melting, cooling and cutting the mixed material at 270 ℃ and 220r/min to obtain heat storage functional master batch;
(4) Putting the master batch into a melt spinning machine, melting the master batch into a bundle-shaped high polymer melt at high temperature, feeding filaments formed by cooling and condensing the high polymer melt extruded from a spinning nozzle into a rotary collector to obtain rare earth heat accumulating fibers, monitoring the pressure at the tail end of a spinning component to be 4.5Mpa at the spinning temperature of 280 ℃ for keeping the spinning stable, and collecting the heat accumulating fibers at the winding speed of 2400 m/min;
(5) Dividing the collected 80D heat storage fibers into warp yarns and weft yarns, weaving plain weave fabric with the width of 50cm and the length of 5 meters on a loom to obtain the heat storage fabric, and testing the sunlight heat storage performance and the breaking strength of the fibers by using a near infrared lamp irradiation.
Example 7 preparation of nano-multimetal doped tungsten bronze thermal storage fiber
(1) Taking Cs prepared in example 1 0.22 Ca 0.01 La 0.03 WO 3 30 parts by mass of powder, 10 parts by mass of a silane coupling agent (KH 560), 60 parts by mass of deionized water and 0.5 part by mass of a foam killer Foamex 810, dispersing for 1h by using a dispersing machine, and mixing in an environment with ultrasonic power of 600W to obtain heat storage slurry;
(2) 30 parts by mass of heat storage slurry and 70 parts by mass of PET are put into a high-speed mixer, the rotating speed is 1000r/min, the mixing time is 10min, the interval time is 5min, and the circulation is performed for three times;
(3) Drying the mixed material at 80 ℃ for 20 hours to ensure that the water content is not higher than 200ppm, then placing the mixed material into a double-screw granulator, and melting, cooling and cutting the mixed material at 270 ℃ and 220r/min to obtain heat storage functional master batch;
(4) Putting the master batch into a melt spinning machine, melting the master batch into a bundle-shaped high polymer melt at high temperature, feeding filaments formed by cooling and condensing the high polymer melt extruded from a spinning nozzle into a rotary collector to obtain rare earth heat accumulating fibers, monitoring the pressure at the tail end of a spinning component to be 4.5Mpa at the spinning temperature of 280 ℃ for keeping the spinning stable, and collecting the heat accumulating fibers at the winding speed of 2400 m/min;
(5) Dividing the collected 80D heat storage fibers into warp yarns and weft yarns, weaving plain weave fabric with the width of 50cm and the length of 5 meters on a loom to obtain the heat storage fabric, and testing the sunlight heat storage performance and the breaking strength of the fibers by using a near infrared lamp irradiation.
Comparative example 5
(1) Taking Cs prepared in example 1 0.22 Ca 0.01 La 0.03 WO 3 30 parts by mass of powder, 10 parts by mass of a silane coupling agent (KH 560), 60 parts by mass of deionized water and 0.5 part by mass of a foam killer Foamex 810, dispersing for 1h by using a dispersing machine, and mixing in an environment with ultrasonic power of 600W to obtain heat storage slurry;
(2) 5 parts by mass of heat storage slurry and 70 parts by mass of PET are put into a high-speed mixer, the rotating speed is 1000r/min, the mixing time is 10min, the interval time is 5min, and the circulation is performed for three times;
(3) Drying the mixed material at 80 ℃ for 20 hours to ensure that the water content is not higher than 200ppm, then placing the mixed material into a double-screw granulator, and melting, cooling and cutting the mixed material at 270 ℃ and 220r/min to obtain heat storage functional master batch;
(4) Putting the master batch into a melt spinning machine, melting the master batch into a bundle-shaped high polymer melt at high temperature, feeding filaments formed by cooling and condensing the high polymer melt extruded from a spinning nozzle into a rotary collector to obtain rare earth heat accumulating fibers, monitoring the pressure at the tail end of a spinning component to be 4.5Mpa at the spinning temperature of 280 ℃ for keeping the spinning stable, and collecting the heat accumulating fibers at the winding speed of 2400 m/min;
(5) Dividing the collected 80D heat storage fibers into warp yarns and weft yarns, weaving plain weave fabric with the width of 50cm and the length of 5 meters on a loom to obtain the heat storage fabric, and testing the sunlight heat storage performance and the breaking strength of the fibers by using a near infrared lamp irradiation.
Comparative example 6
(1) Taking Cs prepared in example 1 0.22 Ca 0.01 La 0.03 WO 3 30 parts by mass of powder, 10 parts by mass of a silane coupling agent (KH 560), 60 parts by mass of deionized water and 0.5 part by mass of a foam killer Foamex 810, dispersing for 1h by using a dispersing machine, and mixing in an environment with ultrasonic power of 600W to obtain heat storage slurry;
(2) Putting 40 parts by mass of heat storage slurry and 30 parts by mass of PET into a high-speed mixer, wherein the rotating speed is 1000r/min, the mixing time is 10min, the interval time is 5min, and the circulation is performed for three times;
(3) Drying the mixed material at 80 ℃ for 20 hours to ensure that the water content is not higher than 200ppm, then placing the mixed material into a double-screw granulator, and melting, cooling and cutting the mixed material at 270 ℃ and 220r/min to obtain heat storage functional master batch;
(4) Putting the master batch into a melt spinning machine, melting the master batch into a bundle-shaped high polymer melt at high temperature, feeding filaments formed by cooling and condensing the high polymer melt extruded from a spinning nozzle into a rotary collector to obtain rare earth heat accumulating fibers, monitoring the pressure at the tail end of a spinning component to be 4.5Mpa at the spinning temperature of 280 ℃ for keeping the spinning stable, and collecting the heat accumulating fibers at the winding speed of 2400 m/min;
(5) Dividing the collected 80D heat storage fibers into warp yarns and weft yarns, weaving plain weave fabric with the width of 50cm and the length of 5 meters on a loom to obtain the heat storage fabric, and testing the sunlight heat storage performance and the breaking strength of the fibers by using a near infrared lamp irradiation.
Comparative example 7
The difference from the examples is that no nano-multimetal doped tungsten bronze is added:
(1) Putting 40 parts by mass of PET master batch into a melt spinning machine, melting the master batch into a bundle-shaped high polymer melt at high temperature, feeding filaments obtained by cooling and condensing the high polymer melt extruded from a spinning nozzle into a rotary collector to obtain rare earth heat storage fibers, monitoring the pressure at the tail end of a spinning component to be 4.5Mpa at the temperature of 280 ℃ for keeping the stability of spinning, and collecting the heat storage fibers at the winding speed of 2400 m/min;
(2) The collected 80D PET fibers are divided into warp yarns and weft yarns, a plain weave fabric with the width of 50cm and the length of 5 meters is woven on a loom, namely the PET fabric, and the sunlight heat storage performance and the breaking strength of the fibers are tested by irradiation of a near infrared lamp.
Table 1 comparative table of properties of heat storage fabrics prepared in examples and comparative examples
The solar heat absorption performance and the breaking strength of the fibers of the fabrics of comparative examples 3 to 7 and comparative examples 5 to 7 are shown in table 1, and it can be found that the performance of the fabric prepared from the fibers of the present invention is significantly better than that of the comparative examples, because the nanoscale multi-metal doped tungsten bronze filled in the fibers can be converted into heat energy by absorbing energy in near infrared rays, thereby providing the heat storage and insulation functions, and simultaneously realizing the stabilization of the mechanical properties of the fibers for the control of the filling amount. And when the mass ratio of the heat storage slurry to the polymer material is (20-40): 40, the cloth has more excellent sunlight heat storage performance, can improve the temperature difference of nearly 6 ℃ compared with a blank cloth sample, and has good mechanical properties.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (7)
1. A nanometer multi-metal doped tungsten bronze heat storage fiber is characterized in that: the fiber is prepared from 10-60 parts by mass of heat storage slurry and 40-70 parts by mass of high polymer material through melt spinning, wherein the heat storage slurry is prepared from nano multi-metal doped tungsten bronze, a dispersion medium, a dispersing agent and a defoaming agent, and the chemical formula of the nano multi-metal doped tungsten bronze is A x B y Re (0.33-x-2y)/3 WO 3 ，0<x<0.4、0<y<0.1、0<x+2y is less than or equal to 0.33, A is an alkali metal element, B is an alkaline earth metal element, and Re is a rare earth element;
the alkali metal element, the alkaline earth metal element and the rare earth element are Cs, ca and La respectively, and the molar ratio of Cs to Ca to La in the nano multi-metal doped tungsten bronze is (0.22-0.25): 0.01: (0.01-0.03);
the crystal structure of the nano multi-metal doped tungsten bronze is one of cubic crystal, tetragonal crystal and hexagonal crystal.
2. The nano-multi-metal doped tungsten bronze thermal storage fiber according to claim 1, wherein: the heat storage slurry comprises the following raw materials in parts by mass: 10-40 parts of nano multi-metal doped tungsten bronze, 50-80 parts of dispersion medium, 5-20 parts of dispersing agent and 0.5-5 parts of defoaming agent, wherein the particle size of the nano multi-metal doped tungsten bronze is 70-500nm.
3. The nano-multi-metal doped tungsten bronze thermal storage fiber according to claim 1, wherein: the nano multi-metal doped tungsten bronze is prepared by the following method:
(1) Weighing raw materials of an alkali metal source, an alkaline earth metal source, a rare earth source and a tungsten source according to a proportion, and filling all the raw materials into a ball milling tank with a dispersion medium for ball milling;
(2) Drying the ball-milled powder at 90-120 ℃ for 16-24 hours, and crushing the dried raw materials into powder by a crusher;
(3) And (3) charging the crushed raw materials into a rotary furnace, and calcining the raw materials in a crystallization water removal stage, a first heat preservation stage, a reduction stage, a second heat preservation stage, a reaction water removal stage and a cooling protection stage, and performing ultrasonic treatment to obtain the nano multi-metal doped tungsten bronze powder.
4. The nano-multi-metal doped tungsten bronze thermal storage fiber according to claim 1, wherein: the polymer material is one or more of ethylene terephthalate, polyurethane, polybutylene terephthalate and polystyrene; the dispersing agent is one or more of silane coupling agent KH550, silane coupling agent KH560, silane coupling agent KH570, polyethylene glycol, polyvinyl alcohol and polyvinylpyrrolidone; the dispersion medium is one or more of deionized water, diisobutyl ketone, ethyl acetate and propylene glycol methyl ether acetate; the defoamer is one or two of Foamex 810 and FoamStar A10.
5. A method for preparing the nano multi-metal doped tungsten bronze heat storage fiber according to any one of claims 1 to 4, which is characterized in that: the method comprises the following steps:
(1) Mixing nano multi-metal doped tungsten bronze powder, a dispersing agent, a dispersing medium and a defoaming agent according to a proportion, uniformly dispersing by using a dispersing machine, and performing ultrasonic treatment to 70-500nm to obtain heat storage slurry;
(2) Uniformly mixing 10-60 parts by mass of heat storage slurry and 40-70 parts by mass of high polymer material in a high-speed mixer;
(3) Drying the material obtained in the step (2) until the water content is not higher than 200ppm, then putting the material into a double-screw granulator, and performing high-temperature melt extrusion granulation to obtain heat-storage functional master batch;
(4) And (3) putting the obtained heat accumulating functional master batch into a melt spinning machine, melting the master batch at high temperature to form a beam-shaped high polymer melt, and winding and collecting filaments which are formed by air-cooling condensation of the high polymer melt pressed out of a spinning nozzle to obtain the nano multi-metal doped tungsten bronze heat accumulating fiber.
6. The method for preparing the nano multi-metal doped tungsten bronze heat storage fiber according to claim 5, which is characterized in that: the rotating speed of the high-speed mixer in the step (2) is 500-1200r/min;
the temperature of the drying in the step (3) is 80-120 ℃, the duration time is 12-24h, the rotating speed of the double-screw granulator is 50-250r/min, and the temperature is 220-280 ℃;
the spinning temperature in the step (4) is 220-320 ℃.
7. Use of the nano multi-metal doped tungsten bronze heat accumulating fiber according to any one of claims 1 to 4 in the textile field of home textiles and clothing fabrics.
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