CN115467091B - Bismuth oxide/gadolinium oxide nanofiber membrane alternately-stacked composite material and preparation method thereof - Google Patents
Bismuth oxide/gadolinium oxide nanofiber membrane alternately-stacked composite material and preparation method thereof Download PDFInfo
- Publication number
- CN115467091B CN115467091B CN202211030751.9A CN202211030751A CN115467091B CN 115467091 B CN115467091 B CN 115467091B CN 202211030751 A CN202211030751 A CN 202211030751A CN 115467091 B CN115467091 B CN 115467091B
- Authority
- CN
- China
- Prior art keywords
- bismuth
- gadolinium
- oxide
- polymer
- composite material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4209—Inorganic fibres
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
- D04H1/43838—Ultrafine fibres, e.g. microfibres
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/593—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives to layered webs
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/64—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
- D04H1/66—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions at spaced points or locations
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/732—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by fluid current, e.g. air-lay
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Artificial Filaments (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a bismuth oxide/gadolinium oxide nanofiber membrane alternately stacked composite material and a preparation method thereof, wherein the composite material is formed by alternately stacking bismuth oxide/gadolinium oxide nanofiber membranes, and the preparation method is as follows: introducing a polymer into inorganic sol containing bismuth and gadolinium to obtain a precursor solution; preparing a bismuth oxide/polymer hybridization nanofiber membrane and a gadolinium oxide/polymer hybridization nanofiber membrane by using an electrostatic spinning method; removing the polymer to prepare a bismuth oxide nanofiber membrane and a gadolinium oxide nanofiber membrane; and alternately stacking the bismuth oxide nanofiber membranes and the gadolinium oxide nanofiber membranes to obtain the composite material. Compared with the prior art, the composite material provided by the invention has the advantages that the X-ray shielding efficiency of below 150keV can reach more than 90%, the problems of high brittleness and difficult molding of the existing electrostatic spinning bismuth oxide and gadolinium oxide nanofiber are solved, and the preparation method provided by the invention can be applied in a large scale and has better universality.
Description
Technical Field
The invention relates to the technical field of novel composite materials, in particular to a composite material with alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes and a preparation method thereof.
Background
The X-ray is used as a short-wave ionizing radiation source and is widely applied to the fields of national defense construction, industrial flaw detection, medical treatment and health and the like. However, the X-ray radiation with overdose can cause harm to human body, damage organs and tissues of human body, and cause radiation diseases and even death. The X-ray protective clothing can effectively reduce the damage of X-ray radiation to human bodies, and the traditional preparation material is generally lead-containing material, but the material is harmful to human bodies, is not easy to recycle and pollutes the environment. In recent years, there has been an increasing research on lead-free or lead-free X-ray radiation protection materials.
In recent years, researchers have made a series of studies on lead-free wearable radiation protective clothing. Polypropylene is used as a matrix, powder containing lead and barium is used as a shielding agent, and after mixing granulation, the composite fiber and the non-woven fabric for preventing X-rays are prepared by melt spinning, and the X-ray protective clothing is prepared by the composite fiber and the non-woven fabric; the united states uses modified polyethylene and polyvinyl chloride as shielding fabrics and tantalum metal as a shielding interlayer between the two fabrics to develop the radiation protection fabrics and the whole body radiation protection clothing. Patent CN101137285a discloses a composite shielding material for medical X-ray protection, which is prepared by adding barium, cadmium, tin and lanthanide into polymer materials such as natural rubber, and overcomes the defect of weak absorption area caused by single element, but the addition of multiple elements makes the preparation process of the material complex, the element price expensive, and the industrialized production is not facilitated.
The bismuth and gadolinium elements have complementary K absorption edges, can realize the full-band absorption of X-rays below 150keV, and the raw materials are environment-friendly and easy to obtain, so that the bismuth and gadolinium elements become key points and leading edges of the research in the field of nuclear protection. But it is typically added to the polymer matrix in powder form to provide the protective garment with good mechanical properties to meet the wearable requirements. However, the high polymer material has low interfacial compatibility, and the material has poor dispersibility, low mechanical properties and shielding holes due to the problem of gaps and the like. Therefore, there is a need to develop a pure bismuth oxide/gadolinium oxide composite material that is lightweight, breathable, and can efficiently shield all-band X-rays.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a composite material with alternately stacked bismuth oxide/gadolinium oxide nanofiber films and a preparation method thereof, so as to solve the defects of poor dispersibility, low mechanical property and shielding holes when bismuth and gadolinium are added into a polymer matrix in a powder form, and the X-ray shielding efficiency of the prepared composite material below 150keV can reach more than 90%.
The aim of the invention can be achieved by the following technical scheme:
the first object of the invention is to provide a preparation method of a composite material with alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes, which comprises the following steps:
s1, dissolving a polymer A in N, N-dimethylformamide, and stirring for 2-12 hours at room temperature until a homogeneous system is formed, so as to obtain a polymer solution B;
s2, adding a bismuth source into the polymer solution B obtained in the step S1, and stirring for 2-6 hours at room temperature to obtain a clear and transparent bismuth-containing precursor spinning solution C;
s3, injecting the precursor spinning solution C obtained in the step S2 into an injector to perform air jet assisted electrostatic spinning, adding an air flow traction area in a classical jet flight area, greatly improving the injection rate of the precursor spinning solution C at the spray hole under the synergistic effect of a high-voltage electric field and high-speed air flow, stretching the precursor spinning solution C to form jet flow, and depositing the jet flow on a receiving device to obtain the bismuth oxide/polymer hybrid micro-nano fiber film with uniform appearance and no adhesion;
s4, calcining the bismuth oxide/polymer hybridization micro-nanofiber membrane obtained in the S3 as a template to obtain a bismuth oxide nanofiber membrane;
s5, dissolving the polymer D in absolute ethyl alcohol, and magnetically stirring uniformly to obtain a polymer solution E;
s6, dissolving a gadolinium source in water, mixing with the polymer solution E obtained in the S5, and carrying out ultrasonic magnetic stirring in a water bath for 20-48 hours to obtain a gadolinium-containing precursor solution F;
s7, taking aluminum foil as a receiving base material, and carrying out electrostatic spinning on the precursor solution F obtained in the S6 under 15-100 kV voltage to obtain a gadolinium oxide/polymer hybrid nanofiber membrane;
s8, putting the gadolinium oxide/polymer hybrid nanofiber membrane obtained in the step S7 in an environment with the temperature higher than the decomposition temperature of the polymer and lower than the crystal phase transition temperature of the gadolinium oxide overnight, and removing the polymer in the nanofiber membrane to obtain the gadolinium oxide nanofiber membrane;
and S9, alternately stacking the bismuth oxide nanofiber membrane obtained in the step S4 and the gadolinium oxide nanofiber membrane obtained in the step S8 to obtain the composite material with alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes.
Preferably, the polymer in S1 is any one of polyethylene oxide (PEO, molecular weight 100000-1000000), polyvinyl alcohol (PVA, molecular weight 16000-200000), polyvinyl butyral (PVB, molecular weight 30000-40000), polyvinylpyrrolidone (PVP, molecular weight 45000-58000), and polyacrylonitrile (PAN, molecular weight 50000-150000).
Preferably, the bismuth source in S2 is any one of bismuth nitrate, bismuth isopropoxide, bismuth acetate, bismuth chloride octahydrate, bismuth subcarbonate, and bismuth oxychloride.
Preferably, the mass ratio of the bismuth source to the polymer solution B in S2 is 1: (1.5-5).
Preferably, the electrostatic spinning environment in S3 is: the air humidity is 60-85%, and the temperature is 15-25 ℃.
Preferably, the process parameters of the electrospinning in S3 are as follows: the voltage is 20-120 kV, the pouring speed is 0.5-15 mL/h, the spinning distance is 15-60 cm, the sliding table speed is 1-200 cm/min, the roller speed of the receiving device is 10-50 r/min, and the air flow speed is 1-20 m/s.
Preferably, the temperature rising rate of the calcination in the step S4 is 5 ℃/min-20 ℃/min, the highest calcination temperature is 400-670 ℃, and the calcination time is 10-20 h.
Preferably, in S5, the polymer D is any one of polyethylene oxide (PEO, molecular weight of 100000-1000000), polyvinyl alcohol (PVA, molecular weight of 16000-200000), polyvinyl butyral (PVB, molecular weight of 30000-40000), polyvinylpyrrolidone (PVP, molecular weight of 45000-58000), and polyacrylonitrile (PAN, molecular weight of 50000-150000).
Preferably, the mass fraction of the polymer D in the precursor solution F in the S6 is 2-10%, and the mass fraction of the gadolinium source is 4-15%.
Preferably, the gadolinium source in S6 is any one of gadolinium nitrate, gadolinium acetate, gadolinium isopropoxide, and gadolinium chloride hydrate.
Preferably, the composite material in which the bismuth oxide/gadolinium oxide nanofiber films are alternately stacked in S9 is reinforced by using a full contact lamination hot rolling technology of spot gluing.
Further preferably, the technological parameters of the full-contact lamination hot rolling technology of the adhesive bonding are as follows: the dispensing array is in a multi-array form, the hot rolling temperature is 80-120 ℃, and the dispensing number is 30-100/m 2 The dispensing shape is any one of oval, triangle, square or hexagon.
The second object of the invention is to provide a composite material with alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes, which is prepared based on the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
1) Compared with the existing elastic lead-free nuclear protective clothing, the composite material with the alternately stacked bismuth oxide/gadolinium oxide nanofiber films has the advantage that the inorganic bismuth oxide nanofiber films and gadolinium oxide nanofiber films with the complementary absorption edges of K layers are alternately stacked, so that the X-ray shielding efficiency of the material below 150keV can reach more than 90%.
2) The preparation method of the composite material with alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes is a continuous process, and by combining a sol-gel method and an electrostatic spinning method, an airflow drafting zone is added in an electrostatic jet flow flying area, so that the flexible bismuth oxide nanofiber membrane and gadolinium oxide nanofiber membrane are successfully prepared, the problems that the existing electrostatic spinning bismuth oxide and gadolinium oxide nanofiber membranes are large in brittleness and difficult to form are solved, and the method can be applied in a large scale and has good universality.
Drawings
Fig. 1 is a schematic structural diagram of an alternate stacking of bismuth oxide/gadolinium oxide nanofiber membranes in the present solution.
Fig. 2 is an electron microscopic view and a flexible display view of the bismuth oxide nanofiber membrane in example 1.
Fig. 3 is an electron microscopic view and a flexible display view of the gadolinium oxide nanofiber membrane in example 1.
Description of the embodiments
The invention will now be described in detail with reference to the drawings and specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
In the technical scheme, the characteristics of preparation means, materials, structures or composition ratios and the like which are not explicitly described are regarded as common technical characteristics disclosed in the prior art.
The technical scheme fully realizes the defects that the existing elastic lead-free core protective clothing in the prior art has complicated material preparation process, high element price and adverse industrialized production in the conception process; bismuth and gadolinium are added into a polymer matrix in a powder form, and the high polymer material has the defects of poor dispersibility, low mechanical property and shielding loopholes due to low interfacial compatibility, gap problems of the material and the like. Innovative polymer templates are introduced into inorganic sol containing bismuth and gadolinium to obtain polymer/inorganic sol precursor solution, and flexible bismuth oxide nanofiber and gadolinium oxide nanofiber are prepared by using an electrostatic spinning method. In the process, an air flow drafting area is added in the jet flow flight process, so that the drafting refinement of spinning jet flow and final random deposition on a receiving device are realized. And then, calcining the hybridized nanofiber membrane through gradient heating to remove organic polymer components in the fiber membrane, so that the preparation of the flexible pure bismuth oxide fiber and gadolinium oxide nanofiber is realized. In the gradient heating process, the bismuth source and the gadolinium source are respectively and uniformly distributed in the hybrid nanofiber and on the surface, the form of crystal grains generated by the bismuth source and the gadolinium source can be accurately regulated and controlled in the gradient heating process, the bismuth oxide and gadolinium oxide nanofiber is formed by small bismuth oxide crystal grains, the small crystal grains are continuously fused and grown in the sintering process, the crystal growth process is completed, the original nanofiber becomes thicker gradually due to the growth of the small crystal grains, and the separation trend appears, so that the chain-shaped flexible bismuth oxide and gadolinium oxide nanofiber membrane is formed. And then the bismuth oxide/gadolinium oxide nanofiber films are alternately stacked to obtain the composite material with the alternately stacked bismuth oxide/gadolinium oxide nanofiber films.
Fig. 1 is a schematic structural diagram of a composite material in which bismuth oxide/gadolinium oxide nanofiber membranes are alternately stacked in the present technical solution.
Examples
The preparation method of the composite material with alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes in the embodiment comprises the following steps:
s1, adding 0.5g of polyacrylonitrile (PAN, with molecular weight of 90000) into 9.5g of N, N-Dimethylformamide (DMF), and stirring at room temperature for 4 hours to prepare a homogeneous polymer solution B with 5%wt;
s2 then 2g of bismuth nitrate (Bi (NO) 3 ) 3 ) Adding 10g of polymer solution B obtained by 5%wt of S1, and stirring for 4 hours at room temperature to obtain precursor spinning solution C containing bismuth;
s3, injecting the precursor spinning solution C obtained in the step S2 into an injector, and carrying out electrostatic spinning under the process parameters of 70+/-5% of air humidity, 20+/-2 ℃ of temperature, 30kV of voltage, 0.5mL/h of filling speed, 15cm of spinning distance, 10r/min of receiving device roller speed, 10cm/min of sliding table speed and 10m/S of air flow speed, thereby obtaining the bismuth oxide/polymer hybrid micro-nanofiber membrane with the diameter of 100-1000 nm, and the bismuth source is uniformly distributed in the interior and on the surface of the hybrid nanofiber;
s4, placing the bismuth oxide/polymer hybridization micro-nanofiber membrane obtained in the S3 into a muffle furnace, heating at a speed of 10 ℃/min, and keeping at 450 ℃ for 14 hours to obtain the bismuth oxide nanofiber membrane with a fiber diameter of 200-400 nm, wherein an electron microscope image and a flexible display image of the bismuth oxide nanofiber membrane are shown in the figure 2;
s5, weighing 28g of absolute ethyl alcohol and 2g of polyacrylonitrile (PAN, molecular weight is 90000), and magnetically stirring uniformly to obtain a polymer solution E;
s6, weighing 5g of gadolinium nitrate (Gd (NO) 3 ) 3 •6H 2 O), adding 14g of water to completely dissolve the gadolinium oxide precursor solution, mixing the gadolinium oxide precursor solution with the stirred polymer solution E obtained in the step S5, and magnetically stirring the mixture for 20 hours;
s7, carrying out electrostatic spinning (air humidity 50% and temperature 25 ℃) on the precursor solution under 35kV voltage to obtain a gadolinium oxide/polymer hybrid nanofiber membrane;
s8, placing the gadolinium oxide/polymer hybrid nanofiber membrane obtained in the S7 in a muffle furnace environment at 550 ℃ for overnight to remove the polymer in the nanofiber membrane, and obtaining the gadolinium oxide nanofiber membrane with the thickness of 50 microns and the fiber diameter of 200-800 nm, wherein an electron microscope image and a flexible display image of the gadolinium oxide nanofiber membrane are shown in FIG. 3;
s9, alternately stacking the bismuth oxide nanofiber membrane obtained in the S4 and the gadolinium oxide nanofiber membrane obtained in the S8 for 10 times to obtain the composite material with alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes, wherein the dispensing array is in a multi-array form, the hot rolling temperature is 80 ℃, and the dispensing number is 30/m 2 The dispensing shape is elliptical.
The thickness of the composite material in this embodiment, in which bismuth oxide/gadolinium oxide nanofiber membranes are alternately stacked, is about 2 mm.
Examples
The preparation method of the composite material with alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes in the embodiment comprises the following steps:
s1, adding 1 g polyethylene oxide (PEO) into 9g of DMF, and stirring for 2 hours at room temperature to prepare a homogeneous polymer solution B with the weight of 10%;
s2, 1 g bismuth nitrate (Bi (NO 3 ) 3 ) Adding into 3g of 10%wt of polymer solution B obtained by S1, and stirring for 5 hours at room temperature to obtain bismuth-containing precursor spinning solution C;
s3, injecting the solution C of the precursor spinning solution obtained in the step S2 into an injector, and carrying out electrostatic spinning under the process parameters of 60+/-5% of air humidity, 20+/-2 ℃ of temperature, 32kV of voltage, 1mL/h of pouring speed, 20cm of spinning distance, 12r/min of receiving device roller speed, 15cm/min of sliding table speed and 15m/S of air flow speed, thereby obtaining the bismuth oxide/polymer hybrid micro-nanofiber membrane with the diameter of 100-1000 nm, and the bismuth source is uniformly distributed in the interior and on the surface of the hybrid nanofiber;
s4, placing the bismuth oxide/polymer hybridization micro-nanofiber membrane obtained in the S3 into a muffle furnace, heating at a speed of 20 ℃/min, and keeping at 550 ℃ for 12 hours to obtain the bismuth oxide nanofiber membrane with a fiber diameter of 200-400 nm;
s5, weighing 28 absolute ethyl alcohol and 3g Polyacrylonitrile (PAN), and magnetically stirring uniformly to obtain a polymer solution E;
s6, weighing 4g of gadolinium nitrate (Gd (NO) 3 ) 3 •6H 2 O), adding 12g of water to completely dissolve the gadolinium oxide precursor solution, mixing the gadolinium oxide precursor solution with the stirred polymer solution E obtained in the step S5, and magnetically stirring the mixture for 20 hours;
s7, carrying out electrostatic spinning (air humidity 55% and temperature 27 ℃) on the precursor solution under 30kV voltage to obtain a gadolinium oxide/polymer hybrid nanofiber membrane;
s8, placing the gadolinium oxide/polymer hybrid nanofiber membrane obtained in the S7 in a muffle furnace environment at 600 ℃ overnight to remove the polymer in the nanofiber membrane, and obtaining the gadolinium oxide nanofiber membrane with the thickness of 100 microns and the fiber diameter of 200-800 nm;
s9, alternately stacking the bismuth oxide nanofiber membrane obtained in the S4 and the gadolinium oxide nanofiber membrane obtained in the S8 for 10 times to obtain the composite material with alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes, wherein the dispensing array is in a multi-array form, the hot rolling temperature is 100 ℃, and the dispensing number is 50/m 2 The dispensing shape is triangular.
The thickness of the composite material in this embodiment, in which bismuth oxide/gadolinium oxide nanofiber membranes are alternately stacked, is about 4 mm.
Examples
The preparation method of the composite material with alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes in the embodiment comprises the following steps:
s1, adding 2.5g of polyvinyl butyral (PVB) into 10g of DMF, and stirring for 2h at room temperature to prepare a 20%wt homogeneous polymer solution B;
s2, then 1 g bismuth nitrate (Bi (NO 3 ) 3 ) To 1.5g of a polymer solution B obtained from 20% by weight of S1,stirring for 6 hours at room temperature to obtain a precursor spinning solution C containing bismuth;
s3, injecting the precursor spinning solution C obtained in the step S2 into an injector, and carrying out electrostatic spinning under the process parameters of 80+/-5% of air humidity, 30+/-2 ℃ of temperature, 35kV of voltage, 1.5mL/h of pouring speed, 25cm of spinning distance, 15r/min of receiving device roller speed, 20cm/min of sliding table speed and 20m/S of air flow speed to obtain a bismuth oxide/polymer hybrid micro-nanofiber membrane with the diameter of 100-1000 nm, wherein bismuth sources are uniformly distributed in the interior and on the surface of the hybrid nanofiber;
s4, placing the bismuth oxide/polymer hybridization micro-nanofiber membrane obtained in the S3 into a muffle furnace, heating at a speed of 5 ℃/min, and keeping at 600 ℃ for 10 hours to obtain the bismuth oxide nanofiber membrane with a fiber diameter of 200-400 nm;
s5, weighing 28g of absolute ethyl alcohol and 4g of Polyacrylonitrile (PAN), and magnetically stirring uniformly to obtain a polymer solution E;
s6, weighing 3g of gadolinium nitrate (Gd (NO) 3 ) 3 •6H 2 O), adding 9g of water to completely dissolve the gadolinium oxide precursor solution, mixing the gadolinium oxide precursor solution with the stirred polymer solution E obtained in the step S5, and magnetically stirring the mixture for 48 hours;
s7, carrying out electrostatic spinning (air humidity is 45% and temperature is 20 ℃) on the precursor solution under 35kV voltage to obtain a gadolinium oxide/polymer hybrid nanofiber membrane;
s8, placing the gadolinium oxide/polymer hybrid nanofiber membrane obtained in the S7 in a muffle furnace environment at 580 ℃ overnight to remove the polymer in the nanofiber membrane, and obtaining the gadolinium oxide nanofiber membrane with the thickness of 200 microns and the fiber diameter of 200-800 nm;
s9, alternately stacking the bismuth oxide nanofiber membrane obtained in the S4 and the gadolinium oxide nanofiber membrane obtained in the S8 for 10 times to obtain the composite material with alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes, wherein the dispensing array is in a multi-array form, the hot rolling temperature is 120 ℃, and the dispensing number is 80/m 2 The dispensing shape is hexagonal.
The thickness of the composite material in this embodiment, in which bismuth oxide/gadolinium oxide nanofiber membranes are alternately stacked, is about 8 mm.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. The preparation method of the composite material with alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes is characterized by comprising the following steps of:
s1, dissolving a polymer A in N, N-dimethylformamide, and stirring for 2-12 hours at room temperature until a homogeneous system is formed, so as to obtain a polymer solution B;
s2, adding a bismuth source into the polymer solution B obtained in the step S1, and stirring for 2-6 hours at room temperature to obtain a clear and transparent bismuth-containing precursor spinning solution C;
s3, injecting the precursor spinning solution C obtained in the step S2 into an injector to perform air jet assisted electrostatic spinning, adding an air flow traction area in a classical jet flight area, greatly improving the injection rate of the precursor spinning solution C at the spray hole under the synergistic effect of a high-voltage electric field and high-speed air flow, stretching the precursor spinning solution C to form jet flow, and depositing the jet flow on a receiving device to obtain the bismuth oxide/polymer hybrid micro-nano fiber film with uniform appearance and no adhesion;
s4, calcining the bismuth oxide/polymer hybridization micro-nanofiber membrane obtained in the S3 as a template to obtain a bismuth oxide nanofiber membrane;
s5, dissolving the polymer D in absolute ethyl alcohol, and magnetically stirring uniformly to obtain a polymer solution E;
s6, dissolving a gadolinium source in water, mixing with the polymer solution E obtained in the S5, and carrying out ultrasonic magnetic stirring in a water bath for 20-48 hours to obtain a gadolinium-containing precursor solution F;
s7, taking aluminum foil as a receiving substrate, and carrying out electrostatic spinning on the precursor solution F obtained in the S6 at 15-100 kV voltage, 50-85% air humidity and 20-30 ℃ to obtain a gadolinium oxide/polymer hybrid nanofiber membrane;
s8, putting the gadolinium oxide/polymer hybrid nanofiber membrane obtained in the S7 in an environment with the temperature higher than the decomposition temperature of the polymer D and lower than the crystal phase transition temperature of the gadolinium oxide for overnight, and removing the polymer D in the gadolinium oxide/polymer hybrid nanofiber membrane to obtain the gadolinium oxide nanofiber membrane;
and S9, alternately stacking the bismuth oxide nanofiber membrane obtained in the step S4 and the gadolinium oxide nanofiber membrane obtained in the step S8 to obtain the composite material with alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes.
2. The method for preparing the composite material with alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes according to claim 1, wherein the polymer A in S1 is any one of polyethylene oxide, polyvinyl alcohol, polyvinyl butyral, polyvinylpyrrolidone and polyacrylonitrile.
3. The method for preparing the composite material with the alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes according to claim 1, wherein the bismuth source in S2 is any one of bismuth nitrate, bismuth isopropoxide, bismuth acetate, bismuth chloride octahydrate, bismuth subcarbonate and bismuth oxychloride; the mass ratio of the bismuth source to the polymer solution B in the S2 is 1: (1.5-5).
4. The method for preparing a composite material with alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes according to claim 1, wherein the electrostatic spinning environment in S3 is as follows: the air humidity is 55-85%, and the temperature is 15-35 ℃; the electrostatic spinning process parameters in the step S3 are as follows: the voltage is 20-120 kV, the pouring speed is 0.5-15 mL/h, the spinning distance is 15-60 cm, the sliding table speed is 1-200 cm/min, the roller speed of the receiving device is 10-50 r/min, and the air flow speed is 1-20 m/s.
5. The method for preparing the composite material with the alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes according to claim 1, wherein the temperature rising rate of calcination in S4 is 5-20 ℃/min, the highest calcination temperature is 400-670 ℃, and the calcination time is 10-20 h.
6. The method for preparing a composite material with alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes according to claim 1, wherein the polymer D in S5 is any one of polyethylene oxide, polyvinyl alcohol, polyvinyl butyral, polyvinylpyrrolidone and polyacrylonitrile.
7. The preparation method of the composite material with the alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes, which is characterized in that the mass fraction of the polymer D in the precursor solution F in the step S6 is 2-10%, and the mass fraction of the gadolinium source is 4-15%; and S6, the gadolinium source is any one of gadolinium nitrate, gadolinium acetate, gadolinium isopropoxide and gadolinium chloride hydrate.
8. The method for preparing the composite material with the alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes according to claim 1, wherein the composite material with the alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes in S9 is reinforced by a full contact lamination hot rolling technology of adhesive bonding.
9. The method for preparing the composite material with the alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes according to claim 8, wherein the technological parameters of the full-contact lamination hot rolling technology of the adhesive bonding are as follows: the dispensing array is in a multi-array form, the hot rolling temperature is 80-120 ℃, and the dispensing number is 30-100/m 2 The dispensing shape is any one of oval, triangle, square or hexagon.
10. A composite material based on an alternating stack of bismuth oxide/gadolinium oxide nanofiber membranes prepared by the method according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211030751.9A CN115467091B (en) | 2022-08-26 | 2022-08-26 | Bismuth oxide/gadolinium oxide nanofiber membrane alternately-stacked composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211030751.9A CN115467091B (en) | 2022-08-26 | 2022-08-26 | Bismuth oxide/gadolinium oxide nanofiber membrane alternately-stacked composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115467091A CN115467091A (en) | 2022-12-13 |
| CN115467091B true CN115467091B (en) | 2023-07-04 |
Family
ID=84369589
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211030751.9A Active CN115467091B (en) | 2022-08-26 | 2022-08-26 | Bismuth oxide/gadolinium oxide nanofiber membrane alternately-stacked composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115467091B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116870935A (en) * | 2023-04-27 | 2023-10-13 | 北京理工大学 | Modified bismuth oxychloride photocatalyst and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104645965B (en) * | 2015-03-18 | 2017-10-27 | 重庆文理学院 | One kind is used for light-catalysed bismuth titanium oxide nano-material and preparation method |
| KR101691039B1 (en) * | 2015-05-27 | 2016-12-29 | 국방과학연구소 | 3-dimenstinal nanofiber membrane and Method of manufacturing the same using liquid collector |
| CN110438664B (en) * | 2019-07-10 | 2021-10-26 | 吉林大学 | Bismuth tungstate/tungsten oxide/polymer composite nanofiber membrane for high-energy ray protection and preparation method thereof |
| AU2020103787A4 (en) * | 2020-11-30 | 2021-02-11 | Junada (qingdao) Technology Co., Ltd. | SiO2/PVDF-HFP Composite Fiber Membrane and Its Preparation Method and Application |
| KR20220089302A (en) * | 2020-12-21 | 2022-06-28 | 현대자동차주식회사 | Porous multi-metal oxide nanotube and method for manufacturing the same |
-
2022
- 2022-08-26 CN CN202211030751.9A patent/CN115467091B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN115467091A (en) | 2022-12-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115467091B (en) | Bismuth oxide/gadolinium oxide nanofiber membrane alternately-stacked composite material and preparation method thereof | |
| CN110258021B (en) | High-waterproof high-air-permeability nanofiber membrane and preparation method thereof | |
| CN110772661A (en) | Nontoxic environment-friendly solvent type double-layer nanofiber skin dressing and preparation method thereof | |
| CN109966538B (en) | Microcurrent wound healing-promoting antibacterial dressing and preparation method thereof | |
| EP3058597A1 (en) | Photovoltaic panel and method for producing same | |
| CN104018295A (en) | Infrared-visible light compatible invisible composite fibrous membrane and preparation method thereof | |
| CN112831855B (en) | Preparation method of core-shell structure tungsten/gadolinium oxide functional fiber for X, gamma ray protection | |
| CN106238726B (en) | A kind of flexible compound nano-silver thread and preparation method thereof | |
| CN106245126A (en) | A kind of luminous energy fiber and preparation method thereof | |
| CN105086472A (en) | Carbon-based porous flexible composite wave-absorbing material and preparation method thereof | |
| CN110924161A (en) | PVC polyester coated yarn based on anion generation principle and production process thereof | |
| CN211311787U (en) | High waterproof high ventilative nanofiber membrane | |
| CN102995389B (en) | Method for acquiring neutron protective fabric by doping rare earth element | |
| DE60011246T2 (en) | RADIOACTIVE MICROBALL AND MANUFACTURING METHOD THEREFOR | |
| CN102418156B (en) | Device for preparing nano-scale spiral filaments by electrostatic spinning method, and method | |
| CN110951187A (en) | Anion PVC polyester coated yarn for sun-shading material and production process thereof | |
| Saidin et al. | Fabrication and characterization of ZnO nanofibers by electrospinning | |
| CN115386973A (en) | Method for preparing side-by-side heterojunction nano fibers through single-source double-field electrostatic spinning | |
| CN111074357B (en) | Alumina fiber and preparation method thereof | |
| CN109125298B (en) | Isotropic medicine-containing fiber membrane, preparation method thereof and collector | |
| CN110840862B (en) | Near-infrared excited core-shell structure composite antibacterial nanofiber membrane and preparation method thereof | |
| CN107521201A (en) | A kind of novel C PP casting films and preparation method thereof | |
| KR102274598B1 (en) | Nanofiber Mask sheet composed of soluble and insoluble polymers | |
| CN111764161B (en) | Fiber with X and gamma protection function and preparation method thereof | |
| CN112647189A (en) | Antibacterial melt-blown fabric and preparation process thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |