CN102392321A - Preparation method of vulcanization gadolinium nanometer fiber - Google Patents

Preparation method of vulcanization gadolinium nanometer fiber Download PDF

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Publication number
CN102392321A
CN102392321A CN201110251435XA CN201110251435A CN102392321A CN 102392321 A CN102392321 A CN 102392321A CN 201110251435X A CN201110251435X A CN 201110251435XA CN 201110251435 A CN201110251435 A CN 201110251435A CN 102392321 A CN102392321 A CN 102392321A
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nanofiber
preparation
gadolinium
nanometer
nanometer fiber
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CN201110251435XA
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王进贤
董相廷
高萍
于文生
刘桂霞
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Changchun University of Science and Technology
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Changchun University of Science and Technology
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Abstract

The invention relates to a preparation method of a vulcanization gadolinium nanometer fiber and belongs to the technical field of preparation of nanometer materials. The invention aims at the problem that a vulcanization gadolinium nanometer particle and a nanometer rod are prepared in the prior art. A Gd2S3 nanometer fiber is prepared by adopting a method of combining an electro-spinning technology and a vulcanization technology. The preparation method comprise the two steps of: firstly, preparing a Gd2O3 nanometer fiber: preparing a PVP (Polyvinyl Pyrrolidone)/Gd(NO3)3 composite nanometer fiber by adopting the electro-spinning technology and then carrying out heat treatment to obtain the Gd2O3 nanometer fiber; and secondly, preparing the Gd2S3 nanometer fiber: vulcanizing the Gd2O3 nanometer fiber by adopting GS2 to obtain the pure-phased Gd2S3 nanometer fiber with a novel structure. The obtained Gd2S3 nanometer fiber has good crystal forms and also has a diameter of 105-133 nm and a length of greater than 100mu m. The vulcanization gadolinium nanometer fiber is a novel important functional material and is importantly applied in the fields of high-performance thermoelectric materials, ceramics, nontoxic and environmentally-friendly pigments, nanometer devices and the like. The preparation method is simple and easy, is suitable for batch production and has wide application prospect.

Description

A kind of preparation method of gadolinium sulfide nanofiber
Technical field
The present invention relates to the nano material preparation technical field, relate to a kind of preparation method of gadolinium sulfide nanofiber specifically.
Background technology
Nanofiber is meant the filamentary material that on the three dimensions yardstick of material, has bidimensional to be in nanoscale, and radial dimension is a nanometer scale usually, and length is then bigger.Because the radial dimension of nanofiber is little of nanometer scale; Demonstrate series of characteristics; The most outstanding is that specific area is big; Thereby its surface energy increases with active, and then produces small-size effect, surface or interfacial effect, quantum size effect, macro quanta tunnel effect etc., and therefore shows the specificity of a series of chemistry, physics (heat, light, sound, electricity, magnetic etc.) aspect.In the prior art, a lot of methods that prepare nanofiber are arranged, the method for for example reeling off raw silk from cocoons, template synthetic method, split-phase method and self-assembly method etc.In addition, also has arc evaporation, laser high temperature inustion, compound pyrolysismethod.These three kinds of methods in fact all are after at high temperature making compound (or simple substance) evaporation, make nanofiber or nanotube through pyrolysis (or directly condensation), from essence, all belong to the compound steam sedimentation.
Gadolinium sulfide Gd 2S 3Be a kind of important rare earth compound, thermoelectric material, environmental-friendly pigment and ceramic aspect important application is arranged.Gd 2S 3The research of nano material has caused showing great attention to of people, has adopted direct synthesis technique, microwave method, reducing process, sol-gel process and solvent-thermal method etc., has prepared Gd 2S 3Nano particle and nanometer rods.Gd 2S 3Nanofiber is a kind of important novel nano-material, will obtain important application in fields such as high performance thermoelectric material, pottery, asepsis environment-protecting pigment and nano-devices, has broad application prospects.At present, do not see that Gd is arranged 2S 3The relevant report of nanofiber.
The patent No. is the technical scheme that 1975504 United States Patent (USP) discloses a relevant electrospinning process (electrospinning); This method is a kind of effective ways that prepare continuous, as to have macro length micro nanometer fiber, is at first proposed in 1934 by Formhals.This method mainly is used for preparing high polymer nanometer fiber; It is characterized in that making charged Polymer Solution or melt in electrostatic field, to receive the traction of electrostatic force and spray, invest the receiving screen on opposite, thereby realize wire drawing by nozzle; Then; Solvent evaporation at normal temperatures, perhaps melt is cooled to normal temperature and solidifies, and obtains micro nanometer fiber.Over nearly 10 years, occurred adopting electrospinning process to prepare the technical scheme of inorganic compound such as oxidate nano fiber at the inorfil preparing technical field, described oxide comprises TiO 2, ZrO 2, Y 2O 3, Y 2O 3: RE 3+(RE 3+=Eu 3+, Tb 3+, Er 3+, Yb 3+/ Er 3+), NiO, Co 3O 4, Mn 2O 3, Mn 3O 4, CuO, SiO 2, Al 2O 3, V 2O 5, ZnO, Nb 2O 5, MoO 3, CeO 2, LaMO 3(M=Fe, Cr, Mn, Co, Ni, Al), Y 3Al 5O 12, La 2Zr 2O 7Deng metal oxide and composite oxide of metal.Employing electrostatic spinning techniques such as Wang Jinxian have prepared rare earth fluoride/rare earth oxyfluoride composite nano fibre (Chinese invention patent, application number: 200810050959.0).Electrospinning process can prepare big L/D ratio micrometer fibers or nanofiber continuously.At present, do not see have the electrostatic spinning technique of employing to prepare Gd 2S 3The relevant report of nanofiber.
When utilizing electrostatic spinning technique to prepare nano material, the composition of the kind of raw material, the molecular weight of high polymer templates, spinning solution, spinning process parameter and Technology for Heating Processing all have material impact to the pattern and the size of final products.The present invention adopts electrostatic spinning technique earlier, with gadolinium oxide Gd 2O 3Be raw material,, obtain Gd (NO with evaporating behind the dilute nitric acid dissolution 3) 3Crystal adds solvent N, and dinethylformamide DMF and high polymer templates polyvinylpyrrolidone PVP obtain carrying out electrostatic spinning behind the spinning solution, under the experiment condition of the best, prepare PVP/Gd (NO 3) 3Original nanofiber is heat-treated it in air, obtain Gd 2O 3Nanofiber is with carbon disulfide CS 2For vulcanizing agent vulcanizes, prepared the Gd of the pure phase of novel structure 2S 3Nanofiber.
Summary of the invention
Various in background technology prepare in the method for nanofiber, the shortcoming of the method for reeling off raw silk from cocoons be solution viscosity is required too harsh; The shortcoming of template synthetic method is to prepare the continuous fibers that the root root separates; Split-phase method and self-assembly method production efficiency are all lower; And the compound steam sedimentation is owing to the demand to high temperature, so process conditions are difficult to control.And the nanofiber major diameter of above-mentioned several method preparation is than little.Use electrostatic spinning technique in the background technology has prepared metal oxide, composite oxide of metal nanofiber and rare earth fluoride/rare earth oxyfluoride composite nano fibre.Prior art adopts direct synthesis technique, microwave method, reducing process, sol-gel process and solvent-thermal method etc., has prepared Gd 2S 3Nano particle and nanometer rods.For a kind of novel rare-earth sulfide nanometer fiber material is provided in the nanofiber field, we combine electrostatic spinning technique with sulfurization technology, have invented a kind of preparation Gd 2S 3The method of nanofiber.
The present invention is achieved in that and at first prepares the spinning solution with certain viscosity that is used for electrostatic spinning, uses electrostatic spinning technique and carries out electrostatic spinning, under the experiment condition of the best, prepares PVP/Gd (NO 3) 3Original nanofiber is heat-treated it in air, obtain Gd 2O 3Nanofiber is again with carbon disulfide CS 2For vulcanizing agent vulcanizes, prepared the Gd of the pure phase of novel structure 2S 3Nanofiber.The steps include:
(1) preparation Gd 2O 3Nanofiber
That use in the gadolinium source is gadolinium oxide Gd 2O 3, high polymer templates adopts polyvinylpyrrolidone PVP, and molecular weight is 90000, adopts N, and dinethylformamide DMF is a solvent.Take by weighing a certain amount of gadolinium oxide,, obtain Gd (NO with evaporating behind the dilute nitric acid dissolution 3) 3Crystal adds an amount of DMF solvent, takes by weighing a certain amount of PVP again and joins in the above-mentioned solution, stirs 3h in the room temperature lower magnetic force, and leaves standstill 2h, promptly forms spinning solution.The mass percent of this each part of spinning solution is: gadolinium nitrate content 9%, PVP content 9%, solvent DMF content 82%.The spinning solution for preparing is added in the liquid storage pipe of device for spinning, carry out electrostatic spinning, shower nozzle internal diameter 1mm; The angle of adjustment shower nozzle and horizontal plane is 30 °, applies the DC voltage of 15kV, solidifies apart from 15cm; 16～28 ℃ of room temperatures, relative humidity is 50%～70%, obtains PVP/Gd (NO 3) 3Composite nano fiber.With described PVP/Gd (NO 3) 3Composite nano fiber is put in the temperature programmed control stove and heat-treats, and heating rate is 1 ℃/min, at 700 ℃ of insulation 8h, is cooled to 200 ℃ with the speed of 1 ℃/min, naturally cools to room temperature with body of heater afterwards, obtains Gd 2O 3Nanofiber.
(2) preparation Gd 2S 3Nanofiber
Sulfuration reagent uses carbon disulfide CS 2With described Gd 2O 3Nanofiber is put into the corundum Noah's ark, and Noah's ark places in the vacuum tube furnace, when room temperature, feeds argon Ar 30min, discharges the air in the boiler tube, feeds CS when being warming up to 800 ℃ with the rate of heat addition of 5 ℃/min 2Gas, insulation 2h reduces to 200 ℃ with the rate of temperature fall of 5 ℃/min again, naturally cools to room temperature afterwards, obtains Gd 2S 3Nanofiber, diameter are 105～133nm, and length is greater than 100 μ m.
Prepared Gd in said process 2S 3Nanofiber has good crystal formation, and diameter is 105～133nm, and length has realized goal of the invention greater than 100 μ m.
Description of drawings
Fig. 1 is Gd 2S 3The XRD spectra of nanofiber;
Fig. 2 is Gd 2S 3The SEM photo of nanofiber, this figure double as Figure of abstract;
Fig. 3 is Gd 2S 3The EDS spectrogram of nanofiber;
Fig. 4 is Gd 2S 3The dielectric constant figure of nanofiber;
Fig. 5 is Gd 2S 3The dielectric loss figure of nanofiber;
Fig. 6 is Gd 2S 3The conductivity map of nanofiber.
The specific embodiment
The gadolinium oxide Gd that the present invention selected for use 2O 3Purity be 99.99%, polyvinylpyrrolidone PVP, molecular weight 90000, N, dinethylformamide DMF, carbon disulfide CS 2With nitric acid HNO 3Be commercially available analysis net product; Used glass apparatus, crucible and equipment are instrument and equipments commonly used in the laboratory.
Embodiment: take by weighing a certain amount of gadolinium oxide Gd 2O 3,, obtain Gd (NO with evaporating behind the dilute nitric acid dissolution 3) 3Crystal adds an amount of N, and dinethylformamide DMF solvent takes by weighing a certain amount of polyvinylpyrrolidone PVP again and joins in the above-mentioned solution, stirs 3h in the room temperature lower magnetic force, and leaves standstill 2h, promptly forms spinning solution.The mass percent of this each part of spinning solution is: gadolinium nitrate content 9%, PVP content 9%, solvent DMF content 82%.The spinning solution for preparing is added in the liquid storage pipe of device for spinning, carry out electrostatic spinning, shower nozzle internal diameter 1mm; The angle of adjustment shower nozzle and horizontal plane is 30 °, applies the DC voltage of 15kV, solidifies apart from 15cm; 16～28 ℃ of room temperatures, relative humidity is 50%～70%, obtains PVP/Gd (NO 3) 3Composite nano fiber.With described PVP/Gd (NO 3) 3Composite nano fiber is put in the temperature programmed control stove and heat-treats, and heating rate is 1 ℃/min, at 700 ℃ of insulation 8h, is cooled to 200 ℃ with the speed of 1 ℃/min, naturally cools to room temperature with body of heater afterwards, obtains Gd 2O 3Nanofiber.Sulfuration reagent uses carbon disulfide CS 2, with described Gd 2O 3Nanofiber is put into the corundum Noah's ark, and Noah's ark places in the vacuum tube furnace, when room temperature, feeds argon Ar 30min, discharges the air in the boiler tube, feeds CS when being warming up to 800 ℃ with the rate of heat addition of 5 ℃/min 2Gas, insulation 2h reduces to 200 ℃ with the rate of temperature fall of 5 ℃/min again, naturally cools to room temperature afterwards, obtains Gd 2S 3Nanofiber.Described Gd 2S 3Nanofiber has good crystallinity, the d value of its diffraction maximum and relative intensity and Gd 2S 3The listed d value of PDF standard card (45-0985) consistent with relative intensity, belong to rhombic system, see shown in Figure 1.Described Gd 2S 3The diameter of nanofiber is 105～133nm, and length is seen shown in Figure 2 greater than 100 μ m.Gd 2S 3Nanofiber is formed (the Au conductive layer of surface plating when Au comes from the SEM sample preparation) by Gd and S element, sees shown in Figure 3.Gd 2S 3The dielectric constant of nanofiber reduces with the increase of ac frequency, sees shown in Figure 4.Gd 2S 3Nanofiber does not almost have dielectric loss with the increase of ac frequency, sees shown in Figure 5.Gd 2S 3The electrical conductivity of nanofiber increases along with the increase of ac frequency, sees shown in Figure 6.
Certainly; The present invention also can have other various embodiments; Under the situation that does not deviate from spirit of the present invention and essence thereof; Those of ordinary skill in the art work as can make various corresponding changes and distortion according to the present invention, but these corresponding changes and distortion all should belong to the protection domain of the appended claim of the present invention.

Claims (4)

1. the preparation method of a gadolinium sulfide nanofiber is characterized in that, the method that adopts electrostatic spinning technique to combine with sulfurization technology; Polyvinylpyrrolidone PVP is a high polymer templates; Adopt N, dinethylformamide DMF is a solvent, and sulfuration reagent uses carbon disulfide CS 2, the preparation product is gadolinium sulfide Gd 2S 3Nanofiber the steps include:
(1) preparation Gd 2O 3Nanofiber
Take by weighing a certain amount of gadolinium oxide,, obtain Gd (NO with evaporating behind the dilute nitric acid dissolution 3) 3Crystal adds an amount of DMF solvent, takes by weighing a certain amount of PVP again and joins in the above-mentioned solution, stirs 3h in the room temperature lower magnetic force; And leave standstill 2h, and promptly forming spinning solution, the mass percent of this each part of spinning solution is: gadolinium nitrate content 9%, PVP content 9%; Solvent DMF content 82% adds the spinning solution for preparing in the liquid storage pipe of device for spinning, carries out electrostatic spinning, shower nozzle internal diameter 1mm; The angle of adjustment shower nozzle and horizontal plane is 30 °, applies the DC voltage of 15kV, solidifies apart from 15cm; 16～28 ℃ of room temperatures, relative humidity is 50%～70%, obtains PVP/Gd (NO 3) 3Composite nano fiber is with described PVP/Gd (NO 3) 3Composite nano fiber is put in the temperature programmed control stove and heat-treats, and heating rate is 1 ℃/min, at 700 ℃ of insulation 8h, is cooled to 200 ℃ with the speed of 1 ℃/min, naturally cools to room temperature with body of heater afterwards, obtains Gd 2O 3Nanofiber;
(2) preparation Gd 2S 3Nanofiber
Sulfuration reagent uses carbon disulfide CS 2, with described Gd 2O 3Nanofiber is put into the corundum Noah's ark, and Noah's ark places in the vacuum tube furnace, when room temperature, feeds argon Ar 30min, discharges the air in the boiler tube, feeds CS when being warming up to 800 ℃ with the rate of heat addition of 5 ℃/min 2Gas, insulation 2h reduces to 200 ℃ with the rate of temperature fall of 5 ℃/min again, naturally cools to room temperature afterwards, obtains Gd 2S 3Nanofiber, diameter are 105～133nm, and length is greater than 100 μ m.
2. the preparation method of a kind of gadolinium sulfide nanofiber according to claim 1 is characterized in that, that use in the gadolinium source is gadolinium oxide Gd 2O 3
3. the preparation method of a kind of gadolinium sulfide nanofiber according to claim 1 is characterized in that, high polymer templates is the polyvinylpyrrolidone of molecular weight Mr=90000.
4. the preparation method of a kind of gadolinium sulfide nanofiber according to claim 1 is characterized in that, sulfuration reagent uses carbon disulfide CS 2
CN201110251435XA 2011-08-30 2011-08-30 Preparation method of vulcanization gadolinium nanometer fiber Pending CN102392321A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106400202A (en) * 2016-07-04 2017-02-15 长春理工大学 A method of preparing copper sulphide nanometer fibers
CN109731147A (en) * 2018-12-24 2019-05-10 西安交通大学 Multi-functional PCS Hybrid nanofibers bio-medical method for producing elastomers and application
CN116180259A (en) * 2022-12-22 2023-05-30 南京航空航天大学 In-situ preparation method of gadolinium-containing carbon nano composite fiber for neutron shielding

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CN101863506A (en) * 2010-02-12 2010-10-20 长春理工大学 Rare earth sulfide with network nano structure and preparation method thereof
CN101805942A (en) * 2010-03-26 2010-08-18 福建师范大学 Rare earth doped yttrium oxide fluorescent nano-fiber and preparation method thereof
CN102041583A (en) * 2010-11-19 2011-05-04 长春理工大学 Method for preparing europium and fluorine-doped yttrium oxide nanofibres

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106400202A (en) * 2016-07-04 2017-02-15 长春理工大学 A method of preparing copper sulphide nanometer fibers
CN106400202B (en) * 2016-07-04 2018-09-07 长春理工大学 A method of preparing copper sulphide nano fiber
CN109731147A (en) * 2018-12-24 2019-05-10 西安交通大学 Multi-functional PCS Hybrid nanofibers bio-medical method for producing elastomers and application
CN116180259A (en) * 2022-12-22 2023-05-30 南京航空航天大学 In-situ preparation method of gadolinium-containing carbon nano composite fiber for neutron shielding
CN116180259B (en) * 2022-12-22 2024-01-30 南京航空航天大学 In-situ preparation method of gadolinium-containing carbon nano composite fiber for neutron shielding

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Application publication date: 20120328