CN105803579A - CaCu3Ti4O12 micro/nano-fibers and manufacturing method thereof - Google Patents

CaCu3Ti4O12 micro/nano-fibers and manufacturing method thereof Download PDF

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CN105803579A
CN105803579A CN201610209083.4A CN201610209083A CN105803579A CN 105803579 A CN105803579 A CN 105803579A CN 201610209083 A CN201610209083 A CN 201610209083A CN 105803579 A CN105803579 A CN 105803579A
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cacu
micro nanometer
nanometer fiber
solution
manufacture method
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杨文虎
孙蓉
于淑会
汪明
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
    • C04B35/62231—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on oxide ceramics
    • C04B35/62259—Fibres based on titanium oxide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • C04B2235/3234—Titanates, not containing zirconia
    • C04B2235/3236—Alkaline earth titanates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3281—Copper oxides, cuprates or oxide-forming salts thereof, e.g. CuO or Cu2O

Abstract

The invention relates to CaCu3Ti4O12 micro/nano-fibers. The CaCu3Ti4O12 micro/nano-fibers are mainly prepared from raw materials in parts by weight as follows: 6-30 parts of dimethylformamide, 1-5 parts of calcium nitrate tetrahydrate, 2-10 parts of cupric acetate monohydrate, 1-5 parts of polyvinylpyrrolidone, 0.2-1 part of a spinning aid and 3-15 parts of tetrabutyl titanate. Concentration and viscosity of a calcium source, a copper source and a titanium source in a CaCu3Ti4O12 precursor are selected and controlled, so that the length, particle size and orderliness of the CaCu3Ti4O12 micro/nano-fibers are effectively controlled.

Description

A kind of CaCu 3 Ti 4 O micro nanometer fiber and manufacture method thereof
Technical field
The present invention relates to a kind of CaCu 3 Ti 4 O micro nanometer fiber, the invention still further relates to the manufacture method of a kind of CaCu 3 Ti 4 O micro nanometer fiber, the invention belongs to inorganic fibers field.
Background technology
The material of high-k may be used for the manufacture of small size capacitive device, provide convenience for electronic device microminiaturization, therefore it has purposes widely in fields such as microresonator, wave filter, portable phones, plays more and more important effect in microelectronics industry.
In recent years with CaCu 3 Ti 4 O (CaCu3Ti4O12, CCTO) and for the ACu of representative3Ti4O12(A=Ca, Cd) is that giant dielectric ceramic material causes showing great attention to of scientist.Research shows: CaCu3Ti4O12Pottery not only has significantly high dielectric constant, but also has significant current-voltage nonlinear characteristics, and therefore it has potential application in multifunction electronic components and parts.
At present ceramic block, thin film or powder are concentrated mainly on for the research of CCTO, and the preparation and research for CCTO fiber is still little.The most important science and one of technical activity that nano-fiber material is world's materials science field in recent ten years is prepared by electrostatic spinning technique.Method of electrostatic spinning manufactures the advantages such as device is simple, spinning is with low cost, it is various to spin substance classes, technique is controlled with it, it has also become effectively one of main path preparing nano-fiber material.
Summary of the invention
An object of the present invention is to provide the CaCu 3 Ti 4 O micro nanometer fiber that a kind of size is more uniform, logic is good.
The two of the purpose of the present invention are to provide the manufacture method of a kind of CaCu 3 Ti 4 O micro nanometer fiber, and its technique is simple, mild condition, easily controllable, widely applicable.
CaCu 3 Ti 4 O micro nanometer fiber of the present invention, is mainly prepared by the raw material of following parts by weight and obtains:
Preferably, the diameter of described CaCu 3 Ti 4 O micro nanometer fiber is 200～2000 nanometers.
Preferably, the molecular weight of described polyvinylpyrrolidone is 1300000.
Preferably, described spin finish aid is acetic acid.
The manufacture method of CaCu 3 Ti 4 O micro nanometer fiber of the present invention, comprises the steps:
(1) by proportioning, dimethylformamide, four water-calcium nitrate and a water acetic acid copper are mixed, obtained solution A；
(2) by proportioning, polyvinylpyrrolidone, spin finish aid and butyl titanate are added to solution A, obtained solution B；
(3) electrostatic spinning process is adopted to prepare as-spun fibre described solution B；
(4) CaCu 3 Ti 4 O micro nanometer fiber is prepared with described as-spun fibre for raw material.
Preferably, in step (1), the preparation process of preparation solution A is: under agitation, dimethylformamide, four water-calcium nitrate and a water acetic acid copper are mixed by proportioning, isothermal reaction 1～5 hour at 20～50 DEG C, obtained solution A.
Preferably, in step (2), the preparation process of preparation solution B is: under agitation, by proportioning, polyvinylpyrrolidone, spin finish aid and butyl titanate are added to solution A, isothermal reaction 3～5 hours at 20～50 DEG C, obtained solution B, i.e. electrostatic spinning precursor solution.
Preferably, in step (4), the preparation process of CaCu 3 Ti 4 O micro nanometer fiber is: dried 12～18 hours at 50～70 DEG C by described as-spun fibre, heat to 900～1000 DEG C with the heating rate of 5～10 DEG C/min again, and constant temperature 2～5 hours, prepare CaCu 3 Ti 4 O micro nanometer fiber.
Preferably, in step (3), the voltage preparing the electrostatic spinning process of as-spun fibre is 15～30KV, and solidifying distance is 15～25 centimetres, and reception device is metal forming.
Preferably, in step (3), when preparing as-spun fibre, the rotating speed of receptor is 100～3000r/min, it is preferred to 140r/min or 2500r/min.
Compared with prior art, it is an advantage of the current invention that: it is four water-calcium nitrate that the present invention prepares the calcium source needed for CaCu 3 Ti 4 O micro nanometer fiber, copper source is a water acetic acid copper, and titanium source is butyl titanate, and the present invention is by selecting and regulating and controlling CaCu3Ti4O12Calcium source in presoma, Tong Yuan, the concentration in titanium source and viscosity, and then effectively control CaCu3Ti4O12The length of micro nanometer fiber, particle diameter and logic.
It addition, the present invention is when preparing CaCu 3 Ti 4 O micro nanometer fiber, by controlling the rotating speed of electrostatic spinning process receptor, effectively control CaCu further3Ti4O12The length of micro nanometer fiber, particle diameter and logic.
Additionally, this manufacturing approach craft is simple, mild condition, easily controllable, widely applicable.
Accompanying drawing explanation
Fig. 1 is the CaCu of the embodiment of the present invention 1 preparation3Ti4O12The SEM figure of micro nanometer fiber；
Fig. 2 is the CaCu of the embodiment of the present invention 1 preparation3Ti4O12The XRD figure of micro nanometer fiber；
Fig. 3 is the CaCu of the embodiment of the present invention 2 preparation3Ti4O12The SEM figure of micro nanometer fiber；
Fig. 4 is the CaCu of the embodiment of the present invention 3 preparation3Ti4O12The SEM figure of micro nanometer fiber；
Fig. 5 is the CaCu of the embodiment of the present invention 4 preparation3Ti4O12The SEM figure of micro nanometer fiber；
Fig. 6 is the CaCu of the embodiment of the present invention 5 preparation3Ti4O12The SEM figure of micro nanometer fiber.
Detailed description of the invention
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
Embodiment 1
The present embodiment CaCu3Ti4O12The preparation process of micro nanometer fiber is as follows:
(1) preparation of precursor sol
0.624g four water-calcium nitrate and 1.578g mono-water acetic acid copper are joined in the vial remained silent, the DMF (dimethylformamide) measuring 4ml joins in above-mentioned vial, after magneton is sufficiently stirred for two hours, now exist without obvious solid particle in vial, solution is dark green, obtains solution A.
The butyl titanate and the 0.1ml acetic acid (being about two) that take 3.6ml join in above-mentioned solution A, wherein the effect of acetic acid is the hydrolysis suppressing butyl titanate, magnetic agitation is after two hours afterwards, weigh 0.4g polyvinylpyrrolidone (PVP, mol, wt=1300000) join in above-mentioned mixed solution, at room temperature stir, now obtain the electrostatic spinning precursor solution solution B with certain viscosity.
Chemical drugs used in the present embodiment is traditional Chinese medicines reagent, and purity is analytical pure；Wherein selection PVP as the reason of spinning carrier is: it has good dissolubility in DMF kind, and all has good compatibility with the general precursor solution containing metal ion.
(2) electrostatic spinning process
Electrostatic spinning the whole series experimental provision is placed in lucite control box, is beneficial to control environment temperature and humidity and reduce outside contamination.
The positive pole of high voltage power supply connects a red chuck as anode, and the receptor (namely receiving device is aluminium foil) of aluminium-foil paper cladding is then connected with the negative pole of high voltage power supply as negative electrode.With the plastic injector of insulation as the container carrying precursor liquid, fixing distance between spinning head and receptor is 20cm, the specification 22G of spinning head, internal diameter 0.4mm, and external diameter 0.7mm sets the just extremely 25kv of high voltage power supply, and negative pole is-2kv.After connecting high-tension electricity, the rotating speed of receptor is set to 140r/min, when logical upper high-tension electricity, can obtain the CCTO gelatinous fibre of certain orientation at aluminium-foil paper, maintain this experiment condition until precursor solution is completely converted into CCTO gelatinous fibre as-spun fibre.
(3) synthesis of Ca-Ti ore type CCTO fiber
After spinning terminates, the CCTO gelatinous fibre taken off from aluminium-foil paper is put in baking oven, under 60 DEG C of conditions, dry 12h, make the solvent in presoma fully volatilize.Afterwards CCTO fiber is put into 950 DEG C of sintering in Muffle furnace, with the slow ramp of 10 DEG C/min to 950 DEG C, and stops 2h when 950 DEG C, naturally cool to room temperature afterwards, namely obtain Ca-Ti ore type CCTO fiber.
Embodiment 2
The present embodiment CaCu3Ti4O12The preparation process of micro nanometer fiber is as follows:
(1) preparation of precursor sol
0.624g four water-calcium nitrate and 1.578g mono-water acetic acid copper are joined in the vial remained silent, the DMF measuring 4ml joins in vial, after magneton is sufficiently stirred for two hours, now exists without obvious solid particle in vial, solution is dark green, obtains solution A.
The butyl titanate and the 0.1ml acetic acid (being about two) that take 3.6ml join in above-mentioned solution A, wherein the effect of acetic acid is the hydrolysis suppressing butyl titanate, magnetic agitation is after two hours afterwards, weigh 0.5g polyvinylpyrrolidone (PVP, mol, wt=1300000) join in above-mentioned mixed solution, at room temperature stir, now obtain the electrostatic spinning precursor solution solution B with certain viscosity.
Chemical drugs used in the present embodiment is traditional Chinese medicines reagent, and purity is analytical pure；Wherein selection PVP as the reason of the carrier of spinning is: it has good dissolubility at DMF, and all has good compatibility with the general precursor solution containing metal ion.
(2) electrostatic spinning process
Electrostatic spinning the whole series experimental provision is placed in lucite control box, is beneficial to control environment temperature and humidity and reduce outside contamination.
The positive pole of high voltage power supply connects a red chuck as anode, and the receptor (namely receiving device is aluminium foil) of aluminium-foil paper cladding is then connected with the negative pole of high voltage power supply as negative electrode.With the plastic injector of insulation as the container carrying precursor liquid, fixing distance between spinning head and receptor is 20cm, the specification 22G of spinning head, internal diameter 0.4mm, and external diameter 0.7mm sets the just extremely 25kv of high voltage power supply, and negative pole is-2kv.After connecting high-tension electricity, the rotating speed of receptor is set to 140r/min, when logical upper high-tension electricity, can obtain the CCTO gelatinous fibre of certain orientation at aluminium-foil paper, maintain this experiment condition until precursor solution is completely converted into CCTO gelatinous fibre as-spun fibre.
(3) synthesis of Ca-Ti ore type CCTO fiber
The CCTO gelatinous fibre taken off from aluminium-foil paper is put in baking oven after terminating by spinning, dries 12h, make the solvent in presoma fully volatilize under 60 DEG C of conditions.Afterwards CCTO fiber is put into 950 DEG C of sintering in Muffle furnace, with the slow ramp of 10 DEG C/min to 950 DEG C, and stops 2h when 950 DEG C, naturally cool to room temperature afterwards, namely obtain Ca-Ti ore type CCTO fiber.
Embodiment 3
The present embodiment CaCu3Ti4O12The preparation process of micro nanometer fiber is as follows:
(1) preparation of precursor sol
0.832g four water-calcium nitrate and 2.104g mono-water acetic acid copper are joined in the vial remained silent, the DMF measuring 4ml joins in vial, after magneton is sufficiently stirred for two hours, now exists without obvious solid particle in vial, solution is dark green, obtains solution A.
The butyl titanate and the 0.1ml acetic acid (being about two) that take 4.8ml join in above-mentioned solution A, wherein the effect of acetic acid is the hydrolysis suppressing butyl titanate, magnetic agitation is after two hours afterwards, weigh 0.9g polyvinylpyrrolidone (PVP, mol, wt=1300000) join in above-mentioned mixed solution, at room temperature stir, now obtain the electrostatic spinning precursor solution solution B with certain viscosity.
Chemical drugs used in the present embodiment is traditional Chinese medicines reagent, and purity is analytical pure；Wherein selection PVP as the reason of spinning carrier is: it has good dissolubility in DMF kind, and all has good compatibility with the general precursor solution containing metal ion.
(2) electrostatic spinning process
Electrostatic spinning the whole series experimental provision is placed in lucite control box, is beneficial to control environment temperature and humidity and reduce outside contamination.
The positive pole of high voltage power supply connects a red chuck as anode, and the receptor (namely receiving device is aluminium foil) of aluminium-foil paper cladding is then connected with the negative pole of high voltage power supply as negative electrode.With the plastic injector of insulation as the container carrying precursor liquid, fixing distance between spinning head and receptor is 20cm, the specification 22G of spinning head, internal diameter 0.4mm, and external diameter 0.7mm sets the just extremely 25kv of high voltage power supply, and negative pole is-2kv.After connecting high-tension electricity, the rotating speed of receptor is set to 140r/min, when logical upper high-tension electricity, can obtain the CCTO gelatinous fibre of certain orientation at aluminium-foil paper, maintain this experiment condition until precursor solution is completely converted into CCTO gelatinous fibre as-spun fibre.
(3) synthesis of Ca-Ti ore type CCTO fiber
After spinning terminates, the CCTO gelatinous fibre taken off from aluminium-foil paper is put in baking oven, under 60 DEG C of conditions, dry 12h, make the solvent in presoma fully volatilize.Afterwards CCTO fiber is put into 950 DEG C of sintering in Muffle furnace, with the slow ramp of 10 DEG C/min, stops 2h when being warmed up to 950 DEG C, naturally cool to room temperature afterwards, namely obtain Ca-Ti ore type CCTO fiber.
Embodiment 4
The present embodiment CaCu3Ti4O12The preparation process of micro nanometer fiber is as follows:
(1) preparation of precursor sol
0.624g four water-calcium nitrate and 1.578g mono-water acetic acid copper are joined in the vial remained silent, the DMF measuring 4ml joins in vial, after magneton is sufficiently stirred for two hours, now exists without obvious solid particle in vial, solution is dark green, obtains solution A.
The butyl titanate and the 0.1ml acetic acid (being about two) that take 3.6ml join in above-mentioned solution A, wherein the effect of acetic acid is the hydrolysis suppressing butyl titanate, magnetic agitation is after two hours afterwards, weigh 0.4g polyvinylpyrrolidone (PVP, mol, wt=1300000) join in above-mentioned mixed solution, at room temperature stir, now obtain the electrostatic spinning precursor solution solution B with certain viscosity.
Chemical drugs used in the present embodiment is traditional Chinese medicines reagent, and purity is analytical pure；Wherein selection PVP as the reason of spinning carrier is: it has good dissolubility in DMF kind, and all has good compatibility with the general precursor solution containing metal ion.
(2) electrostatic spinning process
Electrostatic spinning the whole series experimental provision is placed in lucite control box, is beneficial to control environment temperature and humidity and reduce outside contamination.
The positive pole of high voltage power supply connects a red chuck as anode, and the receptor of aluminium-foil paper cladding is then connected with the negative pole of high voltage power supply as negative electrode.With the plastic injector of insulation as the container carrying precursor liquid, fixing distance between spinning head and receptor is 20cm, the specification 22G of spinning head, internal diameter 0.4mm, and external diameter 0.7mm sets the just extremely 25kv of high voltage power supply, and negative pole is-2kv.After connecting high-tension electricity, the rotating speed of receptor is set to 2500r/min, when logical upper high-tension electricity, can obtain the CCTO gelatinous fibre of certain orientation at aluminium-foil paper, maintain this experiment condition until precursor solution is completely converted into CCTO gelatinous fibre as-spun fibre.
(3) synthesis of Ca-Ti ore type CCTO fiber
After spinning terminates, the CCTO gelatinous fibre taken off from aluminium-foil paper is put in baking oven, dry 12h under 60 DEG C of conditions, make the solvent in presoma fully volatilize.Afterwards CCTO fiber is put into 950 DEG C of sintering in Muffle furnace, adopts the slow ramp of 10 DEG C/min, stop 2h during to 950 DEG C, naturally cool to room temperature afterwards, namely obtain Ca-Ti ore type CCTO fiber.
Embodiment 5
The present embodiment CaCu3Ti4O12The preparation process of micro nanometer fiber is as follows:
(1) preparation of precursor sol
0.416g four water-calcium nitrate and 1.052g mono-water acetic acid copper are joined in the vial remained silent, the DMF measuring 4ml joins in vial, after magneton is sufficiently stirred for two hours, now exists without obvious solid particle in vial, solution is dark green, obtains solution A.
The butyl titanate and the 0.1ml acetic acid (being about two) that take 2.4ml join in above-mentioned solution A, wherein the effect of acetic acid is the hydrolysis suppressing butyl titanate, magnetic agitation is after two hours afterwards, weigh 0.4g polyvinylpyrrolidone (PVP, mol, wt=1300000) join in above-mentioned mixed solution, at room temperature stir, now obtain the electrostatic spinning precursor solution solution B with certain viscosity.
Chemical drugs used in the present embodiment is traditional Chinese medicines reagent, and purity is analytical pure；Wherein selection PVP as the reason of spinning carrier is: it has good dissolubility in DMF kind, and all has good compatibility with the general precursor solution containing metal ion.
(2) electrostatic spinning process
Electrostatic spinning the whole series experimental provision is placed in lucite control box, is beneficial to control environment temperature and humidity and reduce outside contamination.
The positive pole of high voltage power supply connects a red chuck as anode, and the receptor of aluminium-foil paper cladding is then connected with the negative pole of high voltage power supply as negative electrode.With the plastic injector of insulation as the container carrying precursor liquid, fixing distance between spinning head and receptor is 20cm, the specification 22G of spinning head, internal diameter 0.4mm, and external diameter 0.7mm sets the just extremely 25kv of high voltage power supply, and negative pole is-2kv.After connecting high-tension electricity, the rotating speed of receptor is set to 140r/min, when logical upper high-tension electricity, can obtain the CCTO gelatinous fibre of certain orientation at aluminium-foil paper, maintain this experiment condition until precursor solution is completely converted into CCTO gelatinous fibre as-spun fibre.
(3) synthesis of Ca-Ti ore type CCTO fiber
The CCTO gelatinous fibre taken off from aluminium-foil paper is put in baking oven after terminating by spinning, dries 12h, make the solvent in presoma fully volatilize under 60 DEG C of conditions.Afterwards CCTO fiber is put into 950 DEG C of sintering in Muffle furnace, adopts the slow ramp of 10 DEG C/min, stop 2h during to 950 DEG C, naturally cool to room temperature afterwards, namely obtain Ca-Ti ore type CCTO fiber.
Fig. 1 is the CaCu of embodiment 1 preparation3Ti4O12The SEM figure of micro nanometer fiber.As can be seen from Figure 1: CaCu3Ti4O12Exist with fibers form and size is homogeneous, but can be seen that its logic is good not enough, CaCu3Ti4O12The diameter of micro nanometer fiber is about 200～500 ran.
Fig. 2 is the CaCu of embodiment 1 preparation3Ti4O12The XRD figure of micro nanometer fiber, it can be seen that, although have an impurity but and inconspicuous, it is believed that CaCu3Ti4O12The structure of fiber is pure CaCu3Ti4O12Phase.
Fig. 3 is the CaCu of embodiment 2 preparation3Ti4O12The SEM figure of micro nanometer fiber, it will thus be seen that CaCu3Ti4O12Exist for fibers form, and diameter is about 400～700 ran.Relative to embodiment 1, it can be deduced that such conclusion: the amount (namely improving solution concentration) improving polyvinylpyrrolidone (PVP, mol, wt=1300000) can improve CaCu3Ti4O12The particle diameter of micro nanometer fiber.
Fig. 4 is the CaCu of embodiment 3 preparation3Ti4O12The SEM figure of micro nanometer fiber, it will thus be seen that CaCu3Ti4O12Existing for fibers form, diameter is about 700～2000 nanometers.Contrast and embodiment 2 and embodiment 1, it will thus be seen that the concentration improving solution viscosity and CCTO presoma can improve CaCu3Ti4O12The particle diameter of micro nanometer fiber.
Fig. 5 is the CaCu of embodiment 4 preparation3Ti4O12The SEM figure of micro nanometer fiber, it will thus be seen that CaCu3Ti4O12For fibers form exist, embodiment 4 (receptor rotating speed is 2500r/min) logic than embodiment 1 (receptor rotating speed is 140r/min) time will be good many, diameter is about 200～500 nanometers.
Fig. 6 is the CaCu of embodiment 5 preparation3Ti4O12The SEM figure of micro nanometer fiber, it will thus be seen that CaCu3Ti4O12Existing for fibers form, but length is shorter, diameter is about 200～500 nanometers.Compared to embodiment 1 and embodiment 2, it can be deduced that such conclusion: when rotating speed and solution viscosity are certain, after CCTO precursor concentration reaches finite concentration, CaCu3Ti4O12Micro nanometer fiber reaches higher value (reaching maroscopic quantity)；When CCTO precursor concentration is below finite concentration, along with the increase of CCTO precursor concentration, CaCu3Ti4O12Micro nanometer fiber is more long；Because when CCTO precursor concentration is relatively low, in CCTO gelatinous fibre, CCTO presoma cannot well connect, and after CCTO gelatinous fibre puts in Muffle furnace 950 DEG C of sintering, Organic substance can be burned off, and CCTO cannot connect together and form longer CaCu3Ti4O12Micro nanometer fiber.
Above content is only presently preferred embodiments of the present invention, for those of ordinary skill in the art, according to the thought of the present invention, all will change in specific embodiments and applications, and this specification content should not be construed as limitation of the present invention.

Claims (10)

1. a CaCu 3 Ti 4 O micro nanometer fiber, it is characterised in that mainly prepared by the raw material of following parts by weight and obtain:
2. CaCu 3 Ti 4 O micro nanometer fiber as claimed in claim 1, it is characterised in that: the diameter of described CaCu 3 Ti 4 O micro nanometer fiber is 200～2000 nanometers.
3. CaCu 3 Ti 4 O micro nanometer fiber as claimed in claim 1 or 2, it is characterised in that: the molecular weight of described polyvinylpyrrolidone is 1300000.
4. CaCu 3 Ti 4 O micro nanometer fiber as claimed in claim 1 or 2, it is characterised in that: described spin finish aid is acetic acid.
5. the manufacture method of the CaCu 3 Ti 4 O micro nanometer fiber as described in any one of Claims 1 to 4, it is characterised in that comprise the steps:
(1) by proportioning, dimethylformamide, four water-calcium nitrate and a water acetic acid copper are mixed, obtained solution A；
(2) by proportioning, polyvinylpyrrolidone, spin finish aid and butyl titanate are added to solution A, obtained solution B；
(3) electrostatic spinning process is adopted to prepare as-spun fibre described solution B；
(4) CaCu 3 Ti 4 O micro nanometer fiber is prepared with described as-spun fibre for raw material.
6. manufacture method as claimed in claim 5, it is characterized in that: in step (1), the preparation process of preparation solution A is: under agitation, by proportioning, dimethylformamide, four water-calcium nitrate and a water acetic acid copper are mixed, isothermal reaction 1～5 hour at 20～50 DEG C, obtained solution A.
7. manufacture method as claimed in claim 5, it is characterized in that: in step (2), the preparation process of preparation solution B is: under agitation, by proportioning, polyvinylpyrrolidone, spin finish aid and butyl titanate are added to solution A, isothermal reaction 3～5 hours at 20～50 DEG C, obtained solution B.
8. manufacture method as claimed in claim 5, it is characterized in that, in step (4), the preparation process of CaCu 3 Ti 4 O micro nanometer fiber is: dried 12～18 hours at 50～70 DEG C by described as-spun fibre, heat to 900～1000 DEG C with the heating rate of 5～10 DEG C/min again, and constant temperature 2～5 hours, prepare CaCu 3 Ti 4 O micro nanometer fiber.
9. manufacture method as claimed in claim 5, it is characterised in that: in step (3), the voltage preparing the electrostatic spinning process of as-spun fibre is 15～30KV, and solidifying distance is 15～25 centimetres, and reception device is metal forming.
10. manufacture method as claimed in claim 5, it is characterised in that: in step (3), when preparing as-spun fibre, the rotating speed of receptor is 100～3000r/min, it is preferred to 140r/min or 2500r/min.
CN201610209083.4A 2016-04-06 2016-04-06 CaCu3Ti4O12 micro/nano-fibers and manufacturing method thereof Pending CN105803579A (en)

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CN106751244A (en) * 2016-12-06 2017-05-31 绥化学院 A kind of preparation method of the polyvinylidene fluoride nanometer composite of functionalization ceramic fibre filling
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CN108017913A (en) * 2018-01-09 2018-05-11 哈尔滨理工大学 A kind of silicon rubber base direct current cables APPENDIX MATERIALSThe and preparation method thereof
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Application publication date: 20160727