CN105295303A - Composite bulk material of resin, ferrite and MXenes and preparation method and application thereof - Google Patents
Composite bulk material of resin, ferrite and MXenes and preparation method and application thereof Download PDFInfo
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- CN105295303A CN105295303A CN201510757001.5A CN201510757001A CN105295303A CN 105295303 A CN105295303 A CN 105295303A CN 201510757001 A CN201510757001 A CN 201510757001A CN 105295303 A CN105295303 A CN 105295303A
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Abstract
The invention discloses a composite bulk material of resin, ferrite and MXenes. Ferrite molecules are dispersed in a laminated structure of the MXenes to form powder particles, and the powder particles are evenly dispersed in the resin to form the bulk material. On the one hand, the composite bulk material has the advantages of the ferrite material and the advantages of the MXenes, has good conductivity, can still keep certain conductivity when the temperature is lower than 260 K, and meanwhile has good impedance matching performance, and therefore the composite bulk material can be applied as a wave-absorbing material, and is especially suitable for being applied to the low-temperature condition; on the other hand, the resin is introduced into the composite bulk material, the powder particles are evenly dispersed in the resin, the composite bulk material is formed and has the advantage of being easy to form and process, and meanwhile, due to the fact that the curing temperature of the resin is lower than the sintering temperature of the powder particles, the problem that the powder particles are easily oxidized at high temperature is effectively solved.
Description
Technical field
The present invention relates to technical field of composite materials, particularly the composite block material of a kind of resin, ferrite and MXenes, its preparation method and application.
Background technology
Along with the develop rapidly of electronics and information industry, the mobile communication equipments such as notebook computer, mobile phone, panel computer are popularized in a large number, and nearly cover is to each family, and becomes a part indispensable in daily life.But along with the sharply increase of these Wireless Telecom Equipments and high-frequency electron device consumption, electromagnetic interference (Electromagneticinterference) phenomenon and electromagnetic pollution problem also grow in intensity.
Ferrite Material is two composite dielectrics, not only there is the ohmic loss of general dielectric material, polarization loss, ion and electron resonance loss, also there is the distinctive domain wall resonance loss of ferrite, magnetic moment natural resonance loss and particle resonant loss, therefore, ferrite, as a kind of absorbing material, is widely used in all kinds of electronic devices and components such as electromagnetism interference antenna, wave filter, inductance element.But, the density ratio of Ferrite Material is higher, to change isolator under low temperature, and there is the brittleness problems of stupalith, these factors limit its application at special dimensions (aerospace) such as high-order mode resorber (accelerator) and space weapon equipments.
Two dimension transition metal carbide or carbonitride, i.e. MXenes are the type materials with two-dimentional laminated structure found cooperation in 2011 by people such as Gogotsi and Barsoum, general available M
n+1x
nt
zrepresent, wherein M refers to magnesium-yttrium-transition metal (as Ti, Zr, Hf, V, Nb, Ta, Cr, Sc etc.), and X refers to C or/and N, n are generally 1-3, T
zrefer to that surface group is (as O
2-, OH
-, F
-, NH
3, NH
4 +deng).At present, MXenes generally derives from ternary layered sintering metal M
n+1aX
nphase (M is transition metal, and A is main group element, and X is that C and/or N, n are generally 1 ~ 3, is called for short MAX phase), obtains by combining more weak A bit element (as atoms such as Al, Si) extraction in MAX phase.Similar with Graphene, MXenes has excellent electrical and thermal conductivity, higher specific surface area.And MXenes is natural has multilayer " class accordion " structure, not easily reunites; Meanwhile, its surface with the group that enriches can as iron/isoionic suitable ligand of nickel/cobalt.
At present, the applied research for two-dimentional transition metal carbide or carbon nitride material mainly concentrates on energy storage direction.Such as, M.Naguib etc. report V
2cT
zelectrode materials as lithium ion battery has excellent specific discharge capacity, and still can keep satisfactory stability (M.Naguibetal, J.Am.Chem.Soc., 2013,135,15966) 140 times in discharge and recharge later.The people such as M.Lukatskaya then have studied lamella Ti
3c
2t
xas the electrode active material of ultracapacitor, find to work as 1MMgSO
4as ionogen, use 1Ag
-1during test current, the ratio capacitance of this material is up to 400Fcm
-3(M.Lukatskaya, etal, Science, 2013,341,1502).Recently, the recent posts display that M.W.Barsoum etc. deliver on Nature, with claylike Ti
3c
2t
zthe ultracapacitor of preparation has 900F/cm
3volumetric capacitance, this value is ruthenium oxide hydration (1000-1500F/cm closely
3), (M.Ghidiuetal, Nature, 2014,516,78).In other Application Areass, Zhou Aiguo etc. have studied the Ti through NaOH activation
3c
2tz nanometer sheet, to the absorption behavior of heavy metal in sewage, finds in 323K, pH=5.8 ~ 6.2 time, and the maximum adsorption capacity of this material to Pb (II) can reach 140mgg
-1(Q.Pengetal, J.Am.Chem.Soc., 2014,136,4113).The solid support material that MXenes also can be used as Pt nanoparticle plays katalysis (Y.P.Gaoetal, SolidStateSciences, 2014,35,62.) at fuel cell, its same Cu
2the matrix material of O can promote the decomposition (X.H.Xieetal, Chem.Commun., 2013,49,10112.) of ammoniumper chlorate.In addition the application aspect of MXenes in field of polymer technology, polymethyl acrylic acid N, N-dimethylamino ethyl ester (PDMAEMA) branch is linked V by Chen etc.
2cT
zin nanometer sheet, can obtain and there is CO
2the hybrid material (Chen, J., etal., Chem.Commun., 2015,51,314) of temperature dual stimuli responsive performance.
It is strong that macromolecule resin material has plasticity-, and production cost is low, is easy to the features such as forming process, shows good application prospect in lightweight electromagnetic shielding material field.Such as, polyetherimide (PEI) is a kind of high-performance polymer resin, it not only has high second-order transition temperature, also has excellent flame retardant properties and mechanical property, is therefore that the best matrix preparing high-performance polymer composite microporous foaming electromagnetic shielding material is selected.
Summary of the invention
The invention provides the composite block material of a kind of resin, ferrite and MXenes, be made up of resin and powder granule, and powder granule is dispersed in resin; Described powder granule is made up of ferrite and MXenes, and ferrite molecular dispersion is in the laminated structure of MXenes.
In described composite block material, the quality of resin and powder granule is adjustable, and according to actual needs, the percentage composition that the quality of resin accounts for described composite block material total mass is adjustable in 5% ~ 99.8% scope.
In described powder granule, the quality of Ferrite Material and MXenes is adjustable, according to actual needs, the percentage composition that the quality of MXenes accounts for described powder granule total mass is adjustable in 0.1 ~ 99.9% scope, and the degree that Ferrite Material accounts for described powder granule total mass is adjustable in 0.1 ~ 99% scope.
Described Ferrite Material is not limit, and comprising chemical formula is MeFe
2o
4, AFe
12o
19, R
3fe
5o
12etc. the Ferrite Material of system.Wherein Me element can be the combination of a kind of element in the elements such as Ni, Mn, Zn, Cu, Co, Fe, Li, Mg, Cr, Ca, Ba or two or more element; Element A can be the combination of a kind of element in the elements such as Ba, Co, Ni, Mn, Zn, Cu, Fe, Li, Mg, Cr, Ca or two or more element; R element can be the combination of a kind of element in the rare earth elements such as Y, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or two or more element.
The preparation method of described MXenes does not limit, and can pass through ternary layered sintering metal M
n+1aX
ncombine more weak A bit element (as atoms such as Al, Si) in phase (M is transition metal, and A is main group element, and X is that C and/or N, n are generally 1 ~ 3) extract out and obtain.
Described resin includes but not limited to one or more the arbitrary combination in polyimide resin (PEI), polystyrene resin, polymethacrylate resin, polycarbonate, acrylic resin, epoxy resin, resol etc.
Present invention also offers a kind of method preparing described composite block material, the method comprises the steps:
Resin is dissolved in solvent, configuration resin solution; Described powder granule is scattered in homogeneous solvent, obtains powder granule solution; Resin solution is mixed with powder granule dissolution homogeneity, standing, deaeration is also evenly coated on carrier surface, solvent evaporates under suitable temperature and humidity condition, excess of solvent is removed in cleaning after cured, then vacuum-drying 0.1 ~ 100h at 30 ~ 200 DEG C, can obtain described composite block material.
The preparation method of described powder granule does not limit, and comprises chemical coprecipitation, solid-phase ball milling method, sol-gel method, self-propagating combustion, co-precipitation-hydrothermal method etc.
Described solvent is not limit, and comprises dimethyl formamide (DMF), toluene or dimethylbenzene etc.
Described drying temperature is preferably 80 ~ 150 DEG C.
As a kind of preferred structure, in described powder granule, ferrite molecule growth in situ is in the laminated structure of MXenes.For this reason, the present invention adopts coprecipitation method to prepare the powder granule with this preferred structure, specifically comprises the steps:
Appropriate MXenes is dissolved in dispersion liquid, obtained finely dispersed MXenes solution;
The preparation of raw material of Ferrite Material is carried out according to the amount of substance of respective element in Ferrite Material chemical formula;
The raw material of Ferrite Material is mixed with MXenes solution, obtains mixing solutions one;
Mixing solutions one is instilled in basic solution, obtain mixing solutions two, the pH value regulating mixing solutions two is 7 ~ 12, and mixing solutions two reacts at 20 ~ 90 DEG C of temperature under agitation, reaction product cleaning, oven dry, obtain the powder granule of Ferrite Material and MXenes.
Described dispersion liquid is not limit, and includes but not limited to a kind of solution etc. of sodium lignosulfonate, Sodium dodecylbenzene sulfonate or oleyl amine.
The described reaction times is preferably 10min ~ 120min.
Described basic solution is not limit, and comprises sodium hydroxide, potassium hydroxide, ammonia soln etc.
In sum, Ferrite Material and MXenes are carried out compound by the present invention, nano level ferrite molecular dispersion forms powder granule in the MXenes laminated structure of submicron order, and this powder granule is dispersed in resin and forms composite block material, and this composite block material tool has the following advantages:
(1) advantage of Ferrite Material and MXenes is had concurrently.On the one hand, MXenes laminated structure forms conductive network, makes this composite block material have good conductivity, when temperature still can keep certain specific conductivity lower than during 260K; On the other hand, this composite block material has good impedance matching performance.Therefore, this composite block material can be applied to as absorbing material in all kinds of electronic devices and components such as electromagnetism interference antenna, wave filter, inductance element, is particularly useful for applying under cryogenic.Such as, can work under the liquid nitrogen cryogenics of 80K, thus can be applied in the free-electron laser light source based on energy recovery type accelerator, meet the low temperature requirements of such accelerator to high-order mode suppressor absorbing material; Can be applied in deep sea submarine Radome part, meet when submarine is in deep sea low temperature, the absorbing material in Radome part normally can play purposes; Can be applied in outer space electromagnetic shielding device, meet when electromagnetic shielding device is in outer space low temperature, absorbing material wherein normally can play purposes; And being applied in other such as electron devices, in anti-EMI materials etc., meet when such device is in normal temperature or low temperature, absorbing material wherein normally can play purposes, to meet the requirement in actual production life under special conditions.
(2) with powder granule is carried out sintering and compared with the composite block material obtained, composite block material of the present invention introduces resin, powder granule is dispersed in resin and is formed, have the advantages that to be easy to forming process on the one hand, on the other hand because the solidification value of resin is low compared with the sintering temperature of powder granule, therefore efficiently solve the powder granule at high temperature problem such as oxidizable.
(3) in this composite block material owing to comprising the MXenes with multilayer " class accordion " structure, therefore density reduces, and quality is light, and not easily reunites, thus can widen the Application Areas as absorbing material.
(4) massfraction of resin, Ferrite Material and MXenes is adjustable, therefore, it is possible to regulate absorbing property according to practical application request.
(5) can need shaping for this composite block material or be processed into the device of desired shape and size according to practical application.
(6) as preferred, adopt coprecipitation method, make full use of the surface group of MXenes, Ferrite Material ion original position is adsorbed in MXenes sheet of material structure, then coprecipitation method in-situ preparation ferrite molecule is utilized, thus make ferrite molecule growth in situ in the laminated structure of MXenes, strengthen the bonding force of ferrite molecule and MXenes laminated structure on the one hand, be conducive to the stable performance of this composite block material on the other hand.
Accompanying drawing explanation
Fig. 1 is the photo in kind of composite block material obtained in the embodiment of the present invention 1;
Fig. 2 is MXenes-20wt.%Ni obtained in the embodiment of the present invention 1
0.5zn
0.5fe
2o
4the XRD spectrum of powder granule;
Fig. 3 is MXenes-20wt.%Ni in the embodiment of the present invention 1
0.5zn
0.5fe
2o
4the SEM photo of powder granule.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the specific embodiment of the present invention is described further, it is pointed out that the following stated embodiment is intended to be convenient to the understanding of the present invention, and any restriction effect is not play to it.
Embodiment 1:
In the present embodiment, resin is polyetherimide resin (PEI), and Ferrite Material is Ni
0.5zn
0.5fe
2o
4, MXenes material is Ti
3c
2t
x.This Ferrite Material and MXenes material form powder granule, and in powder granule, the mass percentage of Ferrite Material is the mass percentage of 20%, MXenes is 80%, and its chemical representation is MXenes-20wt.%Ni
0.5zn
0.5fe
2o
4.Further, powder granule is dispersed in resin and forms composite block material, and the quality of powder granule accounts for 5% of this composite block material total mass, and the quality of resin accounts for 95% of this composite block material total mass.
The concrete preparation method of above-mentioned composite block material is as follows:
(1) 0.5gTi is taken
3c
2t
xbe dissolved in the supersaturated solution of sodium lignosulfonate, ultrasonication 45min, obtained finely dispersed MXenes solution;
(2) Ferrite Material Ni is at room temperature pressed
0.5zn
0.5fe
2o
4mol ratio Ni
2+: Zn
2+: Fe
3+=0.5:0.5:2 takes Ni (NO
3)
26H
2o, Zn (NO
3)
26H
2o and Fe (NO
3)
39H
2o, adds in MXenes solution, obtains mixing solutions one, and wherein Ferrite Material accounts for Ferrite Material and Ti
3c
2t
xthe mass percentage of total mass is 20%;
(3) according to a certain ratio, configure a certain amount of sodium hydroxide solution, mixing solutions one is instilled in this sodium hydroxide solution with the flow velocity of 0.3L/h, obtain mixing solutions two, the pH value regulating mixing solutions two is 10.5, and stir with the rotating speed of 1000rpm, at 70 DEG C of temperature, mixing solutions two reacts 60min; By gained slurry deionized water wash 5 times after having reacted, then 80 DEG C of oven dry, obtain MXenes-20wt.%Ni
0.5zn
0.5fe
2o
4powder granule;
(4) appropriate PEI is dissolved in dimethyl formamide (DMF), configuration PEI/DMF solution; By the MXenes-20wt.%Ni prepared in step (3)
0.5zn
0.5fe
2o
4powder granule ultrasonic disperse, in appropriate DMF, obtains powder granule solution; Gained powder granule solution is mixed with PEI/DMF solution, make the mass ratio of powder granule and PEI be 5:95, ultrasonic, dispersed with stirring 60min, then leave standstill 10h, vacuum defoamation, obtain mixing solutions, and this mixing solutions is evenly coated on clean glass pane surface;
(5) under sheet glass being placed in 25 DEG C and 70% humidity condition, solvent evaporates in mixing solutions, immersed after cured in deionized water and remove unnecessary DMF, then vacuum-drying 12h at 100 DEG C, can obtain composite block material as shown in Figure 1.
To the MXenes-20wt.%Ni prepared in above-mentioned steps (3)
0.5zn
0.5fe
2o
4the thing of powder body material carries out Measurement and analysis mutually, obtains XRD spectrum as shown in Figure 2, as can be seen from Figure 2: with Ni
0.5zn
0.5fe
2o
4after compound, MXenes still keeps original phase structure, has TiO
2dephasign generates.
Fig. 3 is this MXenes-20wt.%Ni
0.5zn
0.5fe
2o
4the SEM photo of powder, as can be seen from Figure 3: Ni
0.5zn
0.5fe
2o
4growth in situ, in the laminated structure of MXenes, defines class accordion structure.
Embodiment 2:
In the present embodiment, resin is polyetherimide resin (PEI), and Ferrite Material is Ni
0.5zn
0.5fe
2o
4, MXenes material is Ti
3c
2t
x.This Ferrite Material and MXenes material form powder granule, and in powder granule, the mass percentage of Ferrite Material is the mass percentage of 98%, MXenes is 2%, and its chemical representation is Ni
0.5zn
0.5fe
2o
4-2wt.%MXenes.Further, powder granule is dispersed in resin and forms composite block material, and the quality of powder granule accounts for 20% of this composite block material total mass, and the quality of resin accounts for 80% of this composite block material total mass.
The concrete preparation method of above-mentioned composite block material is as follows:
(1) 0.5gTi is taken
3c
2t
xbe dissolved in the supersaturated solution of sodium lignosulfonate, ultrasonication 45min, obtained finely dispersed MXenes solution;
(2) Ferrite Material Ni is at room temperature pressed
0.5zn
0.5fe
2o
4mol ratio Ni
2+: Zn
2+: Fe
3+=0.5:0.5:2 takes Ni (NO
3)
26H
2o, Zn (NO
3)
26H
2o and Fe (NO
3)
39H
2o, adds the MXenes solution configured in step (1), obtains mixing solutions one, and wherein MXenes accounts for the mass percentage of Ferrite Material and MXenes total mass is 2%;
(3) according to a certain ratio, configure a certain amount of sodium hydroxide solution, mixing solutions one is instilled in this sodium hydroxide solution with the flow velocity of 0.5L/h, obtain mixing solutions two, the pH value regulating mixing solutions two is 10.8, and stir with the rotating speed of 2000rpm, mixing solutions two reacts 60min at 60 DEG C of temperature; By gained slurry deionized water wash 3 times after having reacted, then 60 DEG C of oven dry, obtain Ni
0.5zn
0.5fe
2o
4-2wt.%MXenes powder granule;
(4) appropriate PEI is dissolved in dimethyl formamide (DMF), configuration PEI/DMF solution; By the Ni prepared in step (3)
0.5zn
0.5fe
2o
4-2wt.%MXenes powder granule ultrasonic disperse, in appropriate DMF, obtains powder granule solution; Gained powder granule solution is mixed with PEI/DMF solution, make the mass ratio of powder granule and PEI be 1:4, ultrasonic, dispersed with stirring 60min, then leave standstill 10h, vacuum defoamation, obtain mixing solutions, and this mixing solutions is evenly coated on clean glass pane surface;
(5) under sheet glass being placed in 25 DEG C and 70% humidity condition, solvent evaporates in mixing solutions, immersed after cured in deionized water and remove unnecessary DMF, then vacuum-drying 12h at 100 DEG C, can obtain composite block material similar to Figure 1.
To the Ni prepared in above-mentioned steps (3)
0.5zn
0.5fe
2o
4the thing of-2wt.%Mxenes powder granule carries out Measurement and analysis mutually, obtains similar XRD spectrum as shown in Figure 2, as can be seen from the figure: with Ni
0.5zn
0.5fe
2o
4after compound, MXenes still keeps original phase structure, has a small amount of TiO
2dephasign generates.
Further with SEM to this Ni
0.5zn
0.5fe
2o
4-2wt.%MXenes powder body material pattern is observed, and can obtain the photo being similar to Fig. 3, can find out Ni
0.5zn
0.5fe
2o
4growth in situ, in the laminated structure of MXenes, forms class accordion structure.
By room temperature magnetic hysteresis loop and the alternating temperature specific conductivity of the composite block material prepared in measuring physical properties systematic survey above-mentioned steps (5), structure shows: this composite block material still keeps good magnetic property; Compared with pure iron ferrite, the room-temperature conductivity of this composite block material improves, and when temperature is lower than 273K, this composite block material still can keep good specific conductivity, has conductivity.
Therefore, this composite block material has low-temperature conductive performance, can be applied in the following device used at low ambient temperatures as absorbing material:
(1) based in the FEL light source of ERL, the low temperature requirements of such accelerator to high-order mode suppressor absorbing material is met;
(2) can be applied in deep sea submarine Radome part, meet when submarine is in deep-sea under low temperature environment, the absorbing material in Radome part normally can play purposes;
(3) be applied in outer space electromagnetic shielding device, meet under outer space electromagnetic shielding device is in low temperature environment, absorbing material wherein normally can play purposes;
(4) be applied in other such as electron devices, in anti-EMI materials etc., meet under this device is in low temperature environment, absorbing material wherein normally can play purposes.
Embodiment 3:
In the present embodiment, resin is epoxy resin (EP), and Ferrite Material is CoFe
2o
4, MXenes material is V
3c
2t
x.This Ferrite Material and MXenes material form powder granule, and in powder granule, the mass percentage of Ferrite Material is the mass percentage of 90%, MXenes is 10%, and its chemical representation is CoFe
2o
4-10wt.%MXenes.Further, powder granule is dispersed in resin and forms composite block material, and the quality of powder granule accounts for 40% of this composite block material total mass, and the quality of resin accounts for 60% of this composite block material total mass.
The concrete preparation method of above-mentioned composite block material is as follows:
(1) 0.5gV is taken
3c
2t
xbe dissolved in the supersaturated solution of Sodium dodecylbenzene sulfonate, ultrasonication 45min, obtained finely dispersed MXenes solution;
(2) Ferrite Material CoFe is at room temperature pressed
2o
4mol ratio Co
2+: Fe
3+=1:2 takes Co (NO
3)
26H
2o and Fe (NO
3)
39H
2o, adds the MXenes solution configured in step (1), obtains mixing solutions one, and wherein MXenes accounts for the mass percentage of Ferrite Material and MXenes total mass is 10%;
(3) according to a certain ratio, configure a certain amount of sodium hydroxide solution, mixing solutions one is instilled in this sodium hydroxide solution with the flow velocity of 0.5L/h, obtain mixing solutions two, the pH value regulating mixing solutions two is 9.5, and stirs with the rotating speed of 1500rpm, at 80 DEG C of temperature, react 30min; By gained slurry deionized water wash 3 times after having reacted, then 60 DEG C of oven dry, obtain CoFe
2o
4-10wt.%MXenes powder granule;
(4) appropriate EP is dissolved in DMF, is configured to EP/DMF solution; By the CoFe prepared in step (3)
2o
4-10wt.%MXenes powder granule ultrasonic disperse, in appropriate DMF, obtains powder granule solution; Gained powder granule solution is mixed with EP/DMF solution, make the mass ratio of powder granule and EP be 2:3, ultrasonic, dispersed with stirring 60min, then leave standstill 12h, vacuum defoamation, obtain mixing solutions, and this mixing solutions is evenly coated on clean glass pane surface;
(5) under sheet glass being placed in 30 DEG C and 60% humidity condition, solvent evaporates in mixing solutions, immersed after cured in deionized water and remove unnecessary DMF, then vacuum-drying 10h at 120 DEG C, can obtain composite block material similar to Figure 1.
To the CoFe prepared in above-mentioned steps (3)
2o
4the thing of-10wt.%MXenes powder granule carries out Measurement and analysis mutually, obtains similar XRD spectrum as shown in Figure 2, as can be seen from the figure: with CoFe
2o
4after powder compound, MXenes still keeps original phase structure, has a small amount of TiO
2dephasign generates.
Further with SEM to this CoFe
2o
4-10wt.%MXenes powder body material pattern is observed, and can obtain the photo being similar to Fig. 3, can find out CoFe
2o
4growth in situ, in the laminated structure of MXenes, forms class accordion structure.
By room temperature magnetic hysteresis loop and the alternating temperature specific conductivity of the composite block material prepared in measuring physical properties systematic survey above-mentioned steps (5), structure shows: this composite block material still keeps good magnetic property; Compared with pure iron ferrite, the room-temperature conductivity of this composite block material improves, and when temperature is lower than 273K, this composite block material still can keep good specific conductivity, has conductivity.
Therefore, this composite block material has low-temperature conductive performance, can be applied in the following device used at low ambient temperatures as absorbing material:
(1) based in the FEL light source of ERL, the low temperature requirements of such accelerator to high-order mode suppressor absorbing material is met;
(2) can be applied in deep sea submarine Radome part, meet when submarine is in deep-sea under low temperature environment, the absorbing material in Radome part normally can play purposes;
(3) be applied in outer space electromagnetic shielding device, meet under outer space electromagnetic shielding device is in low temperature environment, absorbing material wherein normally can play purposes;
(4) be applied in other such as electron devices, in anti-EMI materials etc., meet under this device is in low temperature environment, absorbing material wherein normally can play purposes.
Embodiment 4:
In the present embodiment, resin is acrylic resin (PP), and Ferrite Material is CoFe
2o
4, MXenes material is V
3c
2t
x.This Ferrite Material and MXenes material form powder granule, and in powder granule, the mass percentage of Ferrite Material is the mass percentage of 50%, MXenes is 50%, and its chemical representation is CoFe
2o
4-50wt.%MXenes.Further, powder granule is dispersed in resin and forms composite block material, and the quality of powder granule accounts for 50% of this composite block material total mass, and the quality of resin accounts for 50% of this composite block material total mass.
The concrete preparation method of above-mentioned composite block material is as follows:
(1) 0.5gV is taken
3c
2t
xbe dissolved in the supersaturated solution of Sodium dodecylbenzene sulfonate, ultrasonication 45min, obtained finely dispersed MXenes solution;
(2) Ferrite Material CoFe is at room temperature pressed
2o
4mol ratio Co
2+: Fe
3+=1:2 takes Co (NO
3)
26H
2o and Fe (NO
3)
39H
2o, adds the MXenes solution configured in step (1), obtains mixing solutions one, and wherein MXenes accounts for the mass percentage of Ferrite Material and MXenes total mass is 50%;
(3) according to a certain ratio, configure a certain amount of sodium hydroxide solution, mixing solutions one is instilled in this sodium hydroxide solution with the flow velocity of 0.5L/h, obtain mixing solutions two, the pH value regulating mixing solutions two is 9.5, and stirs with the rotating speed of 1500rpm, at 80 DEG C of temperature, react 30min; By gained slurry deionized water wash 3 times after having reacted, then 60 DEG C of oven dry, obtain CoFe
2o
4-50wt.%MXenes powder granule;
(4) appropriate PP is dissolved in DMF, configuration PP/DMF solution; By the CoFe prepared in step (3)
2o
4-10wt.%MXenes powder granule ultrasonic disperse, in appropriate DMF, obtains powder granule solution; Gained powder granule solution is mixed with PP/DMF solution, make the mass ratio of powder granule and PP be 1:1, ultrasonic, dispersed with stirring 60min, then leave standstill 9h, vacuum defoamation, obtain mixing solutions, and this mixing solutions is evenly coated on clean glass pane surface;
(5) under sheet glass being placed in 25 DEG C and 65% humidity condition, solvent evaporates in mixing solutions, immersed after cured in deionized water and remove unnecessary DMF, then vacuum-drying 9h at 120 DEG C, can obtain composite block material similar to Figure 1.
To the CoFe prepared in above-mentioned steps (3)
2o
4the thing of-50wt.%MXenes powder granule carries out Measurement and analysis mutually, obtains similar XRD spectrum as shown in Figure 2, as can be seen from the figure: with CoFe
2o
4after powder compound, MXenes still keeps original phase structure, has a small amount of TiO
2dephasign generates.
Further with SEM to this CoFe
2o
4-50wt.%MXenes powder body material pattern is observed, and can obtain the photo being similar to Fig. 3, can find out CoFe
2o
4growth in situ, in the laminated structure of MXenes, forms class accordion structure.
By room temperature magnetic hysteresis loop and the alternating temperature specific conductivity of the composite block material prepared in measuring physical properties systematic survey above-mentioned steps (5), structure shows: this composite block material still keeps good magnetic property; Compared with pure iron ferrite, the room-temperature conductivity of this composite block material improves, and when temperature is lower than 273K, this composite block material still can keep good specific conductivity, has conductivity.
Therefore, this composite block material has low-temperature conductive performance, can be applied in the following device used at low ambient temperatures as absorbing material:
(1) based in the FEL light source of ERL, the low temperature requirements of such accelerator to high-order mode suppressor absorbing material is met;
(2) can be applied in deep sea submarine Radome part, meet when submarine is in deep-sea under low temperature environment, the absorbing material in Radome part normally can play purposes;
(3) be applied in outer space electromagnetic shielding device, meet under outer space electromagnetic shielding device is in low temperature environment, absorbing material wherein normally can play purposes;
(4) be applied in other such as electron devices, in anti-EMI materials etc., meet under this device is in low temperature environment, absorbing material wherein normally can play purposes.
The above embodiment has been described in detail technical scheme of the present invention; be understood that and the foregoing is only specific embodiments of the invention; be not limited to the present invention; all make in spirit of the present invention any amendment, supplement or similar fashion substitute etc., all should be included within protection scope of the present invention.
Claims (10)
1. the composite block material of resin, ferrite and MXenes, is characterized in that: be made up of resin and powder granule, and powder granule is dispersed in resin; Described powder granule is made up of ferrite and MXenes, and ferrite molecular dispersion is in the laminated structure of MXenes.
2. the composite block material of resin, ferrite and MXenes as claimed in claim 1, is characterized in that: the quality of resin accounts for 5% ~ 99.8% of described composite block material total mass.
3. the composite block material of resin, ferrite and MXenes as claimed in claim 1, is characterized in that: the quality of MXenes accounts for 0.1 ~ 99.9% of described powder granule total mass.
4. the composite block material of resin, ferrite and MXenes as claimed in claim 1, is characterized in that: it is MeFe that described Ferrite Material comprises chemical formula
2o
4, AFe
12o
19or R
3fe
5o
12the Ferrite Material of system, wherein Me element is the combination of a kind of element in Ni, Mn, Zn, Cu, Co, Fe, Li, Mg, Cr, Ca, Ba element or two or more element; Element A is the combination of a kind of element in Ba, Co, Ni, Mn, Zn, Cu, Fe, Li, Mg, Cr, Ca element or two or more element; R element is the combination of a kind of element in rare earth element y, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or two or more element.
5. the composite block material of resin, ferrite and MXenes as claimed in claim 1, is characterized in that: described MXenes passes through ternary layered sintering metal M
n+1aX
ncombine more weak A bit element mutually extract out and obtain; Wherein, M is transition metal, and A is main group element, and X is C and/or N, n is 1 ~ 3.
6. the composite block material of resin, ferrite and MXenes as claimed in claim 1, is characterized in that: described resin comprises one or more the combination in polyimide resin, polystyrene resin, polymethacrylate resin, polycarbonate, acrylic resin, epoxy resin, resol.
7. the preparation method of the composite block material of resin, ferrite and MXenes as described in claim arbitrary in claim 1 to 6, is characterized in that: comprise the steps:
Resin is dissolved in solvent, configuration resin solution;
Described powder granule is scattered in homogeneous solvent, obtains powder granule solution;
Resin solution is mixed with powder granule dissolution homogeneity, standing, deaeration is also evenly coated on carrier surface, solvent evaporates under suitable temperature and humidity condition, and excess of solvent is removed in cleaning after cured, then vacuum-drying 0.1 ~ 100h at 80 ~ 200 DEG C, obtains described composite block material.
8. the preparation method of the composite block material of resin, ferrite and MXenes as claimed in claim 7, it is characterized in that: in described powder granule, ferrite molecule growth in situ, in the laminated structure of MXenes, adopts coprecipitation method to prepare this powder granule, specifically comprises the steps:
Appropriate MXenes is dissolved in dispersion liquid, obtained finely dispersed MXenes solution;
The preparation of raw material of Ferrite Material is carried out according to the amount of substance of respective element in Ferrite Material chemical formula;
The raw material of Ferrite Material is mixed with MXenes solution, obtains mixing solutions one;
Mixing solutions one is instilled in basic solution, obtain mixing solutions two, the pH value regulating mixing solutions two is 7 ~ 12, and mixing solutions two reacts at 20 ~ 90 DEG C of temperature under agitation, reaction product cleaning, oven dry, obtain the powder granule of Ferrite Material and MXenes.
9. the preparation method of the composite block material of resin, ferrite and MXenes as claimed in claim 7, is characterized in that: described dispersion liquid comprises a kind of solution in sodium lignosulfonate, Sodium dodecylbenzene sulfonate or oleyl amine;
The described reaction times is preferably 10min ~ 120min;
Described basic solution is preferably sodium hydroxide, potassium hydroxide, ammonia soln.
10. the composite block material of resin, ferrite and MXenes as described in claim arbitrary in claim 1 to 6 is as the application of absorbing material.
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