CN107814869A - Polymer/stannic oxide/graphene nano composite aquogel that is tough and tensile, stretchable, compressible and having fabulous self-healing properties - Google Patents
Polymer/stannic oxide/graphene nano composite aquogel that is tough and tensile, stretchable, compressible and having fabulous self-healing properties Download PDFInfo
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Abstract
The present invention provides tough and tensile, stretchable, compressible polymer/stannic oxide/graphene nano composite aquogel, and has fabulous self-healing properties.PAMC/graphene oxide (GO) hydrogel is prepared for by the radical polymerization of acrylamide (AM) and acrylyl oxy-ethyl-trimethyl salmiac (DAC) in the presence of graphene oxide.Mechanical performance and self-reparing capability can be adjusted by the mass ratio of GO contents and AM and DAC.The hydrogen bond between ionic bond and AM and GO between DAC and GO effectively dissipation energy can lay equal stress on establishing network.Resulting composite aquogel has high rigidity (Young's modulus：~1.1MPa), high tenacity (~9.3MJm‑3) and high antifatigue, and high selfreparing rate (>92% tensile strength,>99% elongation strain and>93% toughness).Step is simple and convenient to operate, is practical.
Description
Technical field
The invention belongs to selfreparing hydrogel field, more particularly to tough and tensile, stretchable, compressible polymer/oxidation stone
Black alkene Nanometer composite hydrogel, and have fabulous self-healing properties.
Background technology
Recently, self-repair material has been to be concerned by more and more people, because they can repair the energy of oneself after damage
Power, because this attribute can extend the service life of material, maintenance cost is reduced, improves the overall security of system.Realize
Self-repair material has three kinds of strategies, includes the storage of renovation agent, and dynamic covalent bond is formed, and is also carried out using non-covalent bond mutual
Effect (such as：Hydrogen bond, hydrophobic association, host-guest interaction, pi-pi accumulation, and electrostatic interaction).Hydrogel is as soft
Three-dimensional netted material, not only can because of they biocompatibility and applied in bioengineering, and in waste processing,
Also there is potential application in superabsorbents and electronic equipment.However, relatively poor mechanics performance limits its application.In addition,
Selfreparing property introducing hydrogel is added to the difficulty for preparing high mechanical properties hydrogel.The toughness hydrogel reported is usual
Do not have or the only very weak self-repairability and usual mechanical performance of selfreparing hydrogel is very weak.Therefore, develop both organic
The high hydrogel for having good self-reparing capability again of tool intensity is height requirement.
In order to realize this target, a strategy is design dual network (DN) hydrogel, and this refers to be gathered by highly cross-linked
Polymeric network (being initially formed) and the hydrogel for polymer network (in the rear formation) synthesis being loosely crosslinked.For example, Zheng etc. is carried
A kind of new layout strategy is gone out, has been coagulated by the way that hydrophobic polyacrylamide is introduced into the agar being physical crosslinking completely to improve DN
The anti-fatigue performance and self-repairability of glue.Gong etc. reports one synthesized by the random copolymerization of the ion monomer of opposite charges
Class is new, toughness and viscoelastic polystyrene hydrogel.Hydrogel is due to multiple ionic bonds be present and with the tough of enhancing
Property and self-reparing capability.Although DN hydrogels can realize the raising of mechanical strength and self-reparing capability, complicated conjunction simultaneously
The multiple influence factor formed into process and first network to the second network, limits its practical application.
Another method for obtaining the toughness hydrogel with self-reparing capability is to prepare Nanometer composite hydrogel, this side
Method building-up process is simple, and only by being introduced into Nano filling such as clay, CNT, graphene into hydrogel.
In these Nano fillings, graphene-based material excellent electric conductivity and is led due to the mechanical strength and chemical stability of its superelevation
It is hot to be widely introduced into hydrogel and assign their special performances.For example, Tong et al. is prepared for having enhancing
Mechanical performance and quick self-reparing capability graphene oxide-HECTABRITE DP-poly- (N,N-DMAA) it is mixed
Heshui gel.Although having made significant headway, after most of renewable hydrogels are repaired, the tensile strength of recovery is less than
0.5MPa, self-repair efficiency are less than 90%.Therefore, on the premise of its remediation efficiency is not sacrificed, design synthesis has enhancing machine
The new self-repair material of tool performance still has very big challenge.
The content of the invention
In order to overcome above-mentioned deficiency, the present invention provides a kind of tough and tensile, stretchable, compressible, selfreparing polymer/oxidation
Graphene nano composite aquogel, it shows high self-repair efficiency and excellent mechanical performance.
To achieve these goals, the present invention adopts the following technical scheme that：
A kind of preparation of tough and tensile, stretchable, compressible, selfreparing polymer/stannic oxide/graphene nano composite aquogel
Method, including：
It is to receive by comonomer, graphene oxide GO of acrylamide AM and acrylyl oxy-ethyl-trimethyl salmiac DAC
Rice corpuscles, radical polymerization in situ, it is multiple to produce tough and tensile, stretchable, compressible, selfreparing polymer/stannic oxide/graphene nano
Heshui gel.
At present, selfreparing Nanometer composite hydrogel monomer is limited to acrylic amide material more, and due to lacking to aoxidizing stone
The complete understanding that black alkene is formed with macromolecule interaction with structure, constrains the development of such Nanometer composite hydrogel.Therefore,
Present system have studied graphene oxide and polymer monomer interaction rule and structure Forming Mechanism, in large scale experiment
Chanced in groping：Acrylamide AM and acrylyl oxy-ethyl-trimethyl salmiac DAC are used as comonomer and oxidation stone
The Nanometer composite hydrogel that black alkene is formed not only can realize efficient selfreparing under water auxiliary, also with excellent mechanical performance.
On the other hand, the application research also found：It is former compared with blending polymerization, nano particle surface modifying copolymerization method
Position polymerization ensure that matching effect good between polymer and graphene nano particle, in the graphene oxide with lamellar structure
In being reacted with polymer polymerizing, can obtain have it is excellent stretch, mechanical and self-healing properties Nanometer composite hydrogel.
Preferably, in the home position polymerization reaction, crosslinking agent can be N, N'- methylene-bisacrylamides MBA.
The excellent mechanical performance of P (AM-co-DAC)/GO hydrogels is attributed to the fact that ionic bond and the density of hydrogen bond in the present invention
Between appropriate balance.Therefore, currently preferred acrylamide AM and acrylyl oxy-ethyl-trimethyl salmiac DAC quality
Than for 1：0.5~2, the dosage of graphene is 0.5~2% of polymer monomer gross weight in hydrogel；With by control AM and
DAC ratio and GO content adjust this balance.
Preferably, the radical polymerization in situ concretely comprises the following steps：Acrylamide AM, acrylyl oxy-ethyl will be dissolved with
Bar be present in initiator in trimethyl ammonium chloride DAC, N, N'- methylene-bisacrylamides MBA and graphene oxide the GO aqueous solution
Under part, ice bath stirring, degassing, polymerisation, dehydration, produce.
Test result indicates that：GO hydrogel is not added, because AM hydrogen bond is reduced, the toughness of hydrogel is from A1D0.5G0
~4.12MJ m-3It is reduced to A1D2G0~0.67MJ m-3("~" refers to herein：About).After introducing GO, with corresponding initial condition
Gel is compared, and toughness improves, and increases with the increase of GO contents.
It is furthermore preferred that the pH value of the graphene oxide aqueous dispersions is 10.0.Before polymerization, GO dispersion liquids are added to not
In the monomer solution under pH value (Fig. 2 a).When pH value is less than 9, due to DAC flocculation behavior, mixture becomes uneven.
With the increase of pH value, solution is gradually dimmed, almost opaque when pH value is 12, shows that GO nanometer sheets are preferably disperseed.Table
Show that the Zeta potential of Coulomb repulsion degree between particle is directly relevant with the stability of aqueous colloidal dispersion.With the increase of pH value,
The Zeta potential absolute value of GO and DAC dispersions is higher, shows with higher resistance to aggregation and can form more stable point
Granular media system (Fig. 2 b).In addition, GO nanometer sheets have negative Zeta potential in the solution, and DAC solution has positive Zeta potential.Cause
This, selecting 10.0 optimal pH, this would be even more beneficial to DAC and GO electrostatic phase to polymerize AM and DAC monomers in the presence of GO
Interaction (Fig. 2 b).
Preferably, the initiator be ammonium persulfate APS, double (2- methyl-props amidine) the dihydrochloride AIBA of 2,2'- azos and
Formaldehyde sulfoxylate sodium hydrate ALD.
Present invention also offers the polymer/stannic oxide/graphene nano compound water congealing that can be obtained by any foregoing method
The method of glue selfreparing, including：The above-mentioned hydrogel plane of disruption of cut-off two parts is bonded；Then, water droplet is being broken
On face, stand, produce.Test result indicates that：When the above-mentioned hydrogel of cut-off two parts is placed on the help of no water
When together, they can mutually be bonded at room temperature.However, bonding strength is weaker, easily ruptured in interface.These result tables
Bright, ionic bond and hydrogen bond can be re-formed by the help of water.
Preferably, above-mentioned hydrogel, there is~1.1MPa Young's modulus ,~9.3MJ m-3Toughness.
Present invention also offers with~1.1MPa Young's modulus ,~9.3MJ m-3The hydrogel of toughness, including it is any
Arbitrary characteristics listed by item preceding method.
Present invention also offers acrylamide AM and acrylyl oxy-ethyl-trimethyl salmiac DAC comonomer to prepare
Application in tough and tensile, stretchable, compressible, selfreparing polymer/stannic oxide/graphene nano composite aquogel.
Present invention also offers the filter including the above-mentioned hydrogel of any one, for heavy metal, solvent, oil, gasoline
Absorber material, gas adsorption media, Water warfare medium, electro-chemical device electrode with liquid absorption.
Beneficial effects of the present invention
(1) present invention is prepared for containing cation poly- (nitrile-acrylamide-acrylic acid acyloxyethyls three of the GO as main crosslinking agent
Ammonio methacrylate) (P (AM-co-DAC)) hydrogel, it shows high self-repair efficiency and excellent mechanical performance.Selfreparing is
Aid in realizing by water, without any other stimulation.Deionized water is widely used in the selfreparing of hydrogel and polymer film.
In our system, water is sprayed in fracture faces, is then at room temperature put material and is completed certainly within several hours in atmosphere
Repair process.
(2) by the present invention in that multiple interactions with P (AM-co-DAC) between GO, enhance self-reparing capability
And mechanical strength.It is different from other Nanometer composite hydrogels, in alkaline environment, DAC N (CH3)+With GO COO-Between
Ionic bond acts on as strong cross-linking, there is provided elasticity.AM NH2Hydrogen bond between GO oxy radical as reversible crosslink,
Destroyed during deformation and lay equal stress on new change with dissipation energy (Fig. 1).As a result, the density of ionic bond and hydrogen bond can be used to pass through GO contents
It is controlled with AM and DAC mass ratio.Resulting P (AM-co-DAC)/GO composite aquogels have excellent mechanicalness
Can, such as high rigidity (Young's modulus：~1.1MPa), high tensile is up to 2.1MPa, and high elongation rate is 800-1700% and had
Certain fatigue resistance (circulation and the circulation of 30 second compressions are stretched in 20 tensioning, it is contemplated that>90% elasticity recovery), and it is fabulous from
Remediation efficiency (tensile strength>92%, elongation strain>99%, toughness>93%)
(3) preparation method of the present invention is simple, self-repair efficiency is high, practical, easy to spread.
Brief description of the drawings
The Figure of description for forming the part of the application is used for providing further understanding of the present application, and the application's shows
Meaning property embodiment and its illustrate be used for explain the application, do not form the improper restriction to the application.
Fig. 1 is that AM, DAC and N are prepared in the presence of graphene oxide, the hydrogel of N'- methylene-bisacrylamides (MBA)
The schematic diagram of copolymerization and the loading proposed and the molecular mechanism of recovery process.
Fig. 2 is the photo of GO and DAC mixed dispersion liquids under (a) different pH value, and (b) is respectively the pH value of GO and DAC solution
To zeta current potentials, (c) GO powder, P (AM-co-DAC) and P (AM-co-DAC)/GO Fourier infrared spectrum, (d) is respectively P
(AM-co-DAC) and P (AM-co-DAC)/GO Raman spectrum.
Fig. 3 is the mechanical performance figure of hydrogel, and (a) has the tensile stress of A1D2Gz hydrogels of different GO contents-should
Varied curve, the A that (b) strain is 0.5%1D2GzThe energy storage (G', filling symbol) of hydrogel and loss (G ", open symbols) and modulus
Frequency dependence, (c) have different GO contents hydrogel Young's modulus change, (d) have different GO contents water
The toughness of gel, A1D2G1Hydrogel can (e) bending, (f) knotting, (g) loading and (h, i) stretching.
Fig. 4 is A under (a) continuous strain sweep1D2G1G' and G " be respectively 1%, 50%, 100% and 200% strain
When alternate oscillation power, (b) A1D2G1There is the cyclic tension loading-unloading curve of different recovery times under 800% strain,
(c)A1D2G120 tensile loads-unloading circulation is carried out after recovering 10 minutes between each cycle, (d) 20 stretchings add
A after load-unloading circulation1D2G1Dissipation energy and Young's modulus recovery extent.
Fig. 5 is the A of (a) compression1D2G1Hydrogel (above) and A1D2G0The image of hydrogel (figure below), (b) A1D2G1Not
With the compression curve under compression strain, (c) A1D2G1The circulation of 30 subsequent compression loading-unloadings, recover 40 between each circulation
Second, (d) after 30 second compression relaxation cycles, A1D2G1Dissipation energy and recovery extent.
Fig. 6 is the selfreparing property of hydrogel.By A1D2G1The original cylindrical bars of sample cut in half (a), and two parts are simple
Singly contact, a drop water is dropped on cut surface (b), and after standing a few hours, sample is stretched to big strain (c), (d) with hand
A1D2G1Moisture water content of hydrogel after the different stand-by period of dripping change, (e) different stand-by period after dripping,
A1D2G1Load-deformation curve, (f) A1D2GzHydrogel repairs the load-deformation curve before and after 20 hours, (g) at room temperature
The remediation efficiency of the fracture strength of all composite aquogels with different GO contents.
Fig. 7 is the A of original drying1D2G1The photo of sample (a), water is sprayed to dry A1D2G1(b) on.Stand 40 points
Zhong Hou, can manual expanded material (c, d), (e) primary sample, and absorb water after sample and cut-out selfreparing after sample should
Force-strain curve.
Fig. 8 is GO, P (AM-co-DAC) and P (AM-co-DAC)/GO XRD spectrum.
Fig. 9 is (a) P (AM-co-DAC) and (b) P (AM-co-DAC)/GO XPS spectrum.In P (AM-co-DAC) sample,
Two bands of a spectrum positioned at 399.6 and 402.3eV are belonging respectively to-NH2With-N+(CH3)3Nitrogen-atoms.GO is added in hydrogel
Afterwards ,-NH2N1s peak heights deform and move, and-N+(CH3)3N1s peaks be moved to 403.4eV.These differences show in P
(AM-co-DAC) hydrogen bond and ionic bond are formed between GO.
Figure 10 is A1D4G1Hydrogel (left side) and A1D2D1The image of hydrogel (right side).
Figure 11 is AlD2G1The storage modulus (G') and loss modulus (G ") of sample.
Figure 12 is the A for having different GO contents1D0.5GzAnd A (a)1D1Gz(b) load-deformation curve of sample.
Figure 13 is A1D2G1The optical microscope image of sample self-repair procedure：(a) letter of two planes of disruption (a) is only passed through
Single contact, and 1h (b), 5h (c), 10h (d), 15h (e) and 20h (f) are stood in atmosphere.
Figure 14 is A1D2G1The self-repair efficiency of sample.
Figure 15 is A1D0.5Gz(a) and A1D1Gz (b) has the stress-strain of the sample of different GO contents before and after selfreparing
Curve
Figure 16 is mechanical performance figure of all hydrogels before and after selfreparing；
Figure 17 is mechanical performance and remediation efficiency figure of the sample of the application compared with the document delivered.
Embodiment
It is noted that described further below is all exemplary, it is intended to provides further instruction to the application.It is unless another
Indicate, all technologies used herein and scientific terminology are with usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
Embodiment 1
1 experimental section
1.1 experiment reagents and material
Graphite powder (8000 mesh, purity 99.95%), formaldehyde sulfoxylate sodium hydrate (ALD), N, N'- methylene bisacrylamides
Acid amides (MBA), acrylamide (AM) and double (the 2- methyl-props amidine) dihydrochlorides (AIBA) of 2,2'- azo are carried by Aladdin company
Supply.Ammonium persulfate (APS), the concentrated sulfuric acid (95-98%), concentrated hydrochloric acid (36-38%), ammoniacal liquor, potassium permanganate, all it is that analysis is pure
(being bought from Beijing chemical company (China)).Hydrogen peroxide (H2O2) and sodium nitrate be to be bought from Laiyang City Kant chemical company.Third
Alkene acyloxyethyl trimethyl ammonium chloride, the 80wt% aqueous solution (DAC) are bought from lark prestige company
The preparation of 1.2 graphene oxides
Graphene oxide is prepared from native graphite by Hummers methods.In brief, 36ml sulfuric acid is added to and is placed in ice
In 250ml round-bottomed flasks in bath.By about 1g native graphites, 0.75g NaNO3It is dissolved in cold sulfuric acid and is stirred with magnetic stirring apparatus
Mix.Then, 5g KMnO are slowly added within 15-20 minutes4.Afterwards, reactant mixture is kept for 30 minutes at 40 DEG C, then will
Gained mixture stirs 2 hours.Bath temperature is risen to 80 DEG C, continues reaction 1 hour, to increase the oxidizability of graphite.Then
It is down to room temperature.Gained suspension is diluted with 50ml deionized waters, and uses H2O2Solution is further handled, until color is changed into bright orange
Color.Bright yellow product is washed for several times with mass concentration 10%HCl.By being centrifuged off impurity for several times, until supernatant
PH value is 7 or so, is finally ultrasonically treated 1 hour, obtains graphene oxide (GO).
The preparation of 1.3 P (AM-co-DAC)/GO composite aquogels
By the way that in the presence of GO, DAC and AM radical polymerization in situ synthesize P (AM-co-DAC)/GO composite aquogels.
First, GO (40mg) is dispersed in ultrasonic disperse about 1 hour in water (11mL).By the way that ammoniacal liquor is added dropwise by the pH value of GO aqueous dispersions
Regulation stirs mixture 10 minutes to 10 in ice bath.Then monomer DAC (2.67g) and AM (1.34g) are added under agitation
Enter into GO suspension, add 1mL MBA (3mg/mL) aqueous solution in the mixture.Mixture is stirred for 2 hours, in ice bath
Lower formation homogeneous solution.Finally, initiator A PS (10mg), AIBA (15mg) and ALD (15mg) are added into solution, and in ice
Stirred 1 hour in bath.Then bubble is removed after being then sonicated 5 minutes, mixture is transferred to the internal diameter of 5.5mm glass tubes.
It is aggregated in 35 DEG C of baking oven and carries out 12 hours.Obtained hydrogel is taken out from glass tubule, and in atmosphere in room temperature
Lower dehydration about 20 hours, 30 weight % are down to by moisture.
1.4 self-repair procedure
Prepared cylindrical hydrogel is cut in half, is then placed in contact with each other its plane of disruption together.Disconnected
Drip a drop water on broken face.After standing selfreparing in atmosphere, repair sample and tested in different repair time.
1.5 mechanical test
Tension test is tested using universal test instrument (Hensgrand, WDW-02, China).In 100mm min-1's
The hydrogel sample with 3mm diameters, 50mm length and 10mm full-lengths through preparation is tested at crosshead speed and 25 DEG C.
Tensile stress (σ) is calculated as σ=F/ π R2, wherein F is load, and R is the original radius of sample.Elongation strain (ε) is defined as length
(l) relative to sample initial gage (10) change, ε=(1-10)/10 × 100%.Young's modulus be calculated as ε=0%~
The slope of load-deformation curve in the range of 100%.Fracture toughness is characterised by energy to failure (U, MJ m-3), it passes through correspondingly
Area under force-strain curve carries out integral and calculating：U=∫ σ d ε.
The cyclic tension experiment of 800% maximum strain is carried out on the sample with identical gauge length and identical speed.
The dissipation energy Δ U each circulated is defined as the hysteresis loop area that loading-unloading curve is included：Δ U=∫loadingσdε-
∫unloadingσdε.
The rheology measurement of hydrogel is carried out using the TA DHR-2 rheometers of a diameter of 20mm parallel-plate.(1) first
With 10rad s-1Angular frequency carry out from 0.1% to 10% dynamic strain scanning, to determine linear viscoelasticity area.(2) frequency
Scope is 0.1-100rad s-1, frequency range 0.5%.(3) with fixed angular frequency (10rad s-1) measurement hydrogel
Substep alternate strain (1%, 50%, 100%, 200%) scans.All measurements are controlled at 25 DEG C by Peltier plate.
1.6 characterize
Fourier infrared spectrum is in a Fourier infrared spectrograph IR Prestige-21 (Shimadzu, Japan)
Survey.X-ray diffraction (XRD) obtains Raman spectrums from D8ADVANCE X-ray diffractions instrument (Bruker AXS, Germany)
Measured with LabRAM tHR800Raman spectrometer (HORIBA JY, France).ZETA points position is to use Zetasizer
Nano ZS90 Particle Size Analyzers (Malvern, England) measure
2. experimental result is with discussing
By using N, N'- methylene-bisacrylamides (MBA) are used as chemical cross-linking agent, pass through acrylamide (AM) and third
The free-radical polymerized synthesis cationic PAM hydrogel of alkene acyloxyethyl trimethyl ammonium chloride (DAC) one kettle way.Before polymerization, by GO points
Dispersion liquid is added to (Fig. 2 a) in the monomer solution under different pH value.When pH value is less than 9, due to DAC flocculation behavior, mixture
Become uneven.With the increase of pH value, solution is gradually dimmed, almost opaque when pH value is 12, shows GO nanometer sheets more
Good is scattered.The Zeta potential of Coulomb repulsion degree is directly relevant with the stability of aqueous colloidal dispersion between expression particle.With
The increase of pH value, the Zeta potential absolute value of GO and DAC dispersions is higher, shows to have higher resistance to aggregation and can be formed
More stable dispersion (Fig. 2 b).In addition, GO nanometer sheets have negative Zeta potential in the solution, and DAC solution has just
Zeta potential.Therefore, select 10.0 optimal pH to polymerize AM and DAC monomers in the presence of GO, this would be even more beneficial to DAC and
GO electrostatic interaction (Fig. 2 b).Polymerisation is carried out 12 hours at 35 DEG C, is then put hydrogel and is lost water in atmosphere
Point, obtain gained P (AM-co-DAC)/GO composite aquogels with about 30 weight % water content.X-ray diffraction (XRD) is shown
In 11.3 ° of 2 θ GO spike, and P (AM-co-DAC) shows similar XRD with P (AM-co-DAC)/GO hydrogels
Spectrum, but without any sharp peak, show that GO nanometer sheets are dispersed in P (AM-co-DAC) aquogel system (Fig. 8).
The photo of GO and DAC mixed dispersion liquids under the different pH value of Fig. 2 (a).(b) be respectively GO and DAC solution pH value pair
Zeta current potentials.(c) GO powder, P (AM-co-DAC) and P (AM-co-DAC)/GO Fourier infrared spectrum.(d) it is respectively P
(AM-co-DAC) and P (AM-co-DAC)/GO Raman spectrum.
Our purpose of design is the quaternary ammonium group and GO by controlling hydrogen bond and DAC between AM amino and oxy radical
Carboxyl between Hydrogenbond obtain the hydrogel (Fig. 1) with high-mechanical property and high self-reparing capability.In order to prove two
The presence of kind interaction, we have done Fourier infrared spectrum and Raman spectrum.In P (AM-co-DAC)/GO composite aquogels
In, belong to bands of a spectrum (such as 3062,1730, the 1228 and 1055cm of GO powder-1, the OH stretching vibrations that are belonging respectively in carbonylic acid,
C=O carbonylic stretching vibrations, and the asymmetric and symmetrical C-O stretching vibrations in C-O-C groups) substantially reduce or even disappear,
This is probably because GO contents are low in hydrogel.However, belong to 3413 and 3198cm of AM feature N-H stretching vibrations-1Place
Bands of a spectrum are transferred to 3402,3190cm in P (AM-co-DAC)/GO hydrogels respectively-1.In addition,-CO-NH2The feature C=of group
1663 and 1610cm of the O stretching vibrations from AM-11669 and 1619cm being displaced in P (AM-co-DAC)/GO hydrogels-1(figure
2c).These skews are enough the presence of interaction of hydrogen bond between the oxy radical for the amino and GO pieces for showing PAM chains
In 950cm-1The spike at place, which is highlighted in P (AM-co-DAC) and P (AM-co-DAC)/GO hydrogels, has quaternary ammonium
Group.High alkalinity environment (pH value=10) makes GO nearly all hydroxy-acid group with-COO-Form is present.Therefore, in GO COO-
With DAC N (CH3)3 +Between form strong ionic bond (Fig. 1).Formed in P (AAM-co-DAC)/GO hydrogels after ionic bond,
N (the CH belonged in P (AM-co-DAC)3) symmetrical CH3Stretching vibration, asymmetric and symmetrical CH3The 2945 of deformation vibration,
1480,1406cm-1The peak at place is transferred to 2957,1472,1417cm-1(Fig. 2 c).In addition, Raman spectrum clearly illustrates, DAC
Middle N (CH3)3+Symmetrical and asymmetric CH3Incorporation GO is stretching in afterwards from 2927 and 2971cm-1It is transferred to 2933 and 2960cm-1
(Fig. 2 d), it was demonstrated that formation ionic bond.In addition, before and after GO is added into hydrogel, N1s peaks in P (AM-co-DAC)
Combination can difference also demonstrate the formation (Fig. 9) of hydrogen bonds and ionic bond of the P (AM-co-DAC) between GO.
The excellent mechanical performance of P (AM-co-DAC)/GO hydrogels is attributed to the fact that suitable between ionic bond and the density of hydrogen bond
Work as balance.For the influence of clear and definite two kinds interactions, the content of MBA chemical cross-linking agents is equal in all hydrogels in polymerization process
Fixed.Therefore, we adjust this balance by controlling AM and DAC GO contents and mass ratio.Different hydrogel (contractings
It is written as AxDyGz, wherein A, D and G represent AM, DAC and GO respectively, and x and y represent AM and DAC mass ratio respectively, and z is respectively GO
Content) by using different AM and DAC mass ratioes (1:0.5,1:1,1:2,1:4), and different GO contents (0.5,1,1.5,
2wt%) it is made.For A1D4GzSample, because DAC content is too many, hydrogel is still very weak, it is impossible to keeps its shape (figure
10).Therefore, unless otherwise indicated, for all hydrogels described herein, x：Y is respectively equal to 1：0.5,1：1 and 1：2, z
Respectively equal to 0,0.5,1,1.5,2.
Fig. 3 a show A1D2GzThe tensile stress-strain curve of sample.There is no GO, A1D2G0Hydrogel shows fracture strength
For 96.8kPa.When adding a small amount of GO, A1D2G0.5Fracture strength reach 357.9kPa, almost A1D2G04 times.Accordingly
Ground, breaking strain also increase to~1562% from~1150%.This means formed between GO and P (AM-co-DAC) from
Sub-key and hydrogen bond can significantly improve mechanical strength.When GO contents reach 1wt%, fracture strength and strain increase to
564.1kPa and 1608%.The further increase of GO contents causes the increase of fracture strength and the slight decrease (figure of breaking strain
3a)。
For A1D2Gz series, also passes through influences of the rheology measurement GO to the mechanical strength of hydrogel.In A1D2Gz samples
Vibration range of strain be 1% to 100% and 1rad s-1When measure storage modulus G' and loss modulus G " vibration strain rely on
Property, to determine Linear Viscoelastic Region (Figure 11).Therefore, all test for viscoelastic are all carried out with 0.5% strain, to ensure
Linearly viscoelastic validity and enough sensitivity.Fig. 3 b are shown in 1% to 100% angular frequency range, A1D2Gz water
The G' and G " of gel angular frequency rate dependence.In the range of the observing frequency of all hydrogels, G' is always above G ", and this shows
Cross-linked network is formd in these hydrogels.Higher GO contents produce higher G', and this coincide good with stretch test result.
These results indicate that the crosslinked action that GO is provided do occur in hydrogel.
The mechanical performance of Fig. 3 hydrogels.(a) there is the A of different GO contents1D2The tensile stress of Gz hydrogels-strain is bent
Line.(b) strain is 0.5% A1D2GzThe frequency of the energy storage (G', filling symbol) of hydrogel and loss (G ", open symbols) modulus
Rate dependence.(c) change of the Young's modulus of the hydrogel with different GO contents.(d) there is the hydrogel of different GO contents
Toughness.A1D2G1Hydrogel can (e) bending, (f) knotting, (g) loading and (h, i) stretching.
By adjusting chemical composition, we have been realized in the balance of above-mentioned interaction and designing material, have fabulous
Mechanical performance.The interaction of ionic bond and hydrogen bond in hydrogel is controlled by AM and DAC different quality ratio.A1D0.5Gz
And A1D1The tensile stress-strain curve of Gz hydrogels is as shown in figure 12.For all A1D0.5GzAnd A1D1GzSample, with GO
The increase of content, fracture strength increase, with A1D2The result of Gz hydrogels is similar.For example, A1D0.5G1.5Tensile strength for~
1.9MPa, compare A1D0.5G0(~0.58MPa) increase more than three times, A1D0.5G2It is further increased to~2.1MPa.All hydrogels
Detailed mechanical performance see Figure 16.The Young's modulus (reaction rigidity) of hydrogel is summarized in figure 3 c.By adjust GO contents and
AM and DAC ratio, hydrogel can be from very soft to hard.Under identical GO contents, the rigidity of hydrogel is with AM
The increase of content and increase.Higher AM contents cause higher rigidity.For example, GO is added without, A1D0.5G0 samples show~
304kPa Young's modulus, higher than A1D1G0And A1D2G0(Fig. 3 c).Composition (A with higher AM contents1D0.5GzSeries) permit
Perhaps higher hydrogen bond sum, this causes higher crosslink density., can in hydrogel by the way that GO is mixed due to increased ionic bond
Further to improve rigidity.It is worth noting that, A1D0.5G2The Young's modulus of sample is up to~1056kPa.
The toughness of hydrogel is reflected as shown in Figure 3 d by energy dissipation.When not adding GO, because AM hydrogen bond is reduced,
The toughness of hydrogel is from A1D0.5G0~4.12MJ m-3It is reduced to A1D2G0~0.67MJ m-3.After introducing GO, with corresponding original
Beginning hydrogel is compared, and toughness improves, and increases with the increase of GO contents.Under identical GO contents, A1D2Gz samples it is tough
Property is higher than A1D1Gz, less than A1D0.5Gz, illustrate A1D0.5GzHydrogen bond in series is dominated, A1D2GzIonic bond in series becomes apparent from,
This is due to the change (Figure 16) of AM and DAC ratios.It is noted that under 2wt% GO contents, as described below, GO and polymer
Interaction between chain causes the slight decrease of toughness and self-repair efficiency.A1D0.5G2Highest Young with~1056kPa
Modulus, highest tensile strength when elongation is~810% are~2.1MPa, and toughness is~9.3MJm-3(Figure 16).These machineries
Performance is more much better than these polymer/graphene composite aquogels or elastomer, and with those polyanion hydrogels and
Toughness DN hydrogels are suitable.It is different from the generally conventional hydrogels with high rigidity but low toughness, we it is this with it is reversible from
The hydrogel of sub-key and hydrogen bond shows effective energy dissipation and shows the mechanical strength strengthened really and rigidity without damaging
Evil toughness.For example, A1D2G1It is sufficiently solid to bear high-caliber flexural deformation (Fig. 3 e), knot (Fig. 3 f).Diameter 3mm's
A1D2G1Billet can bear 1.2kg outer bend load (Fig. 3 g), can also high elongation (Fig. 3 h, i).
Except high intensity, outside the good combination of high rigidity and high tenacity, P (AM-co-DAC)/GO composite aquogels also have
There is excellent anti-fatigue performance.An important factor for stress relaxation rate is antifatigue material.As shown in fig. 4 a, first to A1D2G1Apply
Adding 1% small oscillation shear strain, then bring up to 50% from 1%, kept for 100 seconds, energy storage (G') is higher than loss energy (G "), and
And 1% should be once changed back to, they (are less than 10 seconds) immediately recovers original value.Similarly, answered when our applications later are larger
Become (100% and 200%), then using small strain (1%) when, G' also fast quick-recovery initial values, show that hydrogel network is able to
Recover (Fig. 4 a).
A under the continuous strain sweeps of Fig. 4 (a)1D2G1G' and G " be respectively 1%, 50%, 100% and 200% strain when
Alternate oscillation power.(b)A1D2G1There is the cyclic tension loading-unloading curve of different recovery times under 800% strain.(c)
A1D2G120 tensile loads-unloading circulation is carried out after recovering 10 minutes between each cycle.(d) 20 tensile loads-unload
Carry A after circulating1D2G1Dissipation energy and Young's modulus recovery extent.
The recovery deformed by cyclic tension test measurement.As shown in Figure 4 b, A1D2G1Sample under 800% strain,
Big hysteresis curve and about 0.97MJ m are shown in first loading-unloading circulation-3Dissipation energy.There is no any recovery to stop
Second circulation of breath time shows that hysteresis loop becomes smaller (about 0.31MJ m-3).After rest 5 minutes, dissipation energy is obvious
Recover.It is worth noting that, A1D2G1Hysteresis loop area, replied (0.95MJ m at subsequent 10 minutes-3) it is continuous plus
In load-unloading circulation, almost recover (Fig. 4 b) completely.In order to further explore tension cycles ability, we are in identical sample
On carried out the circulation of 20 subsequent tensile loads-unloading, the recovery (Fig. 4 c) between each circulation with 10 minutes.In order to more
The amount of reordering, we lose and (represented by calculating the Young's modulus under different loaded cycles (representing rigidity to recover) and dissipation energy
Toughness is recovered) ratio, determine rigidity and toughness recovery extent respectively.It can be seen from fig. 4d that after 5 circulations, A1D2G1
Hydrogel can make toughness recover 97.5%, and hardness recovers 97.4%.Even across 20 circulations, toughness/rigidity restoring degree is still
68.5%/90.5% so is may remain in, this shows A1D2G1Hydrogel has good reply and anti-fatigue performance.
The A of Fig. 5 (a) compressions1D2G1Hydrogel (above) and A1D2G0The image of hydrogel (figure below).(b)A1D2G1Not
With the compression curve under compression strain.(c)A1D2G1The circulation of 30 subsequent compression loading-unloadings, recover 40 between each circulation
Second.(d) after the circulation of 30 second compressions, A1D2G1Dissipation energy and recovery extent.
Anti-fatigue performance can also be circulated by compressible loading-unloading to reflect.As shown in Figure 5 a, A1D2G1Water-setting
Glue can manually compress release cycle and recover its original-shape in seconds.But A1D2G0It can not complete to recover.Will
Different strains is applied to A1D2G1, and its reset condition (Fig. 5 b) can be recovered completely under 80% big strain.By right
The continuous compression that identical hydrogel carries out circulates 30 circulations, the stand-by period (Fig. 5 c) of 40 seconds between each circulation, further
Strict test A1D2G1Recovery rate of the hydrogel under 80% strain.The load-deformation curve of all circulations is almost overlapping, shows
Plastic deformation eliminates significantly.Fig. 5 d summarize the relative dissipation energy and recovery extent in each cycle.The energy of consumption is reduced simultaneously
More than 66.7% is maintained at, recovery extent is declined slightly, and 86% is still higher than after 30 circulations.This mechanical cycles will not be to water
Gel produces any obvious macroscopic view change.This further demonstrates that P (AM-co-DAC)/GO hydrogels are in pressure operating environments
In reliable mechanical performance.In a word, these results indicate that can be by easily adjusting GO contents by simple one pot polymerization
With AM mass ratio, the P (AM-co- of high rigidity, high tensile and excellent anti-fatigue performance are produced under high elongation rate
DAC)/GO hydrogels and DAC.
Based on reversible electrostatic interaction and hydrogen bond, significant self-reparing capability of the hydrogel in water is realized.Such as figure
Shown in 6a, by A1D2G1The original cylindrical bars of sample cut into two halves, and cutting surfaces are simply in contact with each other and appointed without applying
What pressure.After bursting surface drips a drop water, sample is stood into a few hours (Fig. 6 b).The sample of reparation can be reached with pulling
Big strain (Fig. 6 c).The application also found, when two parts gel is put together with the help of no water, they can be
Mutually bonding at room temperature.However, bonding strength is weaker, easily ruptured in interface.These results indicate that ionic bond and hydrogen bond can
To be re-formed by the help of water.
The selfreparing property of Fig. 6 hydrogels.By A1D2G1The original cylindrical bars of sample cut in half (a).Two parts are simple
Singly contact, a drop water is dropped on cut surface (b).After standing a few hours, sample is stretched to big strain (c) with hand.(d)
A1D2G1Moisture water content of hydrogel after the different stand-by period of dripping change.(e) the different stand-by period after dripping,
A1D2G1Load-deformation curve.(f)A1D2GzHydrogel repairs the load-deformation curve before and after 20 hours at room temperature.(g)
The remediation efficiency of the fracture strength of all composite aquogels with different GO contents.
In order to systematically explore self-regeneration behavior, the influence of moisture and hydrogel repair time are have studied first.
After dripping, due to swelling, the water content of hydrogel increases to~37 weight % by~30 weight %.At room temperature, in hydrogel
Water slowly disappeared with the time.After 20 hours, water content reaches reset condition (about 29.8wt%) (Fig. 6 d).Pass through optical microphotograph
The self-repair procedure in situ (Figure 13) of sem observation difference stand-by period hydrogel.There is a very wide crack during contact start.Add
After water, hydrogel surface changes due to swelling.The addition of water promotes motion of the polymer chain at the plane of disruption.(P(AM-co-
DAC) the Dynamic ion interaction between GO and hydrogen bond can make polymer chain move to opposite side from side, cause hydrogel
Reparation, over time, the crackle at cut surface diminishes, almost without obvious crack (Figure 13) after 20 hours, I
Think the surface reconditioning of not only hydrogel, and the inside of hydrogel also completes repair process, as shown in fig 6e, A1D2G1
The stress diagrams of hydrogel difference stand-by period show that hydrogel can recover its reset condition in 20h repair processes, its
Secondary, the selfreparing of all hydrogels is 20 hours.
Fig. 6 f show the A after original and reparation1D2GzThe load-deformation curve of hydrogel.For A1D2G0, fracture strength
The 63.5% of primary stress can be reached.After adding 0.5wt%GO, A1D2G0.5Fracture strength return to original value
92.8%.This shows that the dependence hydrogen bond of P (AM-co-DAC) polymer chain can realize that selfreparing is inadequate only in hydrogel
, the significant self-repair efficiency for improving hydrogel of the electrostatic interaction of GO and polymer chain after GO is introduced.When GO contents
When reaching 1wt%, A1D2G1Self-repair efficiency reach the 92.3% of fracture strength, 99.5% and toughness of breaking strain
93.6% (Figure 14).Repair A1D2G1Tensile strength reach~503.4kPa in~1592.6% elongation, far above reparation
A afterwards1D2G0.5Tensile strength, further demonstrated that GO effect.However, as GO contents further increase, reactivation is reviewed one's lessons by oneself
It (is respectively A that power, which reduces,1D2G1.5And A1D2G2Fracture strength 61.7% and 47.8%).This is probably due to GO and polymer
Sizable interaction hinders the migration of P (AM-co-DAC) chain to a greater extent between chain, causes the soft of polymer chain
Property decline.
In addition, be investigated with different quality than AM and DAC hydrogel self-reparing capability (Figure 15, Figure 16).
With DAC content increase, the significant raising of self-repair efficiency.For example, when GO contents are 1wt%, self-repair efficiency is respectively
A1D0.5G1, A1D1G1And A1D2G1Fracture strength 58.5%, 84% and 92.3% (Fig. 6 g).Due to quiet between DAC and GO
Electric interactions are bigger, and therefore, DAC contents are higher to improve self-repair efficiency.The design of the application can pass through Reasonable adjustment
The composition of polyalcohol hydrogel and GO compositions, so as to improve mechanical strength, without losing self-reparing capability.The application will be certainly
For the hydrogel that I repairs compared with the data delivered in the past, our hydrogel shows highest self-repair efficiency, and
Its mechanical performance (Figure 17) will not be sacrificed.
The photo of the A1D2G1 samples (a) of the original dryings of Fig. 7.Water is sprayed on dry A1D2G1 (b).Stand 40
, can manual expanded material (c, d) after minute.(e) primary sample, and absorb the sample after water and cut off the sample after selfreparing
Load-deformation curve.
Importantly, the large quantity of moisture in hydrogel causes hydrogel transport difficult.Our hydrogel can be complete
Dry, be readily transported, and by the way that simply water is sprayed on dry sample, it is original mechanical performance can be returned to its
Value.As shown in Figure 7a, A1D2G1Hydrogel is completely dried at 40 DEG C, therefore becomes stone, without original stretching, compression
And self-healing properties.After dry hydrogel surface water spray, sample recovered its reset condition after 40 minutes can high drawing
Stretching property (Fig. 7 b-d).The sample of recovery is shown has similar breaking strain and fracture strength (Fig. 7 e) to primary sample.In addition,
After sample after recovery cuts off and repaired, hydrogel remains in that the self-repair efficiency of about 93% fracture strength of primary sample
(Fig. 7 e).
Conclusion
In a word, we have demonstrated that, simple one kettle way polymerization can prepare high rigidity (Young mould under high elongation rate
Amount：~1.1MPa), P (AM-co-DAC)/GO hydrogel -1700% of high tensile (2.1MPa), fatigue performance is good, from
Excellent (the tensile strength of remediation efficiency>92%, elongation strain>99%, toughness>93%).The mechanical performance of hydrogel can pass through
AM and DAC mass ratioes and GO content are controlled to adjust.Reversible ionic bond and hydrogen bond is responsible for energy dissipation and network reconnection.Phase
These materials are caused to turn into wide the combining properties and simple synthetic method of higher mechanical performance and high self-reparing capability
The ideal chose of general application.
The preferred embodiment of the application is the foregoing is only, is not limited to the application, for the skill of this area
For art personnel, the application can have various modifications and variations.It is all within spirit herein and principle, made any repair
Change, equivalent substitution, improvement etc., should be included within the protection domain of the application.
Claims (10)
- A kind of 1. preparation side of tough and tensile, stretchable, compressible, selfreparing polymer/stannic oxide/graphene nano composite aquogel Method, it is characterised in that including：It is nanoparticle by comonomer, graphene oxide GO of acrylamide AM and acrylyl oxy-ethyl-trimethyl salmiac DAC Son, radical polymerization in situ, produce tough and tensile, stretchable, compressible, selfreparing polymer/stannic oxide/graphene nano Compound Water Gel.
- 2. the method as described in claim 1, it is characterised in that the acrylamide AM and acrylyl oxy-ethyl-trimethyl chlorination Ammonium DAC mass ratio is 1：0.5~2；Or 0.5~2% that the dosage of the graphene is polymer monomer gross weight in hydrogel.
- 3. the method as described in claim 1, it is characterised in that N, N'- methylenes are used in the Raolical polymerizable in situ Base bisacrylamide MBA is crosslinking agent.
- 4. the method as described in claim 1, it is characterised in that the radical polymerization in situ concretely comprises the following steps：Will dissolving There are acrylamide AM, acrylyl oxy-ethyl-trimethyl salmiac DAC, N, N'- methylene-bisacrylamides MBA and graphene oxide The GO aqueous solution ice bath stirring, degassing, polymerisation, dehydration, produces under initiator existence condition.
- 5. method as claimed in claim 4, it is characterised in that the initiator is potassium peroxydisulfate APS, the double (2- of 2,2'- azos Methyl-prop amidine) dihydrochloride AIBA and formaldehyde sulfoxylate sodium hydrate ALD.
- 6. polymer/stannic oxide/graphene nano the composite aquogel that can be obtained by the method for any preceding claims is reviewed one's lessons by oneself Multiple method, including：The above-mentioned hydrogel plane of disruption of cut-off two parts is bonded；Then, by water droplet on the plane of disruption, stand, produce.
- 7. the hydrogel described in claim 6, there is~1.1MPa Young's modulus ,~9.3MJ m-3Toughness.
- 8. with~1.1MPa Young's modulus ,~9.3MJ m-3The hydrogel of toughness, include claim 1-5 any one institute The arbitrary characteristics listed.
- 9. acrylamide AM and acrylyl oxy-ethyl-trimethyl salmiac DAC comonomer prepare it is tough and tensile, stretchable, can press Contract, the application in polymer/stannic oxide/graphene nano composite aquogel of selfreparing.
- 10. include the filter of the hydrogel described in claim any one of 6-8, for heavy metal, solvent, oil, gasoline and liquid Absorber material, gas adsorption media, Water warfare medium, the electro-chemical device electrode of body absorption.
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Application publication date: 20180320 |