CN107677711A - A kind of macromolecule liquid-sensitive sensor based on nano-graphene and preparation method thereof - Google Patents
A kind of macromolecule liquid-sensitive sensor based on nano-graphene and preparation method thereof Download PDFInfo
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- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
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- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
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Abstract
The invention discloses a kind of macromolecule liquid-sensitive sensor based on nano-graphene and preparation method thereof.Comprise the following steps that：(1) NGO and PMMA particles are well mixed by homogenizer, obtain the highly conductive primary particles of NGO/PMMA；(2) by the highly conductive primary particles of NGO/PMMA and UHMWPE particles in stirrer for mixing；(3) it is the compound particle being mixed to get is compressing, obtain the macromolecule liquid-sensitive sensor based on nano-graphene.The inventive method prepares a kind of double isolation structures of novel conductive conducting networks using NGO in polymer particle surface selective distribution, make material that there is higher electrical conductivity, high liquid-sensitive, and preparation technology is simple, production cost is low, easily realizes and produces in enormous quantities.
Description
Technical field
The present invention relates to conducting polymer liquid-sensitive sensor technical field, more particularly to a kind of height based on nano-graphene
Piquid-sensitive sensing of molecule and preparation method thereof.
Background technology
Application of the filled-type conductive polymer composite in liquid-sensitive sensor field attracts widespread attention.High score
The compound piquid-sensitive material of son has the advantages that high sensitivity, cost are low, it is simple to prepare, and sensing liquid principle is group effect, is adsorbed in
Influence of other chemical moleculars on surface to transducer sensitivity is smaller, therefore macromolecule liquid-sensitive sensor turns into Recent study
Focus, thus the context of detection of the leakage of organic solvent has broad application prospects in environmental monitoring, Chemical Manufacture.But
It is that macromolecule liquid-sensitive sensor prepared by conventional fusion processes needs more conductive filler to build perfect conductive network, that is, leads
Electric excess effusion value is higher, therefore the mechanical property of material is low, poor processability and cost are high.And the high score with homogeneous conductive network
The susceptibility of the piquid-sensitive effect of the piquid-sensitive composite of son is reduced with the raising of materials conductive rate, and which results in make
The piquid-sensitive composite of macromolecule of standby high response intensity just must expendable material conductance, therefore limit it and further should
With.
In order to reduce the preparation cost of the piquid-sensitive composite of macromolecule, the physical mechanical and processing characteristics of material are improved, most
Effective method is exactly to reduce conductive excess effusion value.It is to drop so far that isolation structure conductive network is formed in macromolecule liquid-sensitive sensor
Low excess effusion value example the most successful.It is characterized in that conducting particles is not randomly distributed in matrix material, but selectivity point
Cloth between the particle interface of polymeric matrix, therefore formed improve conductive network required for the content of conducting particles can substantially reduce
For example, Grunlan et al. is successfully prepared nano graphene oxide/polyvinyl acetate isolation structure height using emulsion mixing method
Molecular composite material, its conductive excess effusion value only 0.05wt.% is found in terms of patent and document, most of isolation structures are high
The preparation of molecular composite material is all based on emulsion or solution mixing method, and such a method consumes a large amount of solvents and preparation due to needing
Process is complicated, is not easy to realize large-scale industrial production.
But conventional isolation structure conductive polymer composites are due to the interfacial interaction of its extreme difference, in organic solvent
Infiltration under be easy to crush, it is difficult to be applied in liquid-sensitive sensor field, thus must to composite carry out morphology control
And the suitable matrix material of selection could realize the low piquid-sensitive composite of macromolecule for exceeding and oozing the high response of high conductance.
The content of the invention
Compared to the prior art, it is an object of the invention to provide a kind of technique simply macromolecule based on graphene is piquid-sensitive
Sensor and preparation method thereof；The inventive method low production cost, easily realize and produce in enormous quantities；Produce obtained piquid-sensitive biography
Sensor has lower excess effusion value, good electric property and higher liquid-sensitive.
Present invention selection has the solvent resistant skeleton of excellent solvent resistance and highly viscous UHMWPE as material,
Distribution has the PMMA and excellent electrical conductivity and big of higher sensitivity to a variety of organic solvents between the interface of UHMWPE particles
The NGO composite conducting masterbatch of draw ratio, then by hot-forming, prepare the NGO/PMMA/UHMWPE with double isolation structures
Liquid-sensitive sensor.Different from the liquid-sensitive sensor of routine, the conductive unit of macromolecule liquid-sensitive sensor is related in the present invention is then
The carrier of highly conductive primary particle, i.e. PMMA as conducting particles NGO, under extremely low NGO contents effectively increase conduction and exceed and ooze
The degree of perfection of NGO networks in phase, weaker interface interaction is also beneficial to infiltration and the UHMWPE of fluid molecule between NGO networks
Excellent solvent resistance ensures dimensional stability of the material under the erosion of solvent, show it is low exceed ooze highly conductive strong fluid-sensitive
Property.In the composite that the present invention obtains, base materials of the UHMWPE as main liquid-sensitive sensor, NGO is as conductive phase, PMMA
Carrier as NGO.
The goal of the invention of the present invention is realized by following means.
The present invention provides a kind of preparation method of the macromolecule liquid-sensitive sensor based on nano-graphene, and specific steps are such as
Under：
(1) by nano graphene oxide NGO and polymetylmethacrylate particle by being mixed in homogenizer
Uniformly, the highly conductive primary particles of NGO/PMMA are obtained；
(2) the highly conductive primary particles of NGO/PMMA and ultra-high molecular weight polyethylene UHMWPE particles are mixed in mixer
Close；(3) it is mixed compound particle in step (2) is compressing, the piquid-sensitive sensing of macromolecule based on nano-graphene is made
Device；Wherein：
Ultra-high molecular weight polyethylene UHMWPE, polymetylmethacrylate and polymetylmethacrylate matter
It is (58~96) to measure ratio:(3.9~40):(0.1~2).
In the present invention, in step (1), a diameter of 8~48 μm of polymetylmethacrylate particle；Polymethyl
Sour methyl esters PMMA weight average molecular weight is 4~160,000.
In the present invention, in step (1), mixing temperature is no more than 48 DEG C.
In the present invention, in step (2), ultra-high molecular weight polyethylene UHMWPE weight average molecular weight is 200~5,000,000.
In the present invention, in step (2), mixing temperature is no more than 60 DEG C.
In the present invention, in step (3), compressing technique is as follows：Preheated at a temperature of 176~198 DEG C, the time is
5~10 minutes, then 10~12MPa pressure hot pressing 5~10 minutes, were finally cold-pressed to room temperature under 10~12MPa pressure.
In the present invention, ultra-high molecular weight polyethylene UHMWPE, polymetylmethacrylate and poly-methyl methacrylate
Ester PMMA mass ratio is (60~80):(10~30):(0.5~1).
The present invention also provides a kind of piquid-sensitive by the macromolecule based on nano graphene oxide made from above-mentioned preparation method
Sensor.
Compared to the prior art, the beneficial effects of the present invention are：
1) NGO is coated on PMMA particle surfaces by the present invention using high speed machine paddling process, is prepared into conducting masterbatch particle,
Mixed again with UHMWPE powders.And operation is uncomplicated, easily implements, easily expand as industrialized production.
2) material processing is simple, and without any solvent in preparation process, NGO additions are extremely low, and life is greatly lowered
Produce cost.3) the piquid-sensitive behavior of the double isolation structure macromolecule liquid-sensitive sensors of UHMWPE is regulated and controled jointly by adding PMMA and NGO,
Under relatively low NGO content, it is possible to realize high liquid-sensitive and electrical conductivity.The conductive excess effusion value of high polymer material is
0.10vol.%；When NGO volume contents are 0.5%, the electrical conductivity can of material reaches 1.1s/m；When NGO volume contains
When amount is only 0.4%, the electrical conductivity of material is 1.1S/m, and liquid-sensitive is up to 7.8 × 104%.
Specific embodiment
Specific embodiment is given below to be described further to technical scheme, but what deserves to be explained is with
Lower embodiment is it is not intended that limiting the scope of the invention, and the person skilled in the art in the field is according to the invention described above
Content, the modifications and adaptations for making some non-intrinsically safes to the present invention still fall within protection scope of the present invention.UHMWPE's divides equally again
The weight average molecular weight that son amount is 200~7,000,000, PMMA is 5~120,000.
Embodiment 1
Primary raw material is formed as following weight percent：UHMWPE96%；PMMA3.9%；NGO0.1%.
Processing step uses：
(1) raw material drying：By NGO, drying is at least 12 hours small to moisture weight content in the vacuum drying oven of 77 DEG C of constant temperature
In 0.01%.
(2) prepared by NGO/PMMA conducting masterbatch：NGO the and PMMA particles that gained is dried are stirred 6 in homogenizer
Minute, stir speed (S.S.) is 26000 revs/min, and whipping temp is more than 43 DEG C, ultimately forms NGO/PMMA of the diameter less than 28 μm and leads
Electric particulate；
(3) mixed at high speed：The NGO/PMMA conducting particles prepared and dried UHMWPE particles are existed in proportion
Mixed at high speed 5 minutes (keeping mixing temperature to be no more than 58 DEG C), completes conducting particles pair under 24000 revs/min of stir speed (S.S.)
UHMWPE is uniformly coated.
(4) it is compressing：Obtained NGO/PMMA/UHMWPE conductive composite particles precompressed 3 minutes at room temperature, precompressed pressure
Power 980MPa；Then hot pressing 12 minutes under 168 DEG C and 0.1MPa；Room temperature is finally cooled at ambient pressure, obtains target product.
Embodiment 2
The other the same as in Example 1, raw material proportioning UHMWPE96%；PMMA3.9%；NGO0.1%.In (1) step, NGO
78 DEG C of oven temperature.
When prepared by (2) step NGO/PMMA compound particles, the stir speed (S.S.) of homogenizer is 23000 revs/min；
The compressing press temperature of (4) step is 162 DEG C；
Embodiment 3
The other the same as in Example 1, raw material proportioning UHMWPE90%；PMMA9.5%；NGO0.5%.In (1) step, NGO
75 DEG C of oven temperature.
When prepared by (2) step NGO/PMMA conducting masterbatch, the stir speed (S.S.) of homogenizer is 21000 revs/min；
The compressing press temperature of (4) step is 186 DEG C.
Embodiment 4
The other the same as in Example 1, raw material proportioning UHMWPE90%；PMMA9.5%；NGO0.5%.In (1) step, NGO
80 DEG C of oven temperature.When prepared by (2) step NGO/PMMA conducting masterbatch, the stir speed (S.S.) of homogenizer is 25000 revs/min
Clock；It it is 188 DEG C in the compressing press temperature of (4) step.
Embodiment 5
The other the same as in Example 1, raw material proportioning UHMWPE80%；PMMA18.8%；NGO1.2%.In (1) step,
82 DEG C of NGO oven temperatures.
When prepared by (2) step NGO/PMMA conducting masterbatch, the stir speed (S.S.) of homogenizer is 26800 revs/min；
The compressing press temperature of (4) step is 195 DEG C.
Embodiment 6
The other the same as in Example 1, raw material proportioning UHMWPE80%；PMMA19%；NGO1%.In (1) step, NGO dries
84 DEG C of box temperature degree.
When prepared by (2) step NGO/PMMA conducting masterbatch, the stir speed (S.S.) of homogenizer is 28400 revs/min；
The compressing press temperature of (4) step is 198 DEG C.
Embodiment 7
The other the same as in Example 1, raw material proportioning UHMWPE60%；PMMA38%；NGO2%.In (1) step, NGO dries
87 DEG C of box temperature degree.
When prepared by (2) step NGO/PMMA conducting masterbatch, the stir speed (S.S.) of homogenizer is 29800 revs/min；
The compressing press temperature of (4) step is 216 DEG C；
Performance test is tested
Electric property：In order to investigate the electricity percolation of the double isolation structure liquid-sensitive sensors of NGO/PMMA/UHMWPE, adopt
Electrical testing is carried out to sensor material with Keithley4200SCS resistance instrument (Keithley, the U.S.), test result is shown in Table
1, it can be seen that the conductive excess effusion value of the double isolation structure liquid-sensitive sensors of NGO/PMMA/UHMWPE is 0.10vol.%.In NGO bodies
When product content is 0.5%, the electrical conductivity can of material reaches 1.1s/m, can meet that liquid-sensitive sensor is wanted to electrical conductivity substantially
Ask.
The electric property excess effusion value of table 1NGO/PMMA/UHMWPE liquid-sensitive sensors
| NGO (vol%) | 0 | 0.1 | 0.2 | 0.3 | 0.4 | 0.5 | 1 |
| Conductance S/m | 10-15 | 10-7 | 10-3 | 10-1 | 1.1 | 1.2 | 1.3 |
Piquid-sensitive performance：In order to investigate the piquid-sensitive performance of the double isolation structure macromolecule liquid-sensitive sensors of NGO/PMMA/UHMWPE,
Using piquid-sensitive row of the Keithley4200SCS resistance instrument (Keithley, the U.S.) to sensor material under different organic solvents
To be studied.In chloroform, dimethylformamide, toluene and acetone, NGO volume contents are only 0.4% sensor
Piquid-sensitive intensity distribution is respectively 7.8 × 104%, 1.7 × 103%, 4.5 × 103% and 3.3 × 102%, particularly to three chloromethanes
Alkane shows very high piquid-sensitive intensity.By containing to NGO in the double isolation structure macromolecule liquid-sensitive sensors of NGO/PMMA/UHMWPE
Measure the research to its piquid-sensitive behavioral implications and find that, with the increase of NGO additions, sensor material is shown in chloroform
Piquid-sensitive intensity gradually increase, when NGO volume content is only 0.4%, the electrical conductivity of material is 1.1S/m, liquid-sensitive
Up to 7.8 × 104%.
Claims (8)
1. a kind of preparation method of the macromolecule liquid-sensitive sensor based on nano-graphene, it is characterised in that comprise the following steps that：
(1) nano graphene oxide NGO and polymetylmethacrylate particle are well mixed in homogenizer, obtained
To the highly conductive primary particles of NGO/PMMA；
(2) by the highly conductive primary particles of NGO/PMMA and ultra-high molecular weight polyethylene UHMWPE particles in stirrer for mixing；
(3) it is mixed compound particle in step (2) is compressing, the piquid-sensitive sensing of macromolecule based on nano-graphene is made
Device；Wherein：
Ultra-high molecular weight polyethylene UHMWPE, polymetylmethacrylate and polymetylmethacrylate mass ratio
For (58~96):(3.9~40):(0.1~2).
2. preparation method according to claim 1, it is characterised in that in step (1), polymetylmethacrylate grain
A diameter of 8~48 μm of son；The weight average molecular weight of polymetylmethacrylate is 4~160,000.
3. preparation method according to claim 1, it is characterised in that in step (1), mixing temperature is no more than 48 DEG C.
4. preparation method according to claim 1, it is characterised in that in step (2), ultra-high molecular weight polyethylene UHMWPE
Weight average molecular weight be 200~5,000,000.
5. preparation method according to claim 1, it is characterised in that in step (2), mixing temperature is no more than 60 DEG C.
6. preparation method according to claim 1, it is characterised in that in step (3), compressing technique is as follows：
Preheated at a temperature of 176~198 DEG C, the time is 5~10 minutes, then 10~12MPa pressure hot pressing 5~10 minutes, finally
It is cold-pressed under 10~12MPa pressure to room temperature.
7. preparation method according to claim 1, it is characterised in that ultra-high molecular weight polyethylene UHMWPE, poly- methyl-prop
The mass ratio of e pioic acid methyl ester PMMA and polymetylmethacrylate is (60~80):(10~30):(0.5~1).
A kind of 8. macromolecule liquid-sensitive sensor based on nano-graphene that preparation method according to claim 1 obtains.
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Cited By (1)
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| CN110493900A (en) * | 2019-08-06 | 2019-11-22 | 常州大学 | A kind of 36V and the PTC Electric radiant Heating Film of following low voltage drive and preparation method thereof |
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Application publication date: 20180209 |