CN106190051A - The Graphene stack membrane of tool thermal conductance - Google Patents
The Graphene stack membrane of tool thermal conductance Download PDFInfo
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- CN106190051A CN106190051A CN201510223254.4A CN201510223254A CN106190051A CN 106190051 A CN106190051 A CN 106190051A CN 201510223254 A CN201510223254 A CN 201510223254A CN 106190051 A CN106190051 A CN 106190051A
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Abstract
A kind of Graphene stack membrane is deposition or is compressed on polyethylene terephthalate polyester (PET) base material, in order to judge to affect the physical parameter of conduction of heat.The pyroconductivity measurement of Graphene stack membrane be utilize a photo-thermal Raman technology and one group there is the sample that Graphene laminated thickness is 8 microns to 44 microns and carry out.The pyroconductivity of this Graphene stack membrane is at room temperature between 40 watts/ meter Du to 90 watt/ meter Du.It is found that, the average-size of graphene film with regard to conduction of heat define parameter for, more even more important than the mass density of this Graphene lamination.This pyroconductivity can linearly increase significantly with the average-size in the stack membrane of deposition and compression.This plastic material pyroconductivity maximum coating Graphene stack membrane can increase to × 600 class intervals, deeply has essential meaning.
Description
Technical field
The present invention is the Graphene lamination about a tool thermal conductance.
Background technology
Well known, Graphene has high thermoconductivity [XX].First measurement of suspension single-layer graphene shows that the pyroconductivity K value of this Graphene exceeds well over the pyroconductivity of graphite in bulk, and this K value is equal to 2000W/mK under room temperature (RT) [X].Although the dispersibility of phonon is similar with lattice off resonance, but the K value of Graphene is higher than graphite basal plane.Such interesting fact can be by the phonon conduction of specific long wavelength to two dimension (2-D) lattice [X].Long wavelength's phonon in two-dimensional graphene has the mean free path (MFP) of length-specific, though this conduction of heat diffusible [X], but it can be limited to the size of sample.Under different conditions, it means that the thermal balance of the independent diffusion couple approximation of this phonon Umklapp two-dimensional crystal lattice in three-dimensional lattice [X] recovers and insufficient.The latter can cause the pyroconductivity of abnormal few layer graphene (FLG) to have to rely on the atomic plane quantity in sample [X].The logarithm of the Graphene intrinsic heat conductivity of tool sample [X] size dissipates prediction, has been observed that recently and confirms in [X] in experiment.Other interesting feature of phonon thermal conductivity in Graphene, dissipates effect [X] including the non-monotonic dependency of Graphene band widish [X], powerful isotope, and point defect heat.
The superior thermal conductivity of the Graphene of tool Graphene flexibility ratio can be excited by the laminated material in various researchs, and wherein this Graphene and derivant thereof can be as filler [X].Liquid phase is peeled off (LPE) Graphene and can at a low price and be made in large quantities.Liquid phase peels off the suitably mixing of Graphene and FLG sheet can make it as excellent filler in thermal interfacial material (TIMs) [XX] and hot phase-change material (PCMs) [XX].It coupled to described base material due to graphene thermal and low cost liquid phase peels off Graphene preferably, therefore have more prospect as filler than CNT (CNTs) using Graphene.Graphene bearing part in laminated material is relatively low, that is, maximum of up to the 10% of thermal interfacial material (TIMs) [X], and maximum of up to phase-change material [X] 20%.It is generally believed that the Graphene filler in this material will not form percolating network, and its temperature can part be conducted via dilute of graphite and base material.
The different types of Graphene base material of tool heat application is for Graphene lamination (GL).The Graphene that this chemistry generates and the few layer graphene in graphene film can be closely loaded in overlay structure.Graphene film is deposited in polyethylene terephthalate polyester (PET) base material [X] the most universal.Can be rolled after " being sprayed on " on Graphene stack membrane.In view of the heat conductivity coating of various plastic materials is had increasing actual demand, about the thermal conductance research of graphene film also along with increase.Physics thermal conductance in this material but makes graphene film be presented in any overlapping region, the shortcoming such as large-size and thickness distribution.The thermal conductive property of Graphene lamination (GL) and the known materials parameter of restriction conduction of heat contribute to the actual application of the hot coating of Graphene lamination.
Summary of the invention
The main object of the present invention is to provide a kind of Graphene lamination having thermal conductance.
For reaching above-mentioned purpose, by a kind of Graphene stack membrane provided by the present invention, including:
One Graphene lamination, it is to deposit or be compressed on polyethylene terephthalate polyester (PET) base material, and this Graphene lamination includes monolayer, double-deck, and the storehouse portion of number layer graphene sheet.
This PET base material is made up of plastic material and has the pyroconductivity between 0.15 watt/ meter Du to 0.24 watt/ meter Du.
The thickness of this Graphene lamination is to be judged by profile scanning formula ultramicroscope (SEM), and it is the scope between 8 microns to 44 microns.
The mass density of this Graphene lamination is between 1.0 grams/cc to 1.9 grams/cc, and the resistance of this Graphene lamination is in the interval of 1.8 ohm to 6.1 ohm.
Accompanying drawing explanation
The target of the present invention utilizes preferred embodiment to be explained as follows in more detail:
Fig. 1 is for number one sample schematic diagram under profile scanning formula ultramicroscope (SEM), it is shown in the graphene film on polyethylene terephthalate polyester (PET) base material, it has the top layer that a thickness is about 44 microns, storehouse portion, and thickness is about 100 microns and for the lower floor of PET base material, the graphene film thickness under this ultramicroscope (SEM) display image is in different size；
Fig. 2 is the image under sweep electron microscope (SEM) for No. three sample (a) and No. four sample (b), and it is that display one respectively is uncompressed and the stack surface of compression；Wherein, Graphene lamination includes monolayer, double-deck, and the storehouse portion of number layer graphene sheet, and it is in arbitrary shape and direction arrangement；Bright areas shows graphene film arranged vertically, and it is in the graphene film edge of uncompressed sample, and the sample compressed then significantly reduces；
Fig. 3 is to consider that the quantity of graphene film is many, therefore its mean tabular size is in convergence state to its total value, and wherein, it is to represent with the first, four and No. six catalogue number(Cat.No.), and its more than 100 after sheet number converge to end value 1.10,1.18；And 0.96；
Fig. 4 is the fixed mount optical imagery figure for the numerous thin slice samples in photo-thermal Raman Measurement.(in strip person), the Graphene lamination on polyethylene terephthalate polyester (PET) base material (GL-on PET) is to pass one to fix in groove in testing for this, interfixes with two aluminium flakes as fin.This strip sample is to heat with Raman laser.And experimental provision is the enlarged version for being originally used for measuring graphene thermal conductivity；
Fig. 5 be show second and three sample Raman G peak skew with temperature correction measure pass be, wherein, by increase temperature the G peak position of this sample can be made linearly to decline；
Fig. 6 be show first and four sample Raman G peak skew with its laser power pass be, wherein, by increasing laser power, this first and four the G peak position of sample be linearly to decline, and this power is to use OPHIR energy meter to record at sample end face, via this slope of a curve, it is appreciated that this sample pyroconductivity；
Fig. 7 is that the average-size pass of the pyroconductivity and its Graphene lamination that show compression and uncompressed sample is, wherein, when the Graphene lamination average-size of this compression and uncompressed sample increases, this pyroconductivity is to linearly increase, and the pyroconductivity of the uncompressed sample of thermal conductivity ratio of this compression samples is high.
Detailed description of the invention
The present invention investigates the method for Graphene stack membrane, it is available for accurately investigating the thermal conductance of the Graphene lamination on polyethylene terephthalate polyester (PET) base material, it is to use one group of sample being deposited and compressed and have different densities of weight, the thickness range of this graphene film is between 8 microns to 44 microns, wherein this measurement is to use photo-thermal Raman technology [X], and this photothermal technique is initially introduced in deflocculated graphite alkene sample [X] of micron scale, this sample is extended and is applied on suspending film.Sample about the pyroconductivity investigation method of Graphene stack membrane is prepared and material behavior, and this Graphene lamination is deposited in PET base material.Sample group is with uncompressed " and " compression " represent.This PET base material is the plastic material for manufacturing various container.The pyroconductivity scope of this PET base material is 0.15 watt/ meter Du to 0.24 watt/ meter Du under room temperature environment.The too low meeting of K value of PET base material limits its application.The thickness of this Graphene lamination (be called for short GL layer) is to be judged by profile scanning formula ultramicroscope (SEM), and it is between the scope of 8 microns to 44 microns.Due to the heterogeneity of thickness, it is applied in this analysis therefore in the meansigma methods between several positions.The mass density of this GL layer is between 1.0 grams/cc to 1.9 grams/cc.The resistance of each GL layer is measured in the interval of 1.8 ohm to 6.1 ohm.Fig. 1 is that the image that the Graphene in PET base material is stacked under sweep electron microscope, wherein this PET base material and GL layer can be resolved easily.This Graphene stack membrane is made up with few layer graphene of the single layer stack Graphene of tool different size and shape.Quantitative analysis about heat conductivility must measure statistical data accurately according to average graphite alkene chip size.But in the case of and change of shape relatively big in size, this measurement is difficult to carry out.Fig. 2 is the Graphene lamination sample image under sweep electron microscope in this uncompressed and compression PET base material.We study under sweep electron microscope, to determine average graphite alkene chip size D, its minimum being defined as averagely every and maximum gauge.Each sample is all measured exceeding hundreds of graphene films, in order to accumulation can accurately calculate the sufficient statistic evidence of D value.Fig. 3 shows the convergence situation of the mean tabular dimension D value of each sample.Here it will be seen that, analyze the 50th average-size that graphene film is later change in operation until a certain clear and definite definition value.List I provides sample and the title of corresponding lamellar size thereof.
About the measurement of pyroconductivity, it is to use the graceful method of contactless optical hot-drawn to carry out this heat research [X].This is the measurement technology under a kind of direct state, and it can directly determine pyroconductivity, and without being calculated this pyroconductivity by the data of described thermal diffusion.In the art, just having started to measure the heat conductivity of Graphene [X], micro-Raman spectrometer then may be used as thermometer, it is judged that the on-the-spot temperature risen.Raman laser also can be as a heater.This measurement process includes two steps: calibration measurement and power dependent Raman Measurement.This micro-Raman spectrum (Renishaw In Via) is to use the laser of 488 nm and 1 milliwatt to 10 milliwatt power levels.Graphene lamination sample in this PET base material is cut into strip (that is, the length of 3 centimeters and the width of 1 centimeter) and is placed in a specially designed sample and fixes and (see Fig. 4) on seat.Substantial amounts of aluminium flake-clamper can be as preferable fin, it is ensured that good with thermally contacting of GL layer.
Calibration measurement is to carry out can control the cold-hot cell of sample temperature (LINKAM THMS-600).For this controllable temperature of equipment measured between-196 DEG C to 600 DEG C, and this temperature has the temperature stability less than 0.1 DEG C.The low exciting power of Raman laser (-1 milliwatt) may be used to avoid on-the-spot laser induction heating.Owing to low exciting power level can reduce signal-noise (S/N) ratio, therefore we increased time of exposure to 10 seconds, in order to obtain acceptable S/N ratio.This measurement repeats 3 times, and provides each temperature, in order to obtain average temperature value.The Raman G peak position obtained in this calibration measurement can be as the temperature funtion of sample.Fig. 5 demonstrates in the interval of 20 DEG C to 200 DEG C, the Graphene lamination sample that two are uncompressed in PET base material, the G peak spectral position of its temperature funtion T.It may be noted that two approximations being similar to pattern detection temperature range and straight slope meet the condition of preferable laser.This slope can determine the temperature at the Raman G peak of these samples be numerical value be G ≈-1.910-2CM-1/K.It must be kept in mind that this G-value depends not only on sample properties, and depend on its temperature range being acquired.The Part II of this measurement is the Raman G peak position (seeing Fig. 4) of the Graphene lamination sample in record PET base material, as increasing the function exciting laser power.Power in this sample surface is to utilize energy meter (OPHIR) to replace sample to measure.This absorbed power is below the Graphene lamination sample by being replaced by PET base material, be positioned at sample fix seat fix groove energy meter determine.Measurement result shows, most power can be absorbed by the sample, and only fraction (less than 1%) is not absorbed because laser beam spills from sample both sides.Absorbed laser power P increases, and may result in the local heating of Raman G peak skew.Fig. 6 shows that condensation and the measured G peakdeviation of uncooled sample can be as this functions of absorbed power.It is possible to note that the sample of two kinds of tool diverse microcosmic structures (compression is with uncompressed), there is under identical heating power different temperatures and rise result.The slope Δ ω/Δ P of the Graphene lamination sample the 1st to 6 in this PET base material, the most measured be :-0.2451 ,-0.2255 ,-0.1521 ,-0.1776 ,-0.1766-0.1739 and-1/ milliwatt.It can thus be appreciated that the geometry of sample and temperature rise T=G-1, the corresponding power P absorbed, therefore pyroconductivity K can be determined by solving the numerical value of thermic vibrating screen.The details of K acquisition process is specified in following method content.
The RT thermal conductivity measured by Graphene lamination sample in the different uncooled and PET base material of condensation is shown in Fig. 7, and sums up and be shown in list II.Several interesting points that must be noted that are, the overall thermal coefficient of conductivity of the Graphene lamination sample in this PET base material is up to K ≈ 40W/mK to-90W/mK.Consider that PET and relevant plastic material have K ≈ 0.15W/mK and can increase above two orders of magnitude pyroconductivity away from (× 170-× 600) to-0.24W/mK, the PET of applying implenent Graphene lamination.These data recorded show, can obtain high-termal conductivity in compression and uncompressed sample.As seen from Figure 7, uncompressed and compression samples K value has linear relationship with average graphite alkene chip size D.We do not find the mass density tool direct relation of this K value and sample.All K values and K value dependency in graphene film size show, the conduction of heat of GL layer is to be limited by graphene film, rather than are limited by the characteristic of single-layer graphene and few layer graphene.It is compressed may result in these graphene films tool preferably alignment result or being closer to each other, so that the graphene film of each size has higher K value.This conclusion can be supported by the analysis of SEM image top view, but suggestion uses the less graphene film being positioned at vertical direction in by compression samples.This unjustified graphene film is to show (seeing Fig. 2) with bright white point.
It was found that when obtaining higher K value, this numerical value is to uncompressed and had practical significance by the Graphene lamination sample compressed in PET base material.This represents, even in " being sprayed at " Graphene coating, and does not carries out rolling or other process step, still contributes to improving the heat conductivity of plastic material.The new opplication of plastic material, such as, when packing or be coated with electronic building brick, need higher heat conductivity.The latter is about increasing existing electronics and photoelectronic heat radiation density.For in meaning, Graphene overlapping layers has potential thermal coating effect.The GL layer of different-thickness can change flexibly, in order to increase thermal conductance amount via coating layer.
Therefore, the method for the thermal conductance of investigation Graphene thin stack, comprise the following steps:
A) preparing Graphene stack membrane, wherein, the aqueous dispersion of this Graphene nm sheet, Grat ink 101 is to be provided by blue stone whole world science and technology, the coating ink in studying as this, and is normally at the PET film of top as the base material in research.Graphene ink, is coated on PET with the special groove type coating machine of laboratory (Taiwan, Shining Energy company, type SECM02), and carries out the dry place mile of 10 minutes at 80 DEG C, uses the Graphene lamination sample formed in PET base material.One roller press (Taiwan, Shining Energy company, type SERP02) more can be applicable to condense on sample.The sheet resistance of this Graphene stack membrane is by 4 point probes (Britain, Jandel company, type RM3000), measures in difference altogether 10.
B). measuring the density of sample, wherein the Graphene lamination sample in PET base material and PET base material are to utilize a discoid pressing mold (diameter 12mm) to carry out punching press.For reaching the average weight of Graphene coating, the sample having 10 groups of Different Weight is measured by 5 figure place analysers (U.S., Mettler Toledo Inc., type XS 105DU) respectively.The density of this Graphene lamination, coating thickness, pressing mold diameter and weight can be via calculating.
C). obtaining pyroconductivity, the Fourier equation being wherein applied to specific sample geometry can be used to obtain this pyroconductivity.Owing to, in GL layer thickness significantly greater (8 meters to 44 microns), this thermic vibrating screen can be applicable in three-dimensional (3-D) structure.We use formula and the numerical solution having suitable boundary condition in COMSOL software kit.This laser heat point source is assumed the Gauss distribution with power P (X, Y, Z), is sheathed in sample via following equation:
Wherein, PtotBe sample absorbed general power, and σ system is by the standard deviation of gauss of distribution function defined in laser point light size.Full width at half maximum (FWHM) (FWHM) is between 0.5 micron, and it is the radius as laser source.The Graphene lamination strip sample that this is suspended in PET base material is fixed to fin two ends, and this fin is under room temperature.Other boundary condition systems all by defined in environment, that is, the thermograde on whole border is set to zero:
Thermic vibrating screen can be solved by iterative process.Then, in input general power and pyroconductivity to equation, and the simulation result of Temperature Distribution is determined.Emulation temperature rise can be made comparisons with in the temperature measured by laser point.This pyroconductivity can be raised according to comparative result or turn down.This task can be simplified by importing Slope Parameters:
The analog result of K and θ value can provide the actual value of pyroconductivity K as slope measurement.
Claims (1)
1. a Graphene stack membrane, it is characterised in that comprise:
One Graphene lamination, it is deposition or is compressed in polyethylene terephthalate polyester (PET) base material
On, this Graphene lamination includes monolayer, double-deck, and the storehouse portion of number layer graphene sheet, wherein
This PET base material is made up of plastic material and has between 0.15 watt/ meter Du to 0.24 watt/meter
The pyroconductivity of degree；
The thickness of this Graphene lamination be by one profile scanning formula ultramicroscope (SEM) judge, its be between
The scope of 8 microns to 44 microns；
The mass density of this Graphene lamination between 1.0 grams/cc to 1.9 grams/cc, and
The resistance of this Graphene lamination is in the interval of 1.8 ohm to 6.1 ohm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112725742A (en) * | 2019-10-28 | 2021-04-30 | 国家纳米科学中心 | Sandwich structure material and preparation method and device thereof |
| CN114211831A (en) * | 2021-12-24 | 2022-03-22 | 中科合肥智慧农业协同创新研究院 | Preparation method of degradable thickened graphene photothermal conversion mulching film |
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| CN102906015A (en) * | 2011-02-09 | 2013-01-30 | 创业发展联盟技术有限公司 | Method for producing multilayer graphene coated substrate |
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| CN101605658A (en) * | 2007-02-14 | 2009-12-16 | 东丽株式会社 | Highly adhesive multilayer thermoplastic resin film |
| CN101275035A (en) * | 2007-03-27 | 2008-10-01 | 丰田合成株式会社 | Low electric conductivity high heat radiation polymeric composition and molded body |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112725742A (en) * | 2019-10-28 | 2021-04-30 | 国家纳米科学中心 | Sandwich structure material and preparation method and device thereof |
| CN114211831A (en) * | 2021-12-24 | 2022-03-22 | 中科合肥智慧农业协同创新研究院 | Preparation method of degradable thickened graphene photothermal conversion mulching film |
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Application publication date: 20161207 |