Anisotropic heat transfer, electromagnetic interference shielding composite and method for preparation thereof
11612088 · 2023-03-21
Assignee
Inventors
- Chi Ho KWOK (Hong Kong, CN)
- Mei Mei Hsu (Hong Kong, HK)
- Ka I Lee (Hong Kong, CN)
- Chenmin LIU (Hong Kong, CN)
Cpc classification
D01D5/003
TEXTILES; PAPER
D01G13/00
TEXTILES; PAPER
D04H1/74
TEXTILES; PAPER
D06M11/83
TEXTILES; PAPER
H05K7/20481
ELECTRICITY
D01F1/09
TEXTILES; PAPER
H05K9/009
ELECTRICITY
International classification
H05K9/00
ELECTRICITY
D01G13/00
TEXTILES; PAPER
D04H1/74
TEXTILES; PAPER
Abstract
The present invention provides an anisotropic, thermal conductive, electromagnetic interference (EMI) shielding composite including a plurality of aligned polymer nanofibers to form a polymer mat or scaffold having a first and second planes of orientation of the polymer nanofibers. The first plane of orientation of the polymer nanofibers has a thermal conductivity substantially the same as or similar to that of the second plane, and the thermal conductivity of the first or second plane of orientation of the polymer nanofibers is at least 2-fold of that of a third plane of orientation of the polymer nanofibers which is about 90 degrees out of the first and second planes of orientation of the polymer nanofibers, respectively, while the electrical resistance of each of the first and second planes is at least 3 orders lower than that of the third plane. A method for preparing the present composite is also provided.
Claims
1. An anisotropic, electrical conductive and thermal conductive, electromagnetic interference shielding composite comprising: a plurality of aligned polymer nanofibers to form a polymer mat or scaffold having a first plane and a second plane of orientation of the polymer nanofibers with a thermal conductivity of at least 2-fold higher than that of a third plane of orientation of the polymer nanofibers, each of the polymer nanofibers being incorporated with a plurality of thermal conductive fillers and a plurality of a first metal compound electrospun with a polymer to form a plurality of electrospun polymer nanofibers with a core or polymer matrix of the thermal conductive fillers and the first metal compound in the polymer nanofibers and deposited with a plurality of a second metal compound on the surface of the electrospun polymer nanofibers to form the plurality of aligned polymer nanofibers, the composite having the thermal conductivity of at least about 110 W/mK along the first and second planes of orientation of the polymer nanofibers and an electromagnetic interference shielding effectiveness against electromagnetic waves at lower frequency from 100 MHz to 1.5 GHz or higher frequency from 1.5 GHz to 30.0 GHz comparable to or slightly higher than that of the corresponding pure metal of the first or second metal compound, and the first and second planes of orientation of the aligned polymer nanofibers having substantially identical or similar electrical conductivities and resistances which the electrical resistance of each of the first and second planes of orientation is at least 3 orders lower than that of a third plane of orientation of the polymer nanofibers.
2. The composite of claim 1, wherein the thermal conductive fillers and first metal compound are jointly or independently one or more of carbon nanotubes, boron nitrates, aluminum nitride, ceramic polymers and metal nanoparticles.
3. The composite of claim 1, wherein the second metal compound comprises one or more of silver, nickel, platinum and copper, or the metal alloy thereof.
4. The composite of claim 1, wherein the polymer comprises one or more of polyacrylonitrile (PAN), poly(vinylidene fluoride) (PVDF), polyimide (PI), poly(lactic acid) (PLA), caboxymethyl cellulose (CMC), and poly(vinyl pyrrolidone) (PVP).
5. The composite of claim 1, wherein the polymer:thermal conductive fillers:first metal compound is in a weight ratio of about 50:1-4:8-32.
6. The composite of claim 1, wherein the first metal compound:second metal compound is in a weight ratio of about 1.8:1.
7. The composite of claim 1, wherein the second metal compound is deposited on the electrospun polymer nanofibers by one or more of electroless plating, chemical vapor deposition, physical vapor deposition, plasma-enhanced chemical vapor deposition and thermal evaporation methods.
8. A method for preparing the composite of claim 1, comprising: providing a solution of the thermal conductive fillers including dispersing the thermal conductive fillers into a solvent for a first period of time; dissolving the polymer into the solution of the thermal conductive fillers at a temperature for a second period of time to obtain a solution of the thermal conductive fillers and polymer; mixing the first metal compound with the solution of the thermal conductive fillers and polymer for a third period of time to obtain a solution of the thermal conductive fillers, polymer and first metal compound; electrospinning the solution of the thermal conductive fillers, polymer and first metal compound to generate a plurality of aligned, electrospun polymer nanofibers; drying the aligned, electrospun polymer nanofibers; reducing the first metal compound to become metal nanoparticles; compressing the aligned, electrospun polymer nanofibers to obtain a mat or scaffold of aligned, electrospun polymer nanofibers; depositing a solution of the second metal compound onto each of the aligned, electrospun polymer nanofibers electrolessly; and sintering the mat or scaffold of the aligned, electrospun polymer nanofibers to obtain the composite.
9. The method of claim 8, wherein the solvent used to dissolve the thermal conductive fillers comprises dimethylformamide (DMF), dimehtylacetamide (DMAC), N-Methyl-2-pyrrolidone (NMP) and acetone.
10. The method of claim 8, wherein the electrospinning is carried out by an electrospinning device set at a voltage of about 20 to 40 kV, feed rate of about 1 to 5 ml/hour, and a rotational speed of about 150 to 300 rpm.
11. The method of claim 8, wherein the reducing of the first metal compound into nanoparticles comprises subjecting the aligned, electrospun polymer nanofibers to high intensity UV light with about 70% of power and for about 5 minutes on each side of the aligned, electrospun polymer nanofibers.
12. The method of claim 8, wherein the compressing of the aligned, electrospun polymer nanofibers is carried out at about 100° C. to 300° C., 100N to SOON and for about 30 to 300 seconds.
13. The method of claim 8, wherein the depositing of the solution of the second metal compound onto the each of the aligned, electrospun polymer nanofibers electrolessly comprises immersing the aligned, electrospun polymer nanofibers into a solution containing one or both of silver nitrates and copper (II) sulfate for about 20-40 minutes at about 25 to 40° C., followed by rinsing in sufficient amount of deionized water and air drying.
14. The method of claim 8, wherein the sintering is carried out in tube furnace at about 500° C. to 700° C. and for about 10 to 60 minutes.
15. The method of claim 8, wherein the thermal conductive fillers and first metal compounds are one or more of carbon nanotubes, boron nitrates, aluminum nitride, and ceramic polymers and metal nanoparticles.
16. The method of claim 8, wherein the polymer comprises one or more of polyacrylonitrile (PAN), poly(vinylidene fluoride) (PVDF), polyimide (PI), poly(lactic acid) (PLA), caboxymethyl cellulose (CMC), and poly(vinyl pyrrolidone) (PVP).
17. The method of claim 8, wherein the polymer:thermal conductive fillers:first metal compound is in a weight ratio of about 50:1-4:8-32.
18. The method of claim 8, wherein the first metal compound: second metal compound is in a weight ratio of about 1.8:1.
19. An anisotropic heat transfer material comprising the composite of claim 1.
20. An electromagnetic interference shielding apparatus comprising the composite of claim 1.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) The disclosure will become more fully understood from the detailed description given herein below for illustration only, and thus not limitative of the disclosure, wherein:
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(16) The following detailed description explains the preferred embodiments of the invention, together with advantages and features, by way of example with reference to the drawings.
Definitions
(17) The terms “a” or “an” are used to include one or more than one and the term “or” is used to refer to a nonexclusive “or” unless otherwise indicated. In addition, it is to be understood that the phraseology or terminology employed herein, and not otherwise defined, is for the purpose of description only and not of limitation. Furthermore, all publications, patents, and patent documents referred to in this document are incorporated by reference herein in their entirety, as though individually incorporated by reference. In the event of inconsistent usages between this document and those documents so incorporated by reference, the usage in the incorporated reference should be considered supplementary to that of this document; for irreconcilable inconsistencies, the usage in this document controls.
(18) In the methods of preparation described herein, the steps can be carried out in any order without departing from the principles of the invention, except when a temporal or operational sequence is explicitly recited. Recitation in a claim to the effect that first a step is performed, and then several other steps are subsequently performed, shall be taken to mean that the first step is performed before any of the other steps, but the other steps can be performed in any suitable sequence, unless a sequence is further recited within the other steps. For example, claim elements that recite “Step A, Step B, Step C, Step D, and Step E” shall be construed to mean step A is carried out first, step E is carried out last, and steps B, C, and D can be carried out in any sequence between steps A and E, and that the sequence still falls within the literal scope of the claimed process. A given step or sub-set of steps can also be repeated. Furthermore, specified steps can be carried out concurrently unless explicit claim language recites that they be carried out separately. For example, a claimed step of doing X and a claimed step of doing Y can be conducted simultaneously within a single operation, and the resulting process will fall within the literal scope of the claimed process.
DETAILED DESCRIPTION
(19) The present invention will be described in detail through the following embodiments/examples with appending drawings. It should be understood that the specific embodiments are provided for an illustrative purpose only, and should not be interpreted in a limiting manner.
Examples
(20) Referring to
(21) In contrast, the non-aligned polymer nanofibers as shown in
(22) Referring to
(23) Referring to
(24) s301: preparing a solution of CNT by dispersing about 0.056 g of CNT-COOH into about 38.4 g of DMF solvent with stirring for 2 hours, followed by completely dissolving about 5.6 g of PAN into the CNT solution at 90° C. for around 6 hours to form a PAN/CNT solution;
(25) s302: adding about 1.8 g of AgNO.sub.3 into the PAN/CNT solution with stirring for 1 hours to form a PAN/CNT/AgNO.sub.3 solution;
(26) s303: electrospinning the PAN/CNT/AgNO.sub.3 solution by MECC machine with the conditions as follows: 1) Voltage: 27 kV; 2) Feed rate: 1.7 ml/h; 3) Rotation speed: 150 rpm, in order to form a plurality of PAN/CNT/AgNO.sub.3 nanofibers (NF);
(27) s304: drying the PAN/CNT/AgNO.sub.3 NF by vacuum oven at 100° C.;
(28) s305: reducing the PAN/CNT/AgNO.sub.3 NF to PAN/CNT/Ag nanoparticles (NP) NF by high intensity UV light under the following conditions: 70% power, 5 mins on each side;
(29) s306: compressing PAN/CNT/AgNP NF by Carver press under the following conditions: 100° C., 300N, 30 s;
(30) s307: electrolessly depositing AgNP or CuNP on the PAN/CNT/AgNP NF to form a plurality of PAN/CNT/AgNP—Ag NF or PAN/CNT/AgNP—Cu NF;
(31) s308: sintering the PAN/CNT/AgNP—Ag NF or PAN/CNT/AgNP—Cu NF using tube furnace at inert environment under the following conditions: 500° C., 10 mins.
(32) Table 1 provides the composition of the electrospinning solution for the polymer nanofibers incorporated with the anisotropic heat transfer and metal nanoparticles into the core and polymer matrix of the nanofibers:
(33) TABLE-US-00001 TABLE 1 PAN CNT-COOH AgNO.sub.3 DMF Solution (g) (g) (g) (ml) *PAN/CNT/AgNO.sub.3 5.6 0.112 1.8 38.4
Remarks: *Possible polymers: high molecular weight polymers such as PAN, PVDF, PI, PAN, PLA, CMC, PVP, etc.; possible fillers: high thermal conductive materials such as CNT, BN, AIN, metal nanoparticles, ceramic, etc.
(34) In one embodiment, the electroless plating of the Ag nanoparticles include: dissolving about 1.0 g of AgNO.sub.3 and about 1.0 g of KOH into a 100 mL DI water with stirring to form a brown solution with precipitates; completely dissolving the brown solution by adding sufficient amount of NH.sub.3 (˜6 mL) and then adding 4.0 g of glucose into the brown solution; immersing the PAN/CNT/AgNP NF into the solution for the Ag deposition at 25-30° C. for 40 mins; rinsing the PAN/CNT/AgNP NF with water and drying at room temperature to obtain PAN/CNT/AgNP—Ag NF.
(35) Table 2 summarizes the concentration of Ag deposition solution for said electroless plating:
(36) TABLE-US-00002 TABLE 2 AgNO.sub.3 KOH NH.sub.3 Glucose DI water (g) (g) (ml) (g) (ml) PAN/CNT/AgNP—Ag 1.0 1.0 ~6 4.0 100
(37) In another embodiment, the electroless plating of Cu nanoparticles includes: dissolving 1.0 g of CuSO.sub.4, 1.8 g of KNaC.sub.4H.sub.4O.sub.6.4H.sub.2O (g), 1.2 g of NaOH and 1 mL of HCHO in a 100 mL DI water to form a dark blue solution at 40° C. with stirring; immersing the PAN/CNT/AgNP NF into the dark blue solution for the Cu deposition at 25-40° C. for 20 mins; rinsing the PAN/CNT/AgNP NF and drying at room temperature to obtain PAN/CNT/AgNP—Cu NF.
(38) Table 3 summarizes the concentration of Cu deposition solution for said electroless plating:
(39) TABLE-US-00003 TABLE 3 CuSO.sub.4 KNaC.sub.4H.sub.4O.sub.6•4H2O NaOH HCHO DI water (g) (g) (g) (mL) (ml) PAN/CNT/AgNP—Cu 1.0 1.8 1.2 1.0 100
(40) Other possible metals that can be used for electroless plating and/or incorporation into the core or polymer matrix of the nanofibers include gold, tin, zinc, cadmium, chromium, nickel, platinum, and lead.
(41) Referring to
(42) Referring to
(43) TABLE-US-00004 TABLE 4 Direction Electrical Hot Sintering Density of heat Tc resistivity Sample Press (temp) (g/cm3) transfer (W/mK) (Ohm/cm) Ag foil (control) No No 10.49 X, Y and Z 429 — Cu foil (control) No No 8.96 X, Y and Z 385 — PAN polymer No No 1.18 X, Y and Z 0.1-0.2 — (control) 1 PAN/2% CNT/ No No 1.15 X 34.59 — AgNP—Ag (alone fiber) 2 PAN/2% CNT/ No Yes 1.32 X 77.94 — AgNP—Ag (500° C.) (alone fiber) Y 74.82 — (bisect fiber) Z 0.3752 — (through plane) 3 PAN/2% CNT/ Yes Yes 1.55 X 120.05 0.49 AgNP—Ag (500° C.) (alone fiber) Y 110.81 0.47 (bisect fiber) Z 0.4483 114 (through plane) 4 PAN Nanofibers No No 1.18 Z 0.02832 — (through plane) Z 0.02824 — (through plane)
(44) As it can be seen, there is a significant difference in thermal conductivity along the x-direction of fiber after sintering (sample 1 and 2), which can be about 2.25 times higher than the non-annealed one. While in x- and y-directions of the orientation of the aligned polymer nanofibers between the sample composites without and with hot press treatment (i.e., samples 2 and 3), which can be from about 40% to 60%, but that along the z-direction does not have significant difference between the sample composites without and with hot press. Beside thermal anisotropy, it was found that aligned nanofiber mat also showed electrical anisotropic properties. It was found that fiber with x and y direction is more electrical, which can be about 3 orders lower than that of z-direction.
(45) Referring to
(46) TABLE-US-00005 TABLE 5 Density Resistance EMI SE (dB) (g/cm.sup.3) (Ω) 0.5 GHz 1.0 GHz 1.5 GHz Cu foil (Ref) 5.56 0.94 −91.6 −92.5 −92.3 PAN NF (Ref) 0.28 ∞ −5.9 −3.1 −1.1 PAN/CNT/AgNP—Cu NF 0.44 1.54 −69.8 −70.7 −71.8 PAN/CNT/AgNP—Ag NF 1.42 0.81 −83.4 −87.4 −90.7 Remarks: Test sample size: Ø 15.8 mm
(47) TABLE-US-00006 TABLE 6 Density Resistance EMI SE (dB) (g/cm.sup.3) (Ω) 2.5-2.7 GHz 3.4-3.6 GHz 4.8-4.9 GHz 5-10 GHz Cu foil (Ref) 5.56 0.94 −87.7 −87.9 −91.8 −87.6 PAN NF (Ref) 0.28 ∞ −0.7 −0.3 −0.2 −0.2 PAN/CNT/AgNP—Cu NF 0.44 1.54 −75.1 −77.8 −78.2 −83.6 PAN/CNT/AgNP—Ag NF 1.42 0.81 −88.0 −88.1 −91.5 −87.9 Remarks: Test sample size: Ø 15.8 mm
(48) At low frequency of EM waves, the EMI SE of the composite made of PAN/CNT/AgNP—Ag NF is comparable to that of copper foil at the same thickness while the composite made of PAN/CNT/AgNP—Cu NF is not as good as that made of PAN/CNT/AgNP—Ag NF in terms of EMI SE at low frequency.
(49) At high frequency of EM waves, the EMI SE of the composite made of PAN/CNT/AgNP—Ag NF is similar to or even better than that of copper foil at the same thickness while the composite made of PAN/CNT/AgNP—Cu NF is again not as good as that made of PAN/CNT/AgNP—Ag NF in terms of EMI SE at high frequency of EM waves.
(50) From the EMI SE test results in the present disclosure, it can be concluded that the composite made of PAN/CNT/AgNP NF deposited with silver nanoparticles (AgNP) on the surface thereof is better than that deposited with copper nanoparticles (CuNP), and the composite made of PAN/CNT/AgNP—Ag NF performs well in low and high frequencies of EM waves in terms of EMI SE, especially at high frequency range. The high frequency range used in this series of EMI SE tests is that the EM waves of 5G communication protocol fall within. It therefore also gives an insight that the present composite made of PAN/CNT/AgNP—Ag NF can be a potential candidate of EMI shielding materials used in 5G communication module and infrastructure.
(51) It is also noted from the result of Tables 5 and 6 that the sheet resistance of the composite of PAN/CNT/AgNP—Ag NF is even slightly lower than that of copper foil, at both low and high frequencies of EM waves.
(52) The aligned side of the composite made of PAN incorporated with CNT and AgNP into the core or polymer matrix thereof and deposited with AgNP (PAN/CNT/AgNP—Ag NF) prepared according to the method of the present invention is subject to a bending test with a bending radius of 2.5 cm for 1000 cycles. Thermal conductivity of the composite before and after the bending test for 1000 cycles is compared. The result is summarized in Table 7.
(53) TABLE-US-00007 TABLE 7 Tc (W/mK) Thickness Power Time Before After bending (μm) (mW) (s) bending (1000 times) PAN/CNT/AgNP—Ag NF 350 120 2 68.80 63.95 (Aligned side)
(54) As it can be seen from the results in Table 7, the change in thermal conductivity on the aligned side of the composite made of PAN/CNT/AgNP—Ag NF before and after 1000 cycles of bending at bending radius of 2.5 cm is about 7.05% decrease, which is in an acceptable range when it is applied to devices such as wearables which require sufficient flexibility of the thermal conductive material.
INDUSTRIAL APPLICABILITY
(55) The present invention is applicable in many different electronic devices and a wide range of telecommunication systems and infrastructures because of its dual functions in efficient heat dissipation and EMI shielding property from low to high frequency ranges of EM waves.