CN113831897A - Preparation method and application of high-thermal-conductivity graphene-based hydrogel - Google Patents
Preparation method and application of high-thermal-conductivity graphene-based hydrogel Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
Abstract
The invention discloses a preparation method of high-thermal-conductivity graphene-based hydrogel, which is characterized in that a graphene dispersion liquid with specific composition is uniformly mixed with a gel matrix solution through an ultrasonic technology, thermal crosslinking and freezing-unfreezing are carried out to prepare the high-thermal-conductivity graphene-based hydrogel, and the thermal conductivity coefficient of the hydrogel can reach 1.732 W.m at most‑1·K‑1The tensile strength was 243KPa, and the electrical conductivity was 0.3256S/m. The hydrogel product has simple preparation process, mild condition and excellent product performance. The product can be used as a thermal interface material and a flexible electronic material for high-end fields such as electronic skins, sensors, supercapacitors, integrated circuit cooling fins and the like.
Description
Technical Field
The invention relates to the field of clean preparation of functional hydrogel, in particular to a preparation method and application of graphene-based hydrogel with high thermal conductivity and excellent comprehensive performance.
Background
With the development and progress of modern high-tech and industry, the miniaturization and integration of microelectronic devices become a new normal state, the power consumption of most product designs based on semiconductors and internet of things is continuously increased, so that the heat management becomes one of the most important problems in the microelectronic industry, and proper and efficient heat management equipment and measures are required to be provided to ensure the further upgrading and multi-functionalization of electronic equipment.
Currently, there are two main forms of thermal management for electronic devices, namely, active thermal management and passive thermal management. The choice of these two management modes is based primarily on the best energy efficiency of the device in the operating system. Active thermal management typically uses technical devices that generate energy from the outside, such as fans, liquid coolers, and thermoelectric coolers (TECs), to enhance heat transfer in the system, such management typically being used in large devices; passive Thermal management involves the interaction of small components in the microdevice with a cooling system, and is suitable for use in low-cost, easy-to-handle small devices, including heat sinks, Thermal Interface Materials (TIMs), and the like.
The TIMs serve as a heat conductor between the heat source and the heat sink, and effective heat dissipation of the heat source can be achieved only by using a thermal interface material with a high thermal conductivity coefficient. The performance analysis of various types of thermal management materials currently in use is listed in table 1 below.
TABLE 1 analysis of the Properties of various thermal interface materials currently in use
With the development and application popularization of flexible and wearable electronic products, new technical requirements are put forward on the TIMs: firstly, the method comprises the following steps: the adhesive property and the bonding property are high, surface gaps are filled as much as possible, air thermal resistance is reduced, and the heat dissipation efficiency is improved; II, secondly: low Young's modulus, certain stretchability and compressibility; thirdly, the method comprises the following steps: has good self-recovery performance to thermal fatigue and mechanical fatigue caused by long-term use.
The hydrogel is a three-dimensional network structure material formed by physically crosslinking or chemically crosslinking natural or synthetic polymer raw materials. The interior of the gel contains a large number of free water molecules, which becomes a research hotspot for preparing novel TIMS materials, and the functions of the gel can be obviously changed after different gel matrixes and additives are introduced.
Graphene is used as a carbon material with a perfect two-dimensional honeycomb structure, and the heat conductivity coefficient of the graphene is as high as 5.3 multiplied by 103W·m-1·K-1The graphene-based heat-conducting hydrogel is used as a filling matrix of the hydrogel to prepare the graphene-based heat-conducting hydrogelThe thermal conductivity, mechanical strength and the like of the material are improved while the hydrogel has excellent performance, so that the novel graphene-based hydrogel TIMs are obtained.
Chen Ying and the like take alanine as a modifier, ball-mill the hexagonal boron nitride as a raw material and the modifier, add hydrochloric acid solution to adjust the pH value to be neutral, and perform suction filtration, washing and drying to obtain modified boron nitride; adding modified boron nitride and polyvinyl alcohol (PVA) into distilled water, uniformly mixing, stirring for 2h at 98 ℃, carrying out ultrasonic defoaming after full dissolution, then dropwise adding a borax solution, continuing ultrasonic treatment for 35min, putting the obtained solution into a mould, and pressing for 2h to obtain PVA heat-conducting hydrogel with the heat conductivity coefficient of 0.7442 W.m-1·K-1The improvement is 38.4 percent compared with the pure PVA hydrogel. (aged, Jihaifeng, Zhang Xiaojie,&qu Xiongwei (2020). application of alanine modified boron nitride in PVA thermal-conductive hydrogel, chemical intermediate 000(003), 128-130)
Lijing and the like adopt a two-step method to prepare the graphene/n-octadecane composite phase-change material, firstly, graphene oxide is used as a raw material, and NaHSO3The graphene aerogel is a reducing agent, the reaction is carried out in a water bath at 95 ℃ for 5 hours, GO is reduced and self-assembled into hydrogel, and then the hydrogel is subjected to freeze drying treatment to obtain graphene aerogel; then putting the aerogel into the n-octadecane solution until the aerogel is completely absorbed to obtain the composite phase change material, and testing the thermal conductivity coefficient to be the highest 0.719 W.m-1·K-1. (lisk, lissawei, zaidi,&liao Yanning, thermophysical research of graphene aerogel composite phase-change material, physical science newspaper, 70(4),9)
Graphene Oxide (GO) is prepared by an improved Hummers method through Wen and Wen of Zhu Wen, and the like, Ethylenediamine (EDA) is used as a reducing agent, and the graphene oxide reacts for 8 hours at 120 ℃ in a hydrothermal kettle. Obtaining a black gelatinous product, namely the three-dimensional porous graphene hydrogel. The lead ion adsorption rule research is carried out by using the hydrogel, when the dosage of the adsorbent is 18mg and the mass fraction of the lead chloride solution is 80 mg/L, the adsorption effect is the best (Wen of Zhu Wen, Xun, Huo Jia, you Feng, Jing Jie.
At present, graphene water condensation mainly makes outstanding contribution in the electrochemical field (super capacitor and the like), the water treatment field (heavy metal adsorption and the like), and the biomedical field (drug release and the like), and few reports are made in the field of thermal management. The mainstream graphene hydrogel preparation technology at present comprises the following three types:
(1) self-contained method: the graphene sheet layer is spontaneously organized or gathered into a process of stabilizing a regular geometric appearance structure under the action of a strong interaction force pi-pi bond. Xu and the like take graphene oxide as a precursor, prepare a graphene oxide aqueous solution, react at 180 ℃ for 12h, and perform hydrothermal reduction to prepare the graphene gel through three-dimensional self-assembly. The graphene hydrogel with excellent conductivity is obtained, and the conductivity of the graphene hydrogel is 5.0S/m. (Xu Y, Sheng K, Li C, et al Self-Assembled Graphene Hydrogel via One-Step Hydrothermal Process [ J ]. Acs Nano,2010,4(7):4324-
(2) Solution mixing method: and dispersing the polymer in the dispersion liquid of the graphene organic solvent, and removing the solvent to prepare the graphene/polymer nano composite material. However, since graphene has super-strong hydrophobicity and inertia, the graphene is often dispersed unevenly, which causes uneven dispersion of graphene in gel, so that the overall performance is not uniform, and the process has environmental problems such as organic solvent pollution.
The surface of the graphite oxide has a large number of oxygen-containing functional groups, so that the graphite oxide is combined with water in an aqueous solution through hydrogen bonds to form stable graphene colloid dispersion liquid. Graphene hydrogel is prepared by this method. Chen and the like take chitosan and graphene oxide as raw materials, and cross-link a chitosan polymer chain and a graphene oxide lamella to form a three-dimensional network structure, so that graphene oxide hydrogel is prepared and used for treating dyes and heavy metals in sewage. (Chen Y Q., Chen L.B., Bai H., Li L., Graphene oxide-chitosan composites as broad-spectra adhesives for water purification [ J ]. J.Mater. chem.A.,2013,1:1992-
(3) Redox polymerization process: mixing the pretreated graphene oxide, the polymer and the macromolecular crosslinking substance together to form a three-dimensional network structure, and further breaking oxygen-containing functional groups on the surface of the graphene oxide to reduce the graphene oxide into graphene. Piao et al take graphene oxide and polyamide as raw materials, synthesize GO/PAMAM composite hydrogel through a one-step method, and the hydrogel has high mechanical force and self-healing property. (Piao Y, Wu T, Chen B. one-Step Synthesis of Graphene Oxide-polyamine derivative Nanocomposite Hydrogels by Self-Assembly [ J ]. Industrial & Engineering Chemistry Research,2016,55(21))
The in-situ polymerization method has two advantages: ensuring uniform dispersion of the filler particles in the polymer matrix; the prepared nano composite material has large interaction force between filler particles and polymers, and is beneficial to stress transfer.
However, this method has disadvantages in that the viscosity of the polymerization system increases after introducing graphene, so that the polymerization reaction becomes complicated and the operation becomes difficult.
In summary, the large specific surface area of graphene makes the graphene easy to undergo irreversible agglomeration, and in addition, the hydrophobicity and chemical inertness of graphene are low in dispersion performance, so how to disperse efficiently is a bottleneck problem, and further application of graphene is greatly limited. At present, graphene oxide is mostly used as a precursor, and a target reducing agent is added to reduce the graphene oxide in a synthesis process so as to prepare the graphene-based hydrogel. But the reduction process is toxic, the process is complex and the reaction conditions are harsh.
The graphene is used as a raw material, the production process is clean, the gel preparation process is simple and convenient, and the prepared heat-conducting hydrogel has excellent heat-conducting property, high mechanical strength, good self-recovery property and the application requirement of a composite thermal interface material.
Disclosure of Invention
The invention aims to provide a preparation method of a thermal interface material, which ensures that the hydrogel material has high thermal conductivity while having good tensile and compression properties.
The invention is realized by the following technical scheme.
The preparation of the hydrogel with high thermal conductivity is carried out in two steps.
(1) Preparing a graphene dispersion liquid: graphene dispersions of different concentrations and compositions were prepared using high pressure shear technology (patent application 2021107609449).
(2) Preparing graphene-based hydrogel: mixing the mass (g) of the gel matrix and the volume (mL) of water according to a certain proportion, fully stirring and dissolving at 90 ℃, mixing and crosslinking the graphene dispersion liquid and the gel solution according to a certain volume ratio by stirring and ultrasonic technology, and freezing and thawing for multiple times to prepare the graphene hydrogel.
The selected graphene has radial sizes of 150 μm, 74 μm, 6.5 μm, 2.6 μm, 1.6 μm, 1.3 μm and 1 μm. Preferably 74 mu m, 6.5 mu m, 2.6 mu m, 1.6 mu m and 1.3 mu m, the number of graphene layers is 1-10, and the graphene accounts for 0.01-1.0% of the total mass of the raw materials.
The surfactant is one or more of Sodium Dodecyl Benzene Sulfonate (SDBS), polyvinylpyrrolidone (PVP), Sodium Dodecyl Sulfate (SDS) and Dodecyl Trimethyl Ammonium Chloride (DTAC), and the mass of the surfactant accounts for 1.0-15.0% of the total mass of the solution; preferably 2.0% to 9.0%.
The concentration of the used graphene dispersion liquid is 1.0 mg/mL-24.5 mg/mL; preferably 3mg/mL to 15 mg/mL.
The gel matrix is one or more of polyvinyl alcohol (PVA), Polyacrylamide (PAM), polyvinylidene fluoride (PVDF) and polymethyl methacrylate (PAAM), and accounts for 2.0-25.0% of the total mass; preferably 5.0% to 20.0%.
The dissolving temperature of the gel matrix is 70-100 ℃, and preferably 85-95 ℃; the stirring time is 10min to 90 min; preferably 30min to 60 min.
The ultrasonic power is 20W-100W; preferably 60 to 80W.
The ultrasonic time is 10 min-120 min; preferably 30min to 60 min.
The freezing-unfreezing times are 1-10 times; preferably 3 to 5 times.
Compared with the prior art, the invention has the following beneficial effects.
(1) According to the invention, through the combination of ultrasonic and thermal stirring, a cross-linking agent is not needed, and a three-dimensional graphene-based hydrogel network structure with chemical cross-linking and physical cross-linking can be constructed only after freezing and thawing;
(2) the graphene raw material used in the preparation process is easy to obtain, the hydrogel preparation process is clean and pollution-free, and toxic and harmful reagents such as reducing agents, cross-linking agents and the like are not needed;
(3) the experimental conditions are mild, high-temperature and high-pressure conditions are not needed, the energy consumption is low, and the preparation period is short.
(4) The thermal conductivity coefficient of the hydrogel can reach 1.732 W.m at most-1·K-1(ii) a After twisting, stretching and bending, the self-recovery rate reaches 100 percent.
(5) The hydrogel is used as the thermal interface material of electronic products, the invention can meet the condition requirement of the thermal interface material used by electronic devices, and provides a new idea and a new method for the performance optimization and application direction of the thermal interface material of the electronic devices.
Detailed description of the invention
Materials and the like used in the following examples are commercially available unless otherwise specified.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Hydrogel testing method
First, thermal conductivity: DZDR-S rapid heat conduction instrument of Nanjing Dazhang electromechanical technical research institute
(1) Preparing a sample: the thickness of the hydrogel is 5mm, and the diameter is 2 cm; sample number: 2;
(2) after the instrument is connected, adjusting the power to 0.25W, clamping the sample on two sides of the heat conduction probe, and starting to test;
(3) carrying out three tests on each group of experiments, and taking the average value of the three data as final data;
II, mechanical property: testing by universal extensometer
(1) Preparing a sample: the length is 5cm, and the diameter is 1 cm; sample number: 3;
(2) clamping the hydrogel on a universal stretching instrument according to the operation requirements of the instrument, starting testing, and recording data;
(3) each set of experiments was tested 3 times, and the average of the data of the 3 experiments was taken as the final data.
Thirdly, self-recovery: universal extensometer testing
(1) Preparing a sample: the length is 5cm, and the diameter is 1 cm; sample number: 3;
(2) clamping the hydrogel on a testing machine according to the operation requirement of an instrument, and applying a fixed stretching force; recording the length before stretching, the length when stretching and the length after self-recovery;
(3) calculating the deformation quantity and the self-recovery rate of the material;
(4) each set of experiments was tested 3 times, and the average of the data of the 3 experiments was taken as the final data.
Fourthly, evaluating the heat dispersion performance of the hydrogel:
preparing a heat dissipation model, namely preparing two 250mL plastic jacket beakers (numbered as #1 and #2), taking #1 as an experimental group, amplifying by using experimental steps in the embodiment to prepare 150mL graphene dispersion, adding the graphene dispersion into a gel solution according to a certain proportion, uniformly stirring, and adding the graphene dispersion into a jacket layer until the graphene dispersion is filled;
the #2 control group was prepared by adding a gel solution of the corresponding concentration only to the jacket layer of the beaker until the jacket layer was filled, and freezing and thawing the #1 and #2 beakers for a plurality of times to obtain a heat dissipation model.
And (3) evaluating heat dissipation performance: the model #1 and model #2 are added with an insulating layer, and hot water with the same temperature is added at the same time. And (3) inserting a thermometer into the beaker, observing the temperature, and recording the temperature change conditions of the #1 beaker and the #2 beaker, thereby calculating the heat dissipation rate.
Example 1 preparation of highly thermally conductive graphene hydrogel
Preparing a graphene dispersion liquid: according to the patent (2021107609449), a surfactant is selected to be SDS, which accounts for 5.0% of the total mass of a dispersion liquid, graphene accounts for 0.5% of the total mass of the dispersion liquid, the concentration of the graphene dispersion liquid is determined to be 4.5mg/mL, and 16.0g of the dispersion liquid is prepared;
(II) preparing graphene hydrogel: weighing 18.0g of deionized water, adding the deionized water into a 100mL beaker, placing the beaker into a constant-temperature water bath kettle, setting the temperature at 95 ℃, simultaneously starting magnetic stirring, adding 2.0g of PVA, after completely dissolving, adding 16.0g of graphene dispersion liquid prepared in the first step, continuously stirring for 30min, carrying out ultrasonic treatment for 30min under the condition of 80W to obtain a mixed solution, pouring the mixed solution into a mold, and placing the mold into a refrigerator for freezing-unfreezing for 5 times to obtain the graphene heat-conducting hydrogel.
The thermal conductivity coefficient of the graphene hydrogel is measured to be 0.5741 W.m-1·K-1(ii) a The conductivity is 0.2157S/m; the tensile strength was 28 Kpa.
Example 2 preparation of highly thermally conductive graphene hydrogel
Preparing a graphene dispersion liquid: according to the patent (2021107609449), a surfactant is selected as SDBS, which accounts for 10.0% of the total mass of a dispersion liquid, graphene accounts for 0.75% of the total mass of the dispersion liquid, the concentration of the graphene dispersion liquid is determined to be 7.3 mg/mL, and 160g of the dispersion liquid is prepared;
(II) preparing graphene hydrogel: weighing 17.0g of deionized water, adding the deionized water into a 100mL beaker, placing the beaker into a constant-temperature water bath kettle, setting the temperature at 95 ℃, simultaneously starting magnetic stirring, adding 3.0g of PVA, after completely dissolving, adding 16.0g of graphene dispersion liquid prepared in the first step, continuously stirring for 30min, carrying out ultrasonic treatment for 60min under the condition of 60W to obtain a mixed solution, pouring the mixed solution into a mold, and placing the mold into a refrigerator for freezing-thawing for 4 times to obtain the graphene heat-conducting hydrogel.
The thermal conductivity coefficient of the graphene hydrogel is measured to be 0.6927 W.m-1·K-1(ii) a The conductivity is 0.2567S/m; the tensile strength was 54.5 Kpa.
Example 3 preparation of highly thermally conductive graphene hydrogel (first) preparation of graphene dispersion: according to the patent (2021107609449), a surfactant DTAC (DTAC) is selected to account for 15.0% of the total mass of a dispersion liquid, graphene accounts for 0.5% of the total mass of the dispersion liquid, the concentration of the graphene dispersion liquid is determined to be 4.5mg/mL, and 16.0g of the dispersion liquid is prepared;
(II) preparing graphene hydrogel: weighing 16.0g of deionized water, adding the deionized water into a 100mL beaker, placing the beaker into a constant-temperature water bath kettle, setting the temperature at 95 ℃, simultaneously starting magnetic stirring, adding 4.0g of PVA, after completely dissolving, adding 16.0g of graphene dispersion liquid prepared in the first step, continuously stirring for 30min, carrying out ultrasonic treatment for 60min under the condition of 70W to obtain a mixed solution, pouring the mixed solution into a mold, and placing the mold into a refrigerator for freezing-thawing for 3 times to obtain the graphene heat-conducting hydrogel.
The thermal conductivity coefficient of the graphene hydrogel is measured to be 0.6722 W.m-1·K-1(ii) a The conductivity is 0.2666S/m; the tensile strength was 99.4 Kpa.
Example 4 preparation of highly thermally conductive graphene hydrogel
Preparing a graphene dispersion liquid: according to the patent (2021107609449), selecting PVP as a surfactant, wherein the PVP accounts for 20% of the total mass of the dispersion liquid, and graphene accounts for 1.25% of the total mass of the dispersion liquid, determining that the concentration of the graphene dispersion liquid is 12.45 mg/mL, and preparing 16.0g of the dispersion liquid;
(II) preparing graphene hydrogel: weighing 16.0g of deionized water, adding the deionized water into a 100mL beaker, placing the beaker into a constant-temperature water bath kettle, setting the temperature at 95 ℃, simultaneously starting magnetic stirring, adding 4.0g of PVA, after completely dissolving, adding 16.0g of graphene dispersion liquid prepared in the first step, continuously stirring for 30min, carrying out ultrasonic treatment for 30min under the condition of 80W to obtain a mixed solution, pouring the mixed solution into a mold, and placing the mold into a refrigerator for freezing-thawing for 3 times to obtain the graphene heat-conducting hydrogel.
The thermal conductivity coefficient of the graphene hydrogel is 1.732 W.m-1·K-1(ii) a The electrical conductivity is 0.3256S/m, and the tensile strength is 243 Kpa;
example 5 Heat dissipation Properties and self-recovery Properties of thermally conductive hydrogels
TABLE 2 comparison of Heat dissipating Performance between Heat dissipating products of the present invention
TABLE 3 self-recovery Properties of thermally conductive hydrogel products
The method of the present invention is illustrated by the following specific examples, but the present invention is not limited thereto, and any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. A preparation method and application of graphene-based hydrogel with high thermal conductivity are characterized in that raw material graphene accounts for 0.01% -1.0% of the total mass; the surfactant accounts for 1.0-15.0% of the total mass; the gel matrix accounts for 2.0-25.0% of the total mass; the deionized water accounts for 60.0-97.0% of the total mass.
2. The preparation method and the application of the graphene-based hydrogel with high thermal conductivity according to claim 1 are characterized by being prepared in two steps, wherein the steps and conditions are as follows:
(1) preparing a graphene dispersion liquid: preparing graphene dispersion liquids with different concentrations and compositions by adopting a high-pressure shearing technology (patent application 2021107609449);
(2) preparing graphene-based hydrogel: the ratio of the mass (g) of the gel matrix to the volume (mL) of water is 1: 3-1: 9, the graphene hydrogel is fully stirred and dissolved at 90 ℃, the graphene dispersion liquid and the gel solution are mixed and thermally crosslinked by stirring and ultrasonic technology according to the volume ratio of 3: 1-10: 1, and the graphene hydrogel is prepared after repeated freezing and thawing.
3. The preparation method and the application of the graphene-based hydrogel with high thermal conductivity according to claim 2, wherein the preparation method comprises the following steps: the radial size of the selected graphene is 1-150 mu m, the number of graphene layers is 1-10, and the graphene accounts for 0.01-1.0% of the total mass of the raw materials.
4. The preparation method and the application of the graphene-based hydrogel with high thermal conductivity according to claim 2, wherein the preparation method comprises the following steps: the selected surfactants are: one or more of Sodium Dodecyl Benzene Sulfonate (SDBS), polyvinylpyrrolidone (PVP), Sodium Dodecyl Sulfate (SDS) and Dodecyl Trimethyl Ammonium Chloride (DTAC), wherein the mass of the one or more of the SDBS, the PVP, the SDS and the DTAC accounts for 1.0-15.0% of the total mass of the solution.
5. The preparation method of the graphene-based hydrogel with high thermal conductivity according to claim 2, wherein the selected gel matrix is one or more of polyvinyl alcohol (PVA), Polyacrylamide (PAM), polyvinylidene fluoride (PVDF) and polymethyl methacrylate (PAAM), and the mass of the gel matrix accounts for 2.0-25.0% of the total mass of the solution.
6. The preparation method and the application of the graphene-based hydrogel with high thermal conductivity according to claim 2, wherein the preparation method comprises the following steps: the deionized water accounts for 60.0-93.0% of the total mass of the solution.
7. The preparation method and the application of the graphene-based hydrogel with high thermal conductivity according to claim 2, wherein the preparation method comprises the following steps: the stirring temperature is 90 ℃, and the stirring time is 10-120 min.
8. The preparation method and the application of the graphene-based hydrogel with high thermal conductivity according to claim 2, wherein the preparation method comprises the following steps: the ultrasonic power is 20W-150W, and the ultrasonic time is 10 min-180 min.
9. The preparation method and the application of the graphene-based hydrogel with high thermal conductivity according to claim 3, wherein the preparation method comprises the following steps: the graphene hydrogel can be used as a high-quality substitute for the traditional medical cold compress patch; the product has the characteristics of high thermal conductivity, high flexibility, simple and easy installation and the like, perfectly meets the ideal characteristics required by thermal interface materials, and can replace the traditional thermal interface materials such as silicone grease, silica gel and the like; the graphene-based hydrogel has high thermal conductivity, completely meets the use requirement of electronic equipment for heat dissipation, and can be used for preparing heat dissipation pastes of electronic equipment such as mobile phones, notebook computers and the like.
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