CN105482511A - Aluminium oxide/graphene oxide sheet-shaped hybrid and preparation method thereof - Google Patents
Aluminium oxide/graphene oxide sheet-shaped hybrid and preparation method thereof Download PDFInfo
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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Abstract
The invention discloses an aluminium oxide/graphene oxide sheet-shaped hybrid. A preparation method for the aluminium oxide/graphene oxide sheet-shaped hybrid comprises the following steps: (1) preparing graphene oxide; (2) preparing modified Al2O3; and (3) preparing aluminium oxide/graphene oxide, concretely, weighing 0.05 g of modified Al2O3, graphene oxide and 100 mL of N,N-dimethylformamide, uniformly mixing, performing ultrasonic dispersion for 30 min, reacting at 105 DEG C for 5 h with stirring, centrifuging, washing the solid substance with anhydrous ethanol, putting the solid in a 60 DEG C vacuum baking oven for drying for 24 h, and grinding to obtain the aluminium oxide/graphene oxide sheet-shaped hybrid. According to the preparation method, nanometer Al2O3 is employed for modifying the graphene oxide sheet layer, relatively strong binding force exists between nanometer Al2O3 and the graphene oxide sheet layer, Al2O3 agglomeration is avoided, and also the graphene oxide multi-sheet-layer accumulation problem is solved. When the aluminium oxide/graphene oxide sheet-shaped hybrid is added into an epoxy coating layer, good compatibility and dispersibility are provided, and the anticorrosion effect of the epoxy coating layer is substantially enhanced.
Description
Technical field
The invention belongs to material chemistry technical field, be specifically related to a kind of aluminum oxide/graphene oxide sheet hybrid and preparation method thereof.
Background technology
Graphene is a kind of two dimensional surface novel materials of the six-ring polynuclear plane be made up of carbon atom, it is a kind of monolayer carbon atom material separated from graphite, also be material the thinnest in the world at present, its special structure makes it have the characteristics such as high electronics current capacity, high conductivity, high thermal conductivity and high strength, from it finds, just cause a upsurge to Graphene and composite structure and performance study.
At present, Graphene can be prepared by methods such as electrochemical process, chemical vapor infiltration, micromechanics stripping methods, but easily produces Graphene agglomeration, and the generation of this phenomenon also can reduce the specific surface area of Graphene, thus affects the performance of Graphene.
Summary of the invention
The present invention is directed to above-mentioned weak point and a kind of aluminum oxide/graphene oxide sheet hybrid provided and preparation method thereof, the method is by the method for covalent linkage grafting, nano aluminium oxide is used to modify graphene oxide (GO), not only can avoid the agglomeration of aluminum oxide, also solve the problem that graphene oxide multi-disc layer is piled up, synthesis aluminum oxide/graphene oxide sheet hybrid adds in epoxy coat, there are good consistency and dispersiveness, effectively can improve the antiseptic power of epoxy coat.
For achieving the above object, the technical solution adopted for the present invention to solve the technical problems is:
A preparation method for aluminum oxide/graphene oxide sheet hybrid, comprises the following steps:
(1) preparation of graphene oxide (GO)
By 1g natural graphite and the mixing of the 24mL98% vitriol oil, stir 30min in ice-water bath, then add 1g SODIUMNITRATE, 5g potassium permanganate, after stirring 1.5h, rise to 39 DEG C of reaction 2h, then add 41mL deionized water, 95 DEG C are stirred 1h, then add 10% hydrogen peroxide 120mL, reaction 30min, continue to add hydrochloric acid 5mL, centrifuging, with deionized water and dehydrated alcohol repetitive scrubbing solid matter 5 times, finally, solid is placed in 60 DEG C of dry 24h of vacuum drying oven, obtains graphene oxide;
(2) Al of modification
2o
3(f-Al
2o
3) preparation
Take 0.2g nanometer Al
2o
3with 8gAPTS ultrasonic disperse 30min in 200g dehydrated alcohol, then add 16g deionized water, stirring reaction 4h at 78 DEG C, centrifuging, with deionized water and dehydrated alcohol repetitive scrubbing solid matter 5 times, finally, solid is placed in 60 DEG C of dry 24h of vacuum drying oven, grinds to obtain f-Al
2o
3;
(3) aluminum oxide/graphene oxide (GO-Al
2o
3) preparation
Take 0.05gf-Al
2o
3, graphene oxide, 100mLN, dinethylformamide (DMF), mixing, ultrasonic disperse 30min, 105 DEG C of stirring reaction 5h, centrifugal, with absolute ethanol washing solid matter 3 times, solid is placed in 60 DEG C of dry 24h of vacuum drying oven, grinds to obtain GO-Al
2o
3product; The wherein Al of modification
2o
3be 1:2-5 with the weight ratio of graphene oxide.
Further, the Al of modification in step (3)
2o
3be 1:4 with the weight ratio of graphene oxide.
A kind of aluminum oxide provided by the invention/graphene oxide sheet hybrid and preparation method thereof, has following several beneficial effect:
(1) the present invention is by the method for covalent linkage grafting, uses nanometer Al
2o
3modification GO lamella, has stronger bonding force between the two, not only can avoid Al
2o
3reunion, and solve GO multi-disc layer pile up problem, join in epoxy coat, realize good consistency and dispersiveness.
(2) GO-Al synthesized
2o
3can the preservative effect of reinforced epoxy coating greatly.
Accompanying drawing explanation
Fig. 1 pure epoxy resin coating cross-section morphology;
Fig. 2 GO content is the GO/ epoxy coating cross-section morphology of 2wt.%; Wherein, enclose part representative not disperse completely;
Fig. 3 nanometer Al
2o
3content is the nanometer Al of 2wt.%
2o
3/ epoxy coating cross-section morphology; Wherein, enclose part representative not disperse completely;
Fig. 4 GO-Al
2o
3content is the GO-Al of 2wt.%
2o
3/ epoxy coating cross-section morphology; Wherein, enclose part and represent better dispersed, present relatively more uniform flake;
The SEM figure of Fig. 5 pure epoxy resin coating before etchant solution soaks;
Fig. 6 GO content is the SEM figure of GO/ epoxy coating before etchant solution soaks of 2wt.%;
Fig. 7 nanometer Al
2o
3content is the nanometer Al of 2wt.%
2o
3the SEM figure of/epoxy coating before etchant solution soaks;
Fig. 8 GO-Al
2o
3content is the GO-Al of 2wt.%
2o
3the SEM figure of/epoxy coating before etchant solution soaks;
Fig. 9 pure epoxy resin coating is soaked the SEM after 20 days and is schemed in etchant solution;
Figure 10 GO content is that the GO/ epoxy coating of 2wt.% soaks the SEM after 20 days and schemes in etchant solution;
Figure 11 nanometer Al
2o
3content is the nanometer Al of 2wt.%
2o
3/ epoxy coating soaks the SEM after 20 days in etchant solution schemes;
Figure 12 GO-Al
2o
3content is the GO-Al of 2wt.%
2o
3/ epoxy coating soaks the SEM after 20 days in etchant solution schemes;
Figure 13 pure epoxy resin coating (pureepoxy), GO content are GO/ epoxy coating (2wt.%GO/epoxy), the nanometer Al of 2wt.%
2o
3content is the nanometer Al of 2wt.%
2o
3/ epoxy coating (2wt.%nano-Al
2o
3/ epoxy), GO-Al
2o
3content is the GO-Al of 2wt.%
2o
3/ epoxy coating (2wt.%Al
2o
3-GO/epoxy) in etchant solution, soak the figure of the Nyquist after 60h, 108h, 142h, 240h respectively;
Figure 14 pure epoxy resin coating (pureepoxy), GO content are GO/ epoxy coating (2wt.%GO/epoxy), the nanometer Al of 2wt.%
2o
3content is the nanometer Al of 2wt.%
2o
3/ epoxy coating (2wt.%nano-Al
2o
3/ epoxy), GO-Al
2o
3content is the GO-Al of 2wt.%
2o
3/ epoxy coating (2wt.%Al
2o
3-GO/epoxy) in etchant solution, soak the figure of the Bodes after 60h, 108h, 142h, 240h respectively;
Figure 15 carries out to EIS data the equivalent-circuit model that model analysis adopts.
Embodiment
Embodiment 1
A preparation method for aluminum oxide/graphene oxide sheet hybrid, comprises the following steps:
(1) preparation of graphene oxide (GO)
By 1g natural graphite and the mixing of the 24mL98% vitriol oil, stir 30min in ice-water bath, then add 1g SODIUMNITRATE, 5g potassium permanganate, after stirring 1.5h, rise to 39 DEG C of reaction 2h, then add 41mL deionized water, 95 DEG C are stirred 1h, then add 10% hydrogen peroxide 120mL, reaction 30min, continue to add hydrochloric acid 5mL, centrifuging, with deionized water and dehydrated alcohol repetitive scrubbing solid matter 5 times, finally, solid is placed in 60 DEG C of dry 24h of vacuum drying oven, obtains graphene oxide;
(2) Al2O3 (f-Al of modification
2o
3) preparation
Take 0.2g nanometer Al
2o
3with 8gAPTS ultrasonic disperse 30min in 200g dehydrated alcohol, then add 16g deionized water, stirring reaction 4h at 78 DEG C, centrifuging, with deionized water and dehydrated alcohol repetitive scrubbing solid matter 5 times, finally, solid is placed in 60 DEG C of dry 24h of vacuum drying oven, grinds to obtain f-Al
2o
3;
(3) aluminum oxide/graphene oxide (GO-Al
2o
3) preparation
Take 0.05gf-Al
2o
3, 0.2gGO, 100mLN, dinethylformamide (DMF), mixing, ultrasonic disperse 30min, 105 DEG C of stirring reaction 5h, centrifugal, with absolute ethanol washing solid matter 3 times, solid is placed in 60 DEG C of dry 24h of vacuum drying oven, grinds to obtain GO-Al
2o
3product.
Embodiment 2
A preparation method for aluminum oxide/graphene oxide sheet hybrid, comprises the following steps:
(1) preparation of graphene oxide (GO)
By 1g natural graphite and the mixing of the 24mL98% vitriol oil, stir 30min in ice-water bath, then add 1g SODIUMNITRATE, 5g potassium permanganate, after stirring 1.5h, rise to 39 DEG C of reaction 2h, then add 41mL deionized water, 95 DEG C are stirred 1h, then add 10% hydrogen peroxide 120mL, reaction 30min, continue to add hydrochloric acid 5mL, centrifuging, with deionized water and dehydrated alcohol repetitive scrubbing solid matter 5 times, finally, solid is placed in 60 DEG C of dry 24h of vacuum drying oven, obtains graphene oxide;
(2) Al2O3 (f-Al of modification
2o
3) preparation
Take 0.2g nanometer Al
2o
3with 8gAPTS ultrasonic disperse 30min in 200g dehydrated alcohol, then add 16g deionized water, stirring reaction 4h at 78 DEG C, centrifuging, with deionized water and dehydrated alcohol repetitive scrubbing solid matter 5 times, finally, solid is placed in 60 DEG C of dry 24h of vacuum drying oven, grinds to obtain f-Al
2o
3;
(3) aluminum oxide/graphene oxide (GO-Al
2o
3) preparation
Take 0.05gf-Al
2o
3, 0.25gGO, 100mLN, dinethylformamide (DMF), mixing, ultrasonic disperse 30min, 105 DEG C of stirring reaction 5h, centrifugal, with absolute ethanol washing solid matter 3 times, solid is placed in 60 DEG C of dry 24h of vacuum drying oven, grinds to obtain GO-Al
2o
3product.
Embodiment 3
A preparation method for aluminum oxide/graphene oxide sheet hybrid, comprises the following steps:
(1) preparation of graphene oxide (GO)
By 1g natural graphite and the mixing of the 24mL98% vitriol oil, stir 30min in ice-water bath, then add 1g SODIUMNITRATE, 5g potassium permanganate, after stirring 1.5h, rise to 39 DEG C of reaction 2h, then add 41mL deionized water, 95 DEG C are stirred 1h, then add 10% hydrogen peroxide 120mL, reaction 30min, continue to add hydrochloric acid 5mL, centrifuging, with deionized water and dehydrated alcohol repetitive scrubbing solid matter 5 times, finally, solid is placed in 60 DEG C of dry 24h of vacuum drying oven, obtains graphene oxide;
(2) Al2O3 (f-Al of modification
2o
3) preparation
Take 0.2g nanometer Al
2o
3with 8gAPTS ultrasonic disperse 30min in 200g dehydrated alcohol, then add 16g deionized water, stirring reaction 4h at 78 DEG C, centrifuging, with deionized water and dehydrated alcohol repetitive scrubbing solid matter 5 times, finally, solid is placed in 60 DEG C of dry 24h of vacuum drying oven, grinds to obtain f-Al
2o
3;
(3) aluminum oxide/graphene oxide (GO-Al
2o
3) preparation
Take 0.05gf-Al
2o
3, 0.15gGO, 100mLN, dinethylformamide (DMF), mixing, ultrasonic disperse 30min, 105 DEG C of stirring reaction 5h, centrifugal, with absolute ethanol washing solid matter 3 times, solid is placed in 60 DEG C of dry 24h of vacuum drying oven, grinds to obtain GO-Al
2o
3product.
Embodiment 4
A preparation method for aluminum oxide/graphene oxide sheet hybrid, comprises the following steps:
(1) preparation of graphene oxide (GO)
By 1g natural graphite and the mixing of the 24mL98% vitriol oil, stir 30min in ice-water bath, then add 1g SODIUMNITRATE, 5g potassium permanganate, after stirring 1.5h, rise to 39 DEG C of reaction 2h, then add 41mL deionized water, 95 DEG C are stirred 1h, then add 10% hydrogen peroxide 120mL, reaction 30min, continue to add hydrochloric acid 5mL, centrifuging, with deionized water and dehydrated alcohol repetitive scrubbing solid matter 5 times, finally, solid is placed in 60 DEG C of dry 24h of vacuum drying oven, obtains graphene oxide;
(2) Al2O3 (f-Al of modification
2o
3) preparation
Take 0.2g nanometer Al
2o
3with 8gAPTS ultrasonic disperse 30min in 200g dehydrated alcohol, then add 16g deionized water, stirring reaction 4h at 78 DEG C, centrifuging, with deionized water and dehydrated alcohol repetitive scrubbing solid matter 5 times, finally, solid is placed in 60 DEG C of dry 24h of vacuum drying oven, grinds to obtain f-Al
2o
3;
(3) aluminum oxide/graphene oxide (GO-Al
2o
3) preparation
Take 0.05gf-Al
2o
3, 0.1gGO, 100mLN, dinethylformamide (DMF), mixing, ultrasonic disperse 30min, 105 DEG C of stirring reaction 5h, centrifugal, with absolute ethanol washing solid matter 3 times, solid is placed in 60 DEG C of dry 24h of vacuum drying oven, grinds to obtain GO-Al
2o
3product.
Experimental example
The present invention, by the method for covalent linkage grafting, uses nanometer Al
2o
3modification GO lamella, has stronger bonding force between the two, not only can avoid Al
2o
3reunion, and solve GO multi-disc layer pile up problem, join in epoxy coat, realize good consistency and dispersiveness.By carrying out dispersiveness experiment, EIS experiment to sample in embodiment 1, the research of preservative challenge test is carried out in the change of observation compound coating pattern before and after corrosion, and experimental result shows GO-Al
2o
3can the preservative effect of reinforced epoxy coating greatly.
(1) dispersed experiment: respectively by GO, nanometer Al
2o
3, GO-Al
2o
3with epoxy resin mixing, ultrasonic disperse 1h, prepares GO, nanometer Al respectively
2o
3, GO-Al
2o
3content is GO/ epoxy coating, the nanometer Al of 2wt.%
2o
3/ epoxy coating, GO-Al
2o
3/ epoxy coating, to be moved in spray gun even application respectively on the matrix steel disc (P110) of sandblasting and welding, coating be sprayed on the sandblasting of matrix steel disc complete after 1 hour in carry out, after having sprayed, the steel disc of coating toasts 60min at 120 DEG C, 120min is toasted at 220 DEG C, then in liquid nitrogen, make its brittle failure obtain compound coating section, with pure epoxy resin in contrast, adopt JSM-7500F sem observation cross-section morphology, the results are shown in accompanying drawing 1-4.
As can be seen from Figure 1 the section of pure epoxy coating comparatively flat smooth, inclusion-free; Fig. 2 shows the thin slice that GO becomes thicker in epoxy coat, illustrates that it there occurs lamella in the coating and has piled up, thus defines reunion; Fig. 3 is nanometer Al
2o
3dispersion situation in epoxy coat, as can be seen from the figure nanometer Al
2o
3large-scale reunion has occurred, and this is due to unmodified nanometer Al
2o
3not good with the consistency of epoxy coat, it is disperseed in epoxy coat and bad; Fig. 4 is Al
2o
3the dispersion situation of – GO in epoxy coat, as can be seen from the figure Al
2o
3– GO matrix material is thin many compared to the GO in Fig. 2 at its lamella, and its lamella is thinner, and Al is described
2o
3the lamella of – GO matrix material is not piled up in large quantities in epoxy coat, can draw Al
2o
3– GO matrix material has good dispersiveness in the epoxy.
(2) EIS experiment: the electrochemical impedance spectroscopy (EIS) adopting CS310 type electrochemical workstation (Wuhan Gastec Instrument Ltd.) testing coating, range of frequency is 10
4~ 10
-1hz, signal is that 20mV is sinusoidal wave, and adopt three-electrode system, platinum electrode is supporting electrode, saturated calomel electrode (SCE) is reference electrode, the steel disc (P110) scribbling compound coating is working electrode, be in the NaCl solution solution of 3.5wt.% at corrosive medium by working electrode successive soaking, until wherein there is not failure morphology and all the other all occur obvious failure morphology in a kind of coating, then JSM-7500F sem observation coating is soaking the pattern of front and rear surfaces, the results are shown in 5-12; Meanwhile, also detection different coating arrives situation when soaking latter stage, makes Nyquist figure and Bodes figure, the results are shown in 13-14.
In the corrosion resistance of research coating, accurately judge that the impregnation stage residing for coating is in immersion process seems very crucial.ZSimpwin software and different equivalent electrical circuit is used to calculate and simulate Nyquist data, its calculating and analog result can reflect the impregnation stage residing for organic coating, and this experiment adopts organic coating to go to analyze impedance spectrum data at immersion model in latter stage according to the situation of data and corrosion process reality.Wherein R
ssolution resistance, CPE
fcoating capacitor, R
fbe coating resistance, Rct is charge transfer resistance, CPE
dlbe electric double layer capacitance, W is Warburg impedance, sees accompanying drawing 15.
Fig. 9 demonstrates pure epoxy resin coating after etchant solution soaks 20 days, has occurred large-scale decomposition and a large amount of point corrosion pits, a large amount of point corrosion pit Sum decomposition causes coating to there occurs large-area coming off on the surface of electrode, thus coating complete failure is described; Figure 10 shows GO/ epoxy coating and has occurred a large amount of spot corrosion ducts, and these spot corrosion cause having occurred relatively many decomposition and decortication at electrode surface; Figure 11 demonstrates nanometer Al
2o
3there is some phenomenons of decomposing in/epoxy coating, these phenomenons caused coating to occur bubble phenomenon; Comparison diagram 8 and Figure 12 known, Al
2o
3after-GO/ epoxy coating soaked through 20 days, pattern does not have greatly changed, and the surface topography of electrode both contrast, obvious change does not occur yet simultaneously.Al as can be seen here
2o
3-GO/ epoxy coating corrosion resistance in four kinds of coatings is best, Al
2o
3-GO matrix material can the corrosion resistance of reinforced epoxy coating.
By Figure 13,14 can find out, the impedance of coating can decline significantly along with the prolongation of soak time, this decline process can be divided into three phases: in the immersion primary stage, the small duct that electrolyte solution is existed by coat inside penetrates in coating, but ionogen does not arrive steel surface; In the intermediate stage of soaking, electrolyte solution has arrived the surface of steel, and corrosion reaction occurs, but corrosion product is not piled up; The terminal stage of soaking, at the corrosion product bulk deposition of steel/coating interface.Therefore, to arrive the time of soaking needed for terminal stage relevant from soaking the primary stage for the corrosion resistance of coating and often kind of coating, and obviously the corrosion resistance of this time longer coating is better.
Figure 15 is coating at the equivalent-circuit diagram soaking latter stage, and wherein W is Warburg impedance, means when present to have occurred a large amount of corrosion products on the interface of coating/metal, and coating from then on enters the rapid failure stage until complete failure.Analog calculation in conjunction with this experiment is known, pureepoxy, 2wt.%GO/epoxy, 2wt.%nano-Al
2o
3/ epoxy and 2wt.%GO-Al
2o
3/ epoxy tetra-kinds of organic corrosion-resistant coatings arrive respectively through immersion 60h, 108h, 142h and 240h and soak latter stage, are not difficult thus to draw 2wt.%Al in these four kinds of corrosion-resistant coatings
2o
3the corrosion resistance of-GO/epoxy is best, GO-Al
2o
3nano composite material can the corrosion resistance of significantly reinforced epoxy coating.
Claims (3)
1. a preparation method for aluminum oxide/graphene oxide sheet hybrid, comprises the following steps:
(1) preparation of graphene oxide
By 1g natural graphite and the mixing of the 24mL98% vitriol oil, stir 30min in ice-water bath, then add 1g SODIUMNITRATE, 5g potassium permanganate, after stirring 1.5h, rise to 39 DEG C of reaction 2h, then add 41mL deionized water, 95 DEG C are stirred 1h, then add 10% hydrogen peroxide 120mL, reaction 30min, continue to add hydrochloric acid 5mL, centrifuging, with deionized water and absolute ethanol washing solid matter, finally, solid is placed in 60 DEG C of dry 24h of vacuum drying oven, obtains graphene oxide;
(2) Al of modification
2o
3preparation
Take 0.2g nanometer Al
2o
3with 8gAPTS ultrasonic disperse 30min in 200g dehydrated alcohol, then add 16g deionized water, stirring reaction 4h at 78 DEG C, centrifuging, with deionized water and absolute ethanol washing solid matter, finally, solid is placed in 60 DEG C of dry 24h of vacuum drying oven, grinds to obtain the Al of modification
2o
3;
(3) preparation of aluminum oxide/graphene oxide
Take the Al of 0.05g modification
2o
3, graphene oxide, 100mLN, dinethylformamide, mixing, ultrasonic disperse 30min, 105 DEG C of stirring reaction 5h are centrifugal, use absolute ethanol washing solid matter, solid is placed in 60 DEG C of dry 24h of vacuum drying oven, grind to obtain aluminum oxide/graphene oxide sheet hybrid; The wherein Al of modification
2o
3be 1:2-5 with the weight ratio of graphene oxide.
2. the preparation method of a kind of aluminum oxide according to claim 1/graphene oxide sheet hybrid, is characterized in that, the Al of modification in step (3)
2o
3be 1:4 with the weight ratio of graphene oxide.
3. aluminum oxide/graphene oxide sheet hybrid of preparing of method according to claim 1 and 2.
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CN109761584A (en) * | 2018-12-29 | 2019-05-17 | 江南大学 | A kind of graphene oxide hydridization aluminium oxide Preparing Anti-corrosion Ceramic Coating and preparation method |
CN109897189A (en) * | 2019-02-27 | 2019-06-18 | 黑龙江省科学院石油化学研究院 | A kind of preparation method of situ-formed graft graphene oxide modified, high temperature resistant epoxy resin composite material |
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CN113831818A (en) * | 2021-10-14 | 2021-12-24 | 成都虹润制漆有限公司 | Water-based epoxy zinc-containing primer based on functionalized graphene and preparation method thereof |
CN115477893A (en) * | 2022-10-18 | 2022-12-16 | 山东奔腾漆业股份有限公司 | Preparation method of water-based alkyd anticorrosive paint |
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CN106047073B (en) * | 2016-07-19 | 2018-05-22 | 无锡市烯翔新材料科技有限公司 | A kind of graphene oxide based high-temp-resistant bicomponent epoxy resin coating |
CN107384112A (en) * | 2017-07-26 | 2017-11-24 | 青岛科技大学 | A kind of graphene-based anticorrosion coating material with the rust construction of water band and preparation method thereof |
CN107384112B (en) * | 2017-07-26 | 2019-07-30 | 青岛科技大学 | A kind of graphene-based anticorrosion coating material and preparation method thereof with the rust construction of water band |
CN109761584A (en) * | 2018-12-29 | 2019-05-17 | 江南大学 | A kind of graphene oxide hydridization aluminium oxide Preparing Anti-corrosion Ceramic Coating and preparation method |
CN109897189A (en) * | 2019-02-27 | 2019-06-18 | 黑龙江省科学院石油化学研究院 | A kind of preparation method of situ-formed graft graphene oxide modified, high temperature resistant epoxy resin composite material |
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CN113480875A (en) * | 2021-07-27 | 2021-10-08 | 雷索新材料(苏州)有限公司 | Aluminum oxide modified graphene, graphene heat dissipation coating and preparation method thereof |
CN113831818A (en) * | 2021-10-14 | 2021-12-24 | 成都虹润制漆有限公司 | Water-based epoxy zinc-containing primer based on functionalized graphene and preparation method thereof |
CN115477893A (en) * | 2022-10-18 | 2022-12-16 | 山东奔腾漆业股份有限公司 | Preparation method of water-based alkyd anticorrosive paint |
CN117362057A (en) * | 2023-12-07 | 2024-01-09 | 河北润丰涂料有限公司 | Light anti-cracking heat-insulating refractory material and preparation method thereof |
CN117362057B (en) * | 2023-12-07 | 2024-02-02 | 河北润丰涂料有限公司 | Light anti-cracking heat-insulating refractory material and preparation method thereof |
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