WO2021133161A1 - Procédé pour la préparation d'une encre pour jet d'encre à base de graphène - Google Patents

Procédé pour la préparation d'une encre pour jet d'encre à base de graphène Download PDF

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Publication number
WO2021133161A1
WO2021133161A1 PCT/MY2020/050142 MY2020050142W WO2021133161A1 WO 2021133161 A1 WO2021133161 A1 WO 2021133161A1 MY 2020050142 W MY2020050142 W MY 2020050142W WO 2021133161 A1 WO2021133161 A1 WO 2021133161A1
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WIPO (PCT)
Prior art keywords
rgo
mixture
graphene
nps
solution
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Application number
PCT/MY2020/050142
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English (en)
Inventor
Nora'zah Abdul Rashid
Aiman Sajidah ABD AZIZ
Suraya Sulaiman
Syed Muhammad Hafiz SYED MOHD JAAFAR
Hing Wah Lee
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Mimos Berhad
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication of WO2021133161A1 publication Critical patent/WO2021133161A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/19—Preparation by exfoliation
    • C01B32/192—Preparation by exfoliation starting from graphitic oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/198—Graphene oxide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks

Definitions

  • This invention relates to graphene-based inkjet printing, and more particularly to a method for preparing a graphene-based ink for inkjet printing.
  • graphene oxide In a chemical reduction process of reduced graphene oxide (rGO), graphene oxide (GO) is used as a precursor.
  • the process would involve a thermal process to produce the graphene-based material, which is similar to pristine graphene, but there are limitations in controlling the consistency of the temperature applied in the reduction process while keeping the graphene pristine. The inconsistency of the temperature setting in the process will eventually affect the yield of the graphene-based material.
  • Inkjet printing is a common commercial process used in printing a variety of applications such as printed coatings and printed electronic devices.
  • Printed electronic devices are used in many commercial applications such as portable electronic devices, signages, displays, and product identifications. They are made mainly by printing inks onto a substrate.
  • there are certain criteria to be met such as viscosity within the range of 2 - 30 centipoise (cP) and a low rate of evaporation to prevent clogging at the printer head.
  • cP centipoise
  • Chinese patent no. CN 102125056 B disclosed a method for preparing silver- graphene material that implements different temperature setting above room temperature throughout the preparation process.
  • United States patent application no. US 20130059143 disclosed a method for preparing graphene-based material that is using temperature as high as 200°C for reducing the graphene oxide.
  • United Statas patent no. US 9165721 is an inkjet-printed graphene-based material having multiple printing layers with a method for preparing thereof involving reduction process at temperature between 140 - 800°C.
  • the present invention relates to a method for preparing a graphene-based inkjet ink comprising the steps of: exfoliating graphene oxide (GO) in deionised water; reducing the GO and silver nitrate (AgNOs) to form a reduced GO (rGO) and silver (Ag) mixture; reacting the rGO and Ag mixture to form a rGO-Ag nanoparticles (rGO/Ag-NPs) mixture; centrifuging the rGO/Ag-NPs mixture; adding deionised water to produce a graphene-based colloidal solution; and dispersing the graphene-based colloidal solution in a dispersant solution to produce the graphene-based inkjet ink.
  • GO graphene oxide
  • AgNOs silver nitrate
  • rGO/Ag-NPs rGO-Ag nanoparticles
  • the step of exfoliating the GO in deionised water further comprises the steps of: mixing GO colloidal solution with deionised water to form a GO solution; sonicating the GO solution at 36.5 to 37.5 kilohertz (kHz) for 30 - 45 minutes; and stirring the GO solution at 15 - 16.7 Hertz (Hz) (900 - 1000 rotation per minutes (rpm)) for 30 - 45 minutes.
  • the method of the present invention is further characterised in that both the step of sonicating the GO solution and the step of stirring the GO solution are conducted at a temperature of 25 - 30°C.
  • the step of reducing the GO and AgN03 to form the rGO and Ag mixture comprises the steps of: adding deionised water, 1.4 - 2.1 %v/v of PAA, and 43.5 -60.7 %v/v of DEA mixture solution, dropwise, into the GO solution; and stirring the GO solution at 15 - 16.7 Hz (900 - 1000 rpm) for 45 - 60 minutes; adding a 5 - 8 M AgN03 solution, dropwise, into the GO solution to form the rGO and Ag mixture; and stirring the rGO and Ag mixture at 15 - 16.7 Hertz (Hz) (900- 1000 rpm) for 30 - 45 minutes at a temperature of 25 - 30°C.
  • the method of the present invention is further characterised in that the step of stirring the GO solution after adding the deionised water, PAA, and DEA, is conducted at a temperature of 25 - 30°C.
  • the step of reacting the rGO and Ag mixture to form the rGO/Ag-NPs mixture comprises the steps of: allowing the rGO and Ag mixture to react for 21 - 24 hours to form the rGO/Ag-NPs mixture; and sonicating the rGO/Ag-NPs mixture for 1 - 1.5 hours.
  • the method of the present invention is further characterised in that the step of allowing the rGO and Ag mixture to react for 21 - 24 hours is conducted without agitation at a temperature of 25 - 30°C, and the step of sonicating the rGO/Ag-NPs mixture for 1 - 1.5 hours is conducted at 65°C to 68°C.
  • the step of centrifuging the rGO/Ag-NPs mixture to produce the graphene-based colloidal solution comprises the steps of: adding ethanol into the rGO/Ag-NPs mixture; centrifuging the rGO/Ag-NPs mixture at 150 - 167 Hz (9000 - 10000 rpm) for 10 - 20 minutes to produce a composite and a liquid layer; removing the liquid layer; collecting and crushing the composite; and adding deionised water into the composite to produce the graphene-based colloidal solution.
  • the dispersant solution comprises deionised water, ethylene glycol, and methanol, preferably 85 - 90 %v/v deionised water, 5 - 6 %v/v of ethylene glycol, and 8 - 9 %v/v of methanol are used in the step of dispersing the graphene-based colloidal solution to produce the graphene-based inkjet ink.
  • the graphene-based inkjet ink comprises a conductivity of 400 - 800 pS/cm, and a dynamic viscosity of 1.5 - 3.5 centipoise (cP) at 24 - 26°C.
  • Figure 1 is a flowchart of a method for preparing a graphene-based inkjet ink.
  • the present invention relates to a method for preparing a graphene-based inkjet ink.
  • the graphene-based inkjet ink of the present invention is able to achieve resistance less than one ohm for one cm square design.
  • the method of the present invention comprises the steps of: exfoliating graphene oxide (GO) in deionised water (100); reducing the GO and silver nitrate (AgN03) to form a reduced GO (rGO) and silver (Ag) mixture (200); reacting the rGO and Ag mixture to form rGO and Ag nanoparticles (rGO/Ag-NPs) mixture (300); sonicating the rGO/Ag-NPs mixture (400); centrifuging the rGO/AgNPs mixture to produce a graphene-based colloidal solution (500); and dispersing the graphene-based colloidal solution in a dispersant solution to produce the graphene-based inkjet ink (600).
  • the method of the present invention is characterised in that: the step of exfoliating the GO in deionised water (100) is conducted at a temperature of 25 - 30°C; the step of reducing the GO and AgN03 to form the rGO and Ag mixture (200) is conducted at a temperature of 25 - 30°C; the step of reacting the rGO and Ag mixture to form the rGO/Ag-NPs mixture (300) is conducted without agitation at a temperature of 25 - 30°C; and the step of sonicating the rGO/Ag-NPs mixture (400) is conducted at 65 - 68°C.
  • the step of exfoliating the GO in deionised water (100) further comprises the steps of: mixing GO colloidal solution with deionised water to form a GO solution; sonicating the GO solution at a temperature of 25 - 30°C for 30 - 45 minutes at 36.5 to 37.5 kilohertz (kHz); and stirring the GO solution at a temperature of 25 - 30°C for 30 - 45 minutes at 15 - 16.7 Hertz (Hz) (900 - 1000 rpm).
  • the step of reducing the GO and AgN03 to form the rGO and Ag mixture (200) further comprises the steps of: adding deionised water, polyacrylic acid (PAA) and diethanolamine (DEA) into the GO solution; stirring the GO solution at a temperature of 25 - 30°C for 45 - 60 minutes at 15 - 16.7 Hz (900 - lOOOrpm); adding dropwise the AgN03 into the GO solution to form the rGO and Ag mixture; and stirring the rGO and Ag mixture at a temperature of 25 - 30°C at 15 - 16.7 Hertz (Hz) for 30 - 45 minutes .
  • a concentration of 5 - 8 M AgN03 is used.
  • the DEA functions to reduce GO and AgN03.
  • the concentration of PAA used is 1.4 - 2.1 %v/v, while the concentration of DEA used is 43.5 - 60.7 %v/v.
  • PAA functions as a silver polymer capping to avoid silver oxidation when dispersing the graphene-based colloidal solution into the dispersant solution.
  • PAA also acts as a surfactant to improve ink wettability and prevent ink agglomeration during inkjet printing.
  • the reduction of the GO is conducted at room temperature of 25 - 30°C, which ensures that the viscosity of the GO is consistent throughout the preparation stages and will not be agglomerated especially during inkjet printing.
  • the step of reacting the rGO and Ag mixture to form the rGO/Ag-NPs mixture (300) comprises the step of: allowing the rGO and Ag mixture to react without agitation at a temperature of 25 - 30°C for 21 - 24 hours to form the rGO/Ag-NPs mixture.
  • AgN03 is reduced without agitation at room temperature of 25 - 30°C to prevent agglomeration during printing.
  • the AgN03 used in the present invention is a conductivity enhancer and a source of metal. It is understood that besides silver as a source of metal, copper, gold or other metal can also be used. Although gold has a higher conductivity and likely to be stable thermally, it is not a sustainable material to procure at large industrial scales due to its high cost. On the other hand, copper is highly oxidised. Silver is an ideal choice for the current application due to its high conductivity and affordability.
  • the step of sonicating the rGO/Ag-NPs mixture (400) is conducted at 65 - 68°C for 1 - 1.5 hours for ripening the silver nanoparticles on the rGO.
  • the method further comprises the steps of: adding ethanol into the rGO/Ag-NPs mixture; centrifuging the rGO/Ag-NPs mixture at 150 - 167Hz (9000 - 10000 rpm) for 10 - 20 minutes to produce a composite and a liquid layer; removing the liquid layer; collecting and crushing the composite; and adding deionised water into the composite to produce the graphene-based colloidal solution.
  • the dispersant solution comprises deionised water, ethylene glycol and methanol. They are introduced into the graphene-based colloidal solution to improve the dispersion properties and to avoid graphene-based agglomeration which could cause nozzle clog during inkjet printing.
  • the dispersant composition is 85 - 90 %v/v deionised water, 5-6 %v/v of ethylene glycol, and 8 - 9 %v/v of methanol and is used to produce the graphene-based inkjet printable ink.
  • the graphene-based inkjet ink comprises a conductivity of 400 - 800 pS/cm, and a dynamic viscosity of 1.5 - 3.5 centipoise (cP) at 24 - 26°C.
  • the example below shows an example of a method for preparing a graphene- based inkjet ink according to the embodiments of the present invention.
  • GO colloidal solution 1 - 2 mg/ml is mixed with deionised water to form the GO solution.
  • the GO solution is sonicated at 36.5 - 37.5 kHz at 25 - 30°C for 30 - 45 minutes and then stirred at 25 - 30°C for 30 - 45 minutes at 15 - 16.7 Hz (900 rpm to 1000 rpm).
  • deionised water 1.4 - 2.1 %v/v of PAA, and 43.5 - 60.7 %v/v of DEA mixture solution, are added dropwise into the GO solution.
  • the GO solution is stirred at 25 - 30°C for 45 - 60 minutes at 15 - 16.7 Hz (900 - 1000 rpm).
  • 4.4 - 4.5 ml of 5- 8 M AgN03 solution is added dropwise into the GO solution to form the rGO and Ag mixture.
  • the rGO and Ag mixture is left to react without agitation for 21 - 24 hours at 25 - 30°C to form rGO/Ag-NPs.
  • the rGO/Ag-NPs mixture is then sonicated at 65°C to 68°C for 1 - 1.5 hours.
  • the liquid layer is removed while the composite is collected, weighed, and crushed. Then, 83.3 - 97.1 wt% of deionised water is added into the crushed composite to produce the graphene-based colloidal solution.
  • the graphene-based colloidal solution mass loading is 0.03 - 0.2 g/ml.
  • the graphene-based colloidal solution is dispersed in 85 - 90 %v/v deionised water, 5 - 6 %v/v of ethylene glycol and 8 - 9 %v/v of methanol to produce the graphene-based inkjet printable ink.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

La présente invention concerne un procédé pour la préparation d'une encre pour jet d'encre à base de graphène, caractérisé par les étapes consistant à : exfolier de l'oxyde de graphène (OG) dans de l'eau désionisée à 25 à 30 °C (100) ; réduire l'OG et du nitrate d'argent (AgNO3) à 25 à 30 °C pour former un mélange d'OG réduit (OGr) et d'argent (Ag) (200) ; faire réagir le mélange d'OGr et d'Ag pour former un mélange de nanoparticules d'OGr/Ag (NP d'OGr/Ag) sans agitation à 25 à 30 °C (300) ; appliquer des ultrasons au mélange de NP d'OGr/Ag à 65 à 68 °C(400) ; centrifuger le mélange de NP d'OGr/Ag pour produire la solution colloïdale à base de graphène (500) ; et disperser la solution colloïdale à base de graphène dans une solution de dispersant pour produire l'encre pour jet d'encre à base de graphène (600).
PCT/MY2020/050142 2019-12-24 2020-11-10 Procédé pour la préparation d'une encre pour jet d'encre à base de graphène WO2021133161A1 (fr)

Applications Claiming Priority (2)

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MYPI2019007770 2019-12-24
MYPI2019007770 2019-12-24

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114590799A (zh) * 2022-03-28 2022-06-07 南通第六元素材料科技有限公司 石墨烯制备方法、石墨烯粉体及产品

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104277592A (zh) * 2014-09-16 2015-01-14 中国科学院化学研究所 一种石墨烯基水性墨水及其喷墨打印透明的图案化导电电极的应用
US20150368804A1 (en) * 2014-04-17 2015-12-24 Research & Business Foundation Sungkyunkwan University Metal-containing graphene hybrid composite, and preparing method of the same
CN106398397A (zh) * 2016-08-23 2017-02-15 中国工程物理研究院材料研究所 一种制备单分散的石墨烯基纳米银复合物的方法
WO2018195170A1 (fr) * 2017-04-21 2018-10-25 The Regents Of The University Of California Procédés et applications pour encres conductrices au graphène
CN109021707A (zh) * 2018-06-05 2018-12-18 沈阳建筑大学 一种石墨烯/银纳米线复合墨水及其制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150368804A1 (en) * 2014-04-17 2015-12-24 Research & Business Foundation Sungkyunkwan University Metal-containing graphene hybrid composite, and preparing method of the same
CN104277592A (zh) * 2014-09-16 2015-01-14 中国科学院化学研究所 一种石墨烯基水性墨水及其喷墨打印透明的图案化导电电极的应用
CN106398397A (zh) * 2016-08-23 2017-02-15 中国工程物理研究院材料研究所 一种制备单分散的石墨烯基纳米银复合物的方法
WO2018195170A1 (fr) * 2017-04-21 2018-10-25 The Regents Of The University Of California Procédés et applications pour encres conductrices au graphène
CN109021707A (zh) * 2018-06-05 2018-12-18 沈阳建筑大学 一种石墨烯/银纳米线复合墨水及其制备方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114590799A (zh) * 2022-03-28 2022-06-07 南通第六元素材料科技有限公司 石墨烯制备方法、石墨烯粉体及产品
CN114590799B (zh) * 2022-03-28 2024-05-10 南通第六元素材料科技有限公司 石墨烯制备方法、石墨烯粉体及产品

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