CN112812376A - 3D printing cellulose/nano inorganic filler composite gel ink and preparation method thereof - Google Patents
3D printing cellulose/nano inorganic filler composite gel ink and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/244—Stepwise homogeneous crosslinking of one polymer with one crosslinking system, e.g. partial curing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2301/02—Cellulose; Modified cellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention discloses cellulose/nano inorganic filler composite gel ink for 3D printing, which is characterized in that cellulose-based composite gel aqueous solution with nano inorganic material as filler and cellulose as a polymer matrix is prepared from 15-20 parts of nano inorganic filler dispersion liquid, 90-100 parts of cellulose dispersion liquid and 1-2 parts of chemical cross-linking agent according to the mass part ratio; the addition amount of the nano inorganic filler in the nano inorganic filler dispersion liquid is 0.5-30 wt%, and the addition amount of the fiber in the cellulose dispersion liquid is 4-6 wt%. The invention also discloses a preparation method of the composition. The invention takes cellulose as the polymer matrix of the 3D printing ink, the preparation method is efficient, the prepared gel ink has good biocompatibility, mechanical property and environmental friendliness, the polymer matrix has wide sources and low raw material cost, and can be used for printing and preparing polymer reinforced composite materials in electronic devices, electronic packaging and other fields.
Description
Technical Field
The invention relates to a preparation method of 3D printing gel ink, and particularly relates to 3D printing cellulose/graphene oxide composite gel ink and a preparation method thereof.
Background
The 3D printing is a technology for printing a three-dimensional object by adopting a mode of reconstructing a reduction track by slicing, a digital model is restored by generally adopting a principle that printing ink is accumulated along with the track, and the three-dimensional object printing method has the advantages of special design freedom degree, short preparation period and the like. In recent years, 3D printing and molding technologies are introduced to the field of polymer composites for enhancing various properties of the composites, such as mechanical properties, electrical conductivity, electromagnetic shielding properties, thermal conductivity, and the like.
At present, common matrix materials of 3D printing reinforced composite material ink are common thermoplastics (such as polyurethane, polypropylene, polyethylene, polyvinyl chloride, polyethylene terephthalate and the like), the thermoplastics are derived from petroleum, the natural degradation speed is slow, and the environment is harmed due to the large-scale use of the thermoplastics. Therefore, with the deep development of the 3D printing and forming technology in the field of reinforced composite materials, it is urgently needed to prepare a novel environment-friendly composite material 3D printing ink with mild forming conditions.
Graphene having a two-dimensional crystal structure is a very excellent material having a very large theoretical specific surface area ((2630 m)2/g-1) Very high physical sign mobility (200000 cm)2V.s), very high Young's modulus (1TPa), and high thermal conductivity (2000-5300 W.m)-1·K-1). Graphene is also used as a transparent conductive electrode by virtue of good optical transmittance (-97.7%) and conductive properties. Due to the excellent properties, the graphene has very wide application in the aspects of improving the mechanical, thermal, optical and electrical properties of the composite material. For example, Chinese patent publication No. CN201710263533.2 discloses "a methodThe method for preparing the conductive graphene/inorganic polymer composite material by using the 3D printing technology comprises the steps of mixing and stirring a continuous fiber reinforced inorganic polymer matrix composite material and a graphene oxide solution at 0 ℃ to obtain printing ink for 3D printing of the conductive graphene/inorganic polymer composite material. However, the method needs to carry out high-temperature treatment under the protection of inert gas from printing ink to a forming member, the high-temperature treatment temperature is 550-1000 ℃, the treatment time is 30-100 min, the forming condition of the printing ink is harsh, the energy consumption is high, a large amount of strong acid and strong oxidizing reagents such as concentrated sulfuric acid, nitric acid, potassium permanganate and the like are used in the preparation process of the ink, and the preparation process of the ink has certain harm to environmental protection.
Therefore, it is necessary to research a new 3D printing reinforced composite ink with environmentally friendly substrate and mild molding conditions.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the cellulose/nano inorganic filler composite gel ink for 3D printing and the preparation method thereof, wherein cellulose is used as a polymer matrix of the 3D printing ink, so that the ink has good biocompatibility, mechanical property, environmental friendliness and mild forming conditions, and can be used for rapid 3D printing and forming of a 3D polymer composite reinforced material.
In order to achieve the purpose, the invention adopts the technical scheme that:
the 3D printing cellulose/nano inorganic filler composite gel ink is characterized by being a cellulose-based composite gel aqueous solution taking a nano inorganic material as a filler and cellulose as a polymer matrix, and prepared from 15-20 parts of nano inorganic filler dispersion liquid, 90-100 parts of cellulose dispersion liquid and 1-2 parts of a chemical cross-linking agent according to the mass part ratio; the addition amount of the nano inorganic filler in the nano inorganic filler dispersion liquid is 1-30 wt%, and the addition amount of the fiber in the cellulose dispersion liquid is 4-6 wt%.
The nano inorganic filler is one of graphene oxide nanosheets, clay nanosheets and carbon nanotubes; the cellulose raw material is cotton linter; the chemical cross-linking agent is epichlorohydrin; the ink is partially cross-linked when the preparation is completed; when in use, the ink is soaked in deionized water at 50-100 ℃, and can be quickly formed by completely crosslinking through thermal induction, and 3D printing and forming are carried out.
The method for preparing the cellulose/nano inorganic filler composite gel ink for 3D printing is characterized by comprising the following steps of:
(1) adding a certain amount of nano inorganic filler into deionized water, and performing ultrasonic dispersion to obtain uniformly dispersed nano inorganic filler dispersion liquid;
(2) taking a certain amount of cotton linter raw material, adding an alkali/urea solution precooled to a specified temperature, and quickly stirring to obtain a cellulose dispersion liquid; adding the nano inorganic filler dispersion liquid obtained in the step (1) into cellulose dispersion liquid, and violently stirring to obtain cellulose/nano inorganic filler mixed dispersion liquid;
(3) violently stirring the cellulose/nano inorganic filler mixed dispersion liquid obtained in the step (2) under a set temperature condition, slowly dropwise adding a chemical cross-linking agent to partially cross-link the cellulose/nano inorganic filler mixed dispersion liquid, centrifugally removing bubbles in the mixed dispersion liquid, and standing under the set temperature condition to obtain the partially cross-linked 3D printing cellulose/nano inorganic filler composite gel ink;
(4) soaking the prepared 3D printing cellulose/nano inorganic filler composite gel ink in deionized water at 50-100 ℃ for storage, wherein the effective storage life is 6 months; when in use, the 3D printing forming can be realized by inducing the complete crosslinking through heat.
In the ultrasonic dispersion process of the nano inorganic filler in the step (1), the ultrasonic power is 20W-80W, and the ultrasonic time is 1 h-12 h.
The alkali/urea solution in the step (2) is a NaOH/urea or LiOH/urea solution system, and the precooling specified temperature range of the alkali/urea solution system is-5 ℃ to-25 ℃.
The cellulose addition amount in the cellulose dispersion liquid in the step (2) is 3-8 wt%, and in the mixed dispersion liquid of cellulose/nano inorganic filler, the sum of the addition amounts of the nano inorganic filler and the cellulose is 5-30 wt%.
And (3) mechanically stirring under an ice-bath condition under the stirring condition, wherein the mechanical stirring rotating speed is 500-1500 r/min.
The standing condition in the step (3) is that the mixture is kept standing for 10min to 30min at the temperature of 10 ℃ to 30 ℃.
The alkali/urea solution in the step (2) is one of NaOH/urea or LiOH/urea solution systems, and the concentration of the alkali/urea solution is as follows: in the NaOH/urea solution system, the concentration of NaOH is 6 wt% -10 wt%, and the concentration of urea is 2 wt% -20 wt%; in the LiOH/urea solution system, the concentration of LiOH is 2 wt% -5 wt%, and the concentration of urea is 4 wt% -30 wt%.
Compared with the prior art, the invention has the beneficial effects that:
1. the 3D printing cellulose/nano inorganic filler composite gel ink and the preparation method thereof provided by the invention overcome the defects of the prior art, synchronously improve the formula and the preparation process, and take cellulose as a polymer matrix of the 3D printing ink, so that the ink has good biocompatibility, mechanical property, environmental friendliness and mild forming conditions, and can be used for rapid 3D printing forming of 3D polymer composite reinforced materials.
2. The composite gel ink material and the preparation method thereof provided by the invention have high efficiency, and the formula is specially designed, so that the composite gel ink is a polymer-based composite gel ink which uses inorganic nano-fillers such as graphene oxide and the like and is used for thermally triggering and rapidly forming a 3D printing composite high polymer material, wherein the addition amount of the inorganic nano-fillers such as graphene oxide and the like is 0.5-30 wt%, and rapid crosslinking and forming can be realized under thermal triggering.
3. The 3D printing composite gel ink provided by the invention takes cellulose as a polymer matrix of the 3D printing ink, has good biocompatibility, mechanical property and environmental friendliness, is wide in source and low in raw material cost, and can be used for printing and preparing polymer reinforced composite materials in electronic devices, electronic packaging and other fields.
4. The 3D printing composite gel ink provided by the invention adopts cellulose as a polymer matrix of the 3D printing ink, the cellulose is polysaccharide which is most widely distributed and contained in nature, accounts for more than 50% of the carbon content of plants, and is a natural material with wide sources. Trees, bamboos, grasses, even crop wastes (wheat straws, bagasse and beet pulp) and other plants in the nature can be used as main sources of cellulose, wherein the cellulose content of cotton is close to 100 percent and is the purest natural cellulose source, and the cellulose content in general wood can reach 40-50 percent. The cellulose-based composite material provided by the invention can be widely applied to many fields due to excellent strength, toughness and transparency, for example: electronic devices, supercapacitors, biomaterials, aerospace, and the like.
The foregoing is a summary of the technical solutions of the present invention, and the present invention is further described below with reference to specific embodiments.
Drawings
Fig. 1 is a scanning electron microscope image of a 3D printed cellulose/graphene oxide composite material in an embodiment of the present invention;
FIG. 2 is a scanning electron microscope image of the graphene oxide nano inorganic filler in the embodiment of the present invention.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the intended purposes, the following detailed description of the embodiments of the present invention is given with reference to the preferred embodiments.
Example (b):
the invention provides 3D printing cellulose/nano inorganic filler composite gel ink which is a cellulose-based composite gel aqueous solution taking a nano inorganic material as a filler and cellulose as a polymer matrix, and is prepared from 15-20 parts of nano inorganic filler dispersion liquid, 90-100 parts of cellulose dispersion liquid and 1-2 parts of a chemical cross-linking agent according to the mass part ratio; the addition amount of the nano inorganic filler in the nano inorganic filler dispersion liquid is 1-30 wt%, and the addition amount of the fiber in the cellulose dispersion liquid is 4-6 wt%.
The nano inorganic filler is one of graphene oxide nanosheets, clay nanosheets and carbon nanotubes; the cellulose raw material is cotton linter; the chemical cross-linking agent is epichlorohydrin; the ink is partially cross-linked when the preparation is completed; when in use, the ink is soaked in deionized water at 50-100 ℃, and can be quickly formed by completely crosslinking through thermal induction, and 3D printing and forming are carried out.
A method for preparing the 3D printing cellulose/nano inorganic filler composite gel ink comprises the following steps:
(1) adding a certain amount of nano inorganic filler into deionized water, and performing ultrasonic dispersion to obtain uniformly dispersed nano inorganic filler dispersion liquid; the ultrasonic power in the ultrasonic dispersion process is 20W-80W, and the ultrasonic time is 1 h-12 h;
(2) taking a certain amount of cotton linter raw material, adding an alkali/urea solution precooled to a specified temperature, and quickly stirring to obtain a cellulose dispersion liquid; adding the nano inorganic filler dispersion liquid obtained in the step (1) into cellulose dispersion liquid, and violently stirring to obtain cellulose/nano inorganic filler mixed dispersion liquid;
the alkali/urea solution is a NaOH/urea or LiOH/urea solution system, and the precooling specified temperature range of the alkali/urea solution system is-5 ℃ to-25 ℃;
the alkali/urea solution is one of NaOH/urea or LiOH/urea solution systems, and the concentration of the alkali/urea solution is as follows: in the NaOH/urea solution system, the concentration of NaOH is 6 wt% -10 wt%, and the concentration of urea is 2 wt% -20 wt%; in a LiOH/urea solution system, the concentration of LiOH is 2-5 wt%, and the concentration of urea is 4-30 wt%;
(3) violently stirring the cellulose/nano inorganic filler mixed dispersion liquid obtained in the step (2) under a set temperature condition, slowly dropwise adding a chemical cross-linking agent to partially cross-link the cellulose/nano inorganic filler mixed dispersion liquid, centrifugally removing bubbles in the mixed dispersion liquid, and standing under the set temperature condition to obtain the partially cross-linked 3D printing cellulose/nano inorganic filler composite gel ink;
the cellulose dispersion liquid contains 3-8 wt% of cellulose, and in the cellulose/nano inorganic filler mixed dispersion liquid, the sum of the addition of the nano inorganic filler and the cellulose is 5-30 wt%;
the stirring condition is that the mechanical stirring is carried out under the ice bath condition, and the mechanical stirring rotating speed is 500r/mim-1500 r/min;
the standing condition is that the mixture is kept standing at the temperature of 10-30 ℃ for 10-30 min.
(4) Soaking the prepared 3D printing cellulose/nano inorganic filler composite gel ink in deionized water at 50-100 ℃ for storage, wherein the effective storage life is 6 months; when in use, the 3D printing forming can be realized by inducing the complete crosslinking through heat.
Specific example 1:
referring to the attached drawings 1-2, in the 3D printing cellulose/nano inorganic filler composite gel ink provided in this embodiment, hydroxylated graphene oxide is used as a nano inorganic filler.
A preparation method of cellulose/graphene composite gel ink for 3D printing of a nano composite material comprises the following steps:
(1) adding a certain amount of hydroxylated graphene oxide into deionized water, and performing ultrasonic dispersion to obtain a uniformly dispersed graphene oxide dispersion liquid; in the graphene oxide ultrasonic dispersion process, the ultrasonic power is 20W-80W, and the ultrasonic time is 1 h-12 h;
(2) taking a certain amount of cotton linter raw material, adding an alkali/urea solution precooled to a specified temperature, and quickly stirring to obtain a cellulose dispersion liquid; adding the graphene oxide dispersion liquid obtained in the step (1) into a cellulose dispersion liquid, and violently stirring to obtain a cellulose/graphene oxide mixed dispersion liquid;
the alkali/urea solution is NaOH/urea, and the pre-cooling specified temperature range of an alkali/urea solution system is-5 ℃ to-25 ℃; in this example, the NaOH concentration was 6 wt%, and the urea concentration was 4 wt%;
the concentration of the cellulose dispersion liquid is 3 wt% -8 wt%, and the total mass sum of the addition amount of graphene oxide and cellulose in the cellulose/graphene oxide mixed dispersion liquid is 5-30 wt%.
(3) Violently stirring the cellulose/graphene oxide mixed dispersion liquid obtained in the step (2) under the condition of set temperature, slowly dropwise adding a chemical cross-linking agent, centrifuging to remove bubbles in the mixed dispersion liquid, standing under the condition of set temperature to obtain partially cross-linked cellulose/graphene oxide composite gel ink, and storing at 0 ℃;
the stirring condition is that the mechanical stirring is carried out under the ice bath condition, and the mechanical stirring rotating speed is 500r/mim-1500 r/min; the chemical cross-linking agent is epichlorohydrin
The standing condition is that the mixture is kept standing at the temperature of 10-30 ℃ for 10-30 min.
More specifically, the preparation method of the cellulose/graphene composite gel ink for 3D printing of the nanocomposite material provided by the embodiment of the invention comprises the following steps:
(1) adding 0.5g of graphene oxide powder into 19.5g of deionized water, and carrying out ultrasonic treatment for 30min under the power of 80W to obtain a graphene oxide dispersion liquid;
(2) weighing 4.5g of dried cotton linter raw material, adding 75.5g of 6 wt% NaOH/12 wt% urea solution precooled to-10 ℃, and rapidly stirring for 5min to obtain cellulose dispersion;
(3) mixing the graphene oxide dispersion liquid obtained in the step (1) and the graphene oxide dispersion liquid obtained in the step (2) with a cellulose dispersion liquid, and mechanically stirring at the rotating speed of 800r/min under the ice bath condition;
(4) slowly dripping 1mL of chemical cross-linking agent epichlorohydrin under the stirring condition of the step (3), and stirring for 30min in ice bath;
(5) putting the cellulose/graphene oxide viscous dispersion liquid obtained in the step (4) into a beaker, sealing and placing at the temperature of 25 ℃, standing and storing for 20min to obtain partially crosslinked cellulose/graphene oxide composite gel ink;
(6) and (3) sealing and storing the part of the cross-linked cellulose/graphene oxide composite gel ink after standing in the step (5) in an environment at 0 ℃ to prepare the 3D printing cellulose/graphene composite gel ink.
The 3D printing cellulose/graphene composite gel ink prepared by the embodiment has excellent comprehensive performance, and through practical tests, the effective storage life of the printing ink is 6 months, and the printing ink can be formed under the induction of high temperature of 50-100 ℃. Meanwhile, the raw material components are safe, the process manufacturing cost is low, and the method is favorable for industrialization and large-scale popularization and application.
Specific example 2:
the preparation method of the cellulose/graphene composite gel ink for 3D printing of the nano composite material, provided by the embodiment of the invention, comprises the following steps:
(1) adding 1.0g of graphene oxide powder into 19.0g of deionized water, and carrying out ultrasonic treatment for 30min under the power of 80W to obtain a graphene oxide dispersion liquid;
(2) weighing 4.5g of dried cotton linter raw material, adding 75.5g of 7 wt% NaOH/20 wt% urea solution precooled to-10 ℃, and rapidly stirring for 5min to obtain cellulose dispersion;
(3) mixing the graphene oxide dispersion liquid obtained in the step (1) and the graphene oxide dispersion liquid obtained in the step (2) with a cellulose dispersion liquid, and mechanically stirring at the rotating speed of 1000r/min under the ice bath condition;
(4) slowly dripping 1mL of chemical cross-linking agent epichlorohydrin under the stirring condition of the step (3), and stirring for 30min in ice bath;
(5) putting the cellulose/graphene oxide viscous dispersion liquid obtained in the step (4) into a beaker, sealing and placing at the temperature of 25 ℃, standing and storing for 20min to obtain partially crosslinked cellulose/graphene oxide composite gel ink;
(6) and (3) sealing and storing the part of the cross-linked cellulose/graphene oxide composite gel ink after standing in the step (5) in an environment at 0 ℃ to prepare the 3D printing cellulose/graphene composite gel ink.
The 3D printing cellulose/graphene composite gel ink prepared by the embodiment has excellent comprehensive performance, and through practical tests, the effective storage life of the printing ink is 6 months, and the printing ink can be formed under the induction of high temperature of 50-100 ℃. Meanwhile, the raw material components are safe, the process manufacturing cost is low, and the method is favorable for industrialization and large-scale popularization and application.
Specific example 3:
the preparation method of the cellulose/graphene composite gel ink for 3D printing of the nano composite material, provided by the embodiment of the invention, comprises the following steps:
(1) adding 1.5g of graphene oxide powder into 18.5g of deionized water, and carrying out ultrasonic treatment for 30min under the power of 80W to obtain a graphene oxide dispersion liquid;
(2) weighing 4.5g of dried cotton linter raw material, adding 75.5g of 10 wt% NaOH/2 wt% urea solution precooled to-10 ℃, and rapidly stirring for 5min to obtain cellulose dispersion;
(3) mixing the graphene oxide dispersion liquid obtained in the step (1) and the graphene oxide dispersion liquid obtained in the step (2) with a cellulose dispersion liquid, and mechanically stirring at the rotating speed of 1200r/min under the ice bath condition;
(4) slowly dripping 1mL of chemical cross-linking agent epichlorohydrin under the stirring condition of the step (3), and stirring for 30min in ice bath;
(5) putting the cellulose/graphene oxide viscous dispersion liquid obtained in the step (4) into a beaker, sealing and placing at the temperature of 25 ℃, standing and storing for 20min to obtain partially crosslinked cellulose/graphene oxide composite gel ink;
(6) and (3) sealing and storing the part of the cross-linked cellulose/graphene oxide composite gel ink after standing in the step (5) in an environment at 0 ℃ to prepare the 3D printing cellulose/graphene composite gel ink.
The preparation method of the cellulose/graphene composite gel ink for 3D printing of the nano composite material, which is prepared by the embodiment, has excellent comprehensive performance, and through practical tests, the effective storage life of the printing ink is 6 months, and the printing ink can be formed under the induction of a high temperature of 50-100 ℃. Meanwhile, the raw material components are safe, the process manufacturing cost is low, and the method is favorable for industry and large-scale popularization and application.
The formula and the mixture ratio (mass fraction ratio) in other examples are shown in the following table:
it should be noted that the above-mentioned embodiments of the present invention are only some examples; in other embodiments, other specific components and ratios and preparation process parameters are selected within the range described in the invention, and the obtained preparation method and materials can achieve the technical effects described in the invention, so that the invention is not listed one by one.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the technical scope of the present invention, so that the technical features similar to or similar to the above-described embodiment of the present invention are all within the protective scope of the present invention.
Claims (10)
1. The 3D printing cellulose/nano inorganic filler composite gel ink is characterized by being a cellulose-based composite gel aqueous solution taking a nano inorganic material as a filler and cellulose as a polymer matrix, and prepared from 15-20 parts of nano inorganic filler dispersion liquid, 90-100 parts of cellulose dispersion liquid and 1-2 parts of a chemical cross-linking agent according to the mass part ratio; the addition amount of the nano inorganic filler in the nano inorganic filler dispersion liquid is 0.5-30 wt%, and the addition amount of the fiber in the cellulose dispersion liquid is 4-6 wt%.
2. The 3D printing cellulose/nano inorganic filler composite gel ink as claimed in claim 1, wherein the nano inorganic filler is one of graphene oxide nanosheets, clay nanosheets, and carbon nanotubes; the cellulose raw material is cotton linter; the chemical cross-linking agent is epichlorohydrin; the ink is partially cross-linked when the preparation is completed; when in use, the ink is soaked in deionized water at 50-100 ℃, and can be quickly formed by completely crosslinking through thermal induction, and 3D printing and forming are carried out.
3. A method for preparing the 3D printed cellulose/nano inorganic filler composite gel ink according to one of claims 1 or 2, characterized in that it comprises the following steps:
(1) adding a certain amount of nano inorganic filler into deionized water, and performing ultrasonic dispersion to obtain uniformly dispersed nano inorganic filler dispersion liquid;
(2) taking a certain amount of cotton linter raw material, adding an alkali/urea solution precooled to a specified temperature, and quickly stirring to obtain a cellulose dispersion liquid; adding the nano inorganic filler dispersion liquid obtained in the step (1) into cellulose dispersion liquid, and violently stirring to obtain cellulose/nano inorganic filler mixed dispersion liquid;
(3) and (3) violently stirring the cellulose/nano inorganic filler mixed dispersion liquid obtained in the step (2) under the condition of a set temperature, slowly dropwise adding a chemical cross-linking agent to partially cross-link the cellulose/nano inorganic filler mixed dispersion liquid, centrifugally removing bubbles in the mixed dispersion liquid, and standing under the condition of the set temperature to obtain the partially cross-linked 3D printing cellulose/nano inorganic filler composite gel ink.
4. The method of claim 3, further comprising the steps of:
(4) soaking the prepared 3D printing cellulose/nano inorganic filler composite gel ink in deionized water at 50-100 ℃ for storage, wherein the effective storage life is 6 months; when in use, the 3D printing forming can be realized by inducing the complete crosslinking through heat.
5. The preparation method according to claim 3, wherein in the step (1), the nano inorganic filler is ultrasonically dispersed at an ultrasonic power of 20W-80W for 1 h-12 h.
6. The method according to claim 3, wherein the alkali/urea solution in step (2) is NaOH/urea solution system or LiOH/urea solution system, and the pre-cooling temperature range of the alkali/urea solution system is-5 ℃ to-25 ℃.
7. The method according to claim 3, wherein the cellulose dispersion liquid in the step (2) contains 3 to 8 wt% of cellulose, and the total amount of the nano inorganic filler and the cellulose in the cellulose/nano inorganic filler mixed dispersion liquid is 5 to 30 wt%.
8. The method according to claim 3, wherein the stirring conditions in step (3) are mechanical stirring under ice bath conditions, and the mechanical stirring speed is 500r/mim to 1500 r/min.
9. The method according to claim 3, wherein the standing condition in the step (3) is a standing at a temperature of 10 to 30 ℃ for 10 to 30 minutes.
10. The method according to claim 3, wherein the alkali/urea solution in step (2) is one of NaOH/urea or LiOH/urea solution system, and the concentration thereof is as follows: in the NaOH/urea solution system, the concentration of NaOH is 6 wt% -10 wt%, and the concentration of urea is 2 wt% -20 wt%;
in the LiOH/urea solution system, the concentration of LiOH is 2 wt% -5 wt%, and the concentration of urea is 4 wt% -30 wt%.
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