CN114058167B - Nano-cellulose modified pecan shell micro powder/thermoplastic material composite 3D printing consumable and preparation method thereof - Google Patents
Nano-cellulose modified pecan shell micro powder/thermoplastic material composite 3D printing consumable and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- 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
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Abstract
The invention discloses a nanocellulose modified pecan shell micro powder/thermoplastic material composite 3D printing consumable and a preparation method thereof, wherein the nanocellulose modified pecan shell micro powder/thermoplastic material composite 3D printing consumable comprises the following components in parts by mass: 60-80 parts of pecan shell, 5-10 parts of talcum powder, 4.8-9 parts of nano-cellulose, 0.1-0.5 part of cationic starch, 0.1-0.5 part of alkyl ketene dimer, 5-10 parts of coupling agent and 5-10 parts of lubricating agent; the thermoplastic material comprises the following components in parts by mass: 50-80 parts of polylactic acid, 5-20 parts of poly (butylene adipate)/terephthalate, 10-20 parts of cellulose biological composite material, 1-5 parts of toughening agent and 1-5 parts of antioxidant; the general formula of the nano-cellulose modified pecan shell micro powder is R-CH 2 -CO-CH (-CO-O-Cellulose) -R, wherein R is hydrophobic group, and Cellulose is Cellulose biological composite material. The preparation method comprises the following steps: mixing, drying, stirring, forming and rolling. The 3D printing consumable prepared by the method has the advantages that the flexural modulus, the thermal deformation temperature, the cantilever beam notch impact and other properties are effectively improved.
Description
Technical Field
The invention relates to the technical field of 3D printing consumables, in particular to a nanocellulose modified pecan shell micro powder/thermoplastic material composite 3D printing consumable and a preparation method thereof.
Background
3D printing is one of the rapid prototyping technologies, which is a technology for constructing an object by using an adhesive material such as powdered metal or plastic and the like in a layer-by-layer printing manner on the basis of a digital model file. 3D printing technology has applications in a variety of fields, such as aerospace, medical, jewelry, industrial design, automotive manufacturing, construction, personalized lighting, education, and others.
Polylactic acid (PLA) is most widely applied to desktop-level (FDM) 3D printing, has good mechanical properties and physical properties, has the characteristics of environmental friendliness, no toxicity, no harm, biodegradability, good biocompatibility and the like, and is widely applied to various fields of medical treatment, food packaging, fast food boxes and the like.
The pure PLA 3D printing consumables have smooth surfaces, poor surface texture, monotonous transmission and reflection light rays and the like, and cannot meet the application requirements of products such as artistic woodcarving, lamp decoration and the like in some fields, particularly the fields of decoration and fitment.
The polylactic acid is used as a matrix, and the nano particles or plant fibers are used as reinforcing components to prepare the composite material, so that the material with improved heat resistance, mechanical property, optical property, surface property and the like can be obtained. Composite materials based on vegetable fibers as reinforcing components, polypropylene (PP) and the like have been used in the industry. The composite material has the advantages of good rigidity, toughness, fracture performance, heat insulation, sound absorption, dimensional stability, weather resistance and the like, but if the composite material is applied to the field of 3D printing, the biggest problem is that simple blending causes that plant fibers are not uniformly dispersed, and non-dispersed agglomerated fibers can cause the problems of nozzle blockage, nozzle abrasion and the like due to the increase of the resistance of a 3D printing wire at a nozzle part caused by the reduction of local thermoplastic energy, and the composite material is unacceptable in the application of 3D printing.
The Nanocellulose (NC) has the advantages of wide source, light weight, degradability, large specific surface area, high specific strength and the like. In terms of mechanical properties, the nano-cellulose has extremely high strength, excellent toughness and higher modulus, the strength of the nano-cellulose is about 5 times that of steel, and the density of the nano-cellulose is only one fifth of that of the steel. In practical applications, the compatibility of unmodified nanocellulose with thermoplastic materials is a problem due to the high specific surface area and high aspect ratio of nanocellulose and the easy formation of agglomeration and entanglement due to the van der waals force between nanocelluloses. From a structural point of view, an interface layer is present between the fibres and the thermoplastic material, the properties of which interface layer have a decisive influence on the properties of the composite material. It is believed that the macromolecular segments may interdiffuse between the interfacial layers and form interfacial chemical bonds. The comprehensive action result of factors such as diffusion, wetting, phase interface morphology, physical and chemical composition, intermolecular force and the like of macromolecular chains determines the mechanical strength of an interface region, and strong hydrogen bond action exists among cellulose macromolecular chains, so that natural plant fibers have strong polarity and hydrophilicity and poor compatibility with hydrophobic and nonpolar thermoplastic materials, and the performance of the composite material is influenced. The chemical modification of natural fibers can effectively solve the problem of compatibility between the fibers and thermoplastic materials.
In order to improve the compatibility between the nanocellulose and the polylactic acid matrix, at present, methods such as acetylation, silanization or graft modification are generally adopted internationally to improve the affinity performance of the nanocellulose and the polylactic acid, and the methods can improve the surface polarity of the nanocellulose to a certain extent, but the complicated chemical modification method inevitably causes the loss of the mechanical properties of the nanocellulose, the increase of the preparation cost, and the increase of the post-treatment difficulty such as separation and purification, solvent recovery and the like. The pecan shell micro powder is used as a byproduct of grinding of a shell left after pecan kernel taking, and is an optional 3D printing consumable powder filler. At present, the pecan shells are mainly used for preparing activated carbon or nutrient soil, but most of the pecan shells are still discarded. The pecan shell mainly contains cellulose, hemicellulose, oil, lignin, etc. Researches report that the pecan shell micro powder has porous performance, which is beneficial to the dispersion and coating modification of nano cellulose. According to the invention, after the pecan shell micro powder is subjected to surface coating, hydrophobic property and coupling modification, the compatibility of the pecan shell micro powder and a thermoplastic material is increased, the thermal stability and the mechanical strength of the material are improved, the obtained composite material is applied to the production of FDM 3D printing consumables, the molded product shows different mechanical strength due to different addition amounts of the pecan shell micro powder, and simultaneously shows a surface texture similar to a wood material, and the surface texture is from white birch color to dark brown, so that a semi-matte or matte surface effect is shown.
Disclosure of Invention
The invention aims to provide a nano-cellulose modified pecan shell micro-powder/thermoplastic material composite 3D printing consumable material and a preparation method thereof, wherein natural high-strength characteristics of pecan shells and the further enhancement synergistic effect of nano-cellulose are utilized, a micro-powder key material is prepared by combining alkylated hydrophobic modification and coupling agent surface modification, the process flow is short, hazardous chemicals and organic solvents are not used, the condition is mild, the further prepared nano-cellulose modified pecan shell micro-powder 3D printing consumable material is smooth in printing, is not easy to absorb water and damp, toxic and irritating harmful components are not contained in the components, the strength of the printed material is higher, and the texture of wood is obvious.
The technical scheme adopted by the invention is as follows:
a nanocellulose modified pecan shell micro powder/thermoplastic material composite 3D printing consumable material is formed by mixing the nanocellulose modified pecan shell micro powder and a thermoplastic material according to a mass ratio of 1:9-1:4;
the nano-cellulose modified pecan shell micro powder comprises the following components in parts by mass: 60-80 parts of pecan shell, 5-10 parts of talcum powder, 4.8-9 parts of nano-cellulose, 0.1-0.5 part of cationic starch, 0.1-0.5 part of alkyl ketene dimer, 5-10 parts of coupling agent and 5-10 parts of lubricating agent;
the thermoplastic material comprises the following components in parts by mass: 50-80 parts of polylactic acid, 5-20 parts of poly (butylene adipate)/terephthalate, 10-20 parts of cellulose biological composite material, 1-5 parts of toughening agent and 1-5 parts of antioxidant;
the general formula of the nano-Cellulose modified pecan shell micro-powder is R-CH2-CO-CH (-CO-O-Cellulose) -R, wherein R is hydrophobic group, and Cellulose is a Cellulose biological composite material.
Furthermore, the talcum powder is magnesium silicate mineral with the fineness of 325-800 meshes; the nano-cellulose is prepared by grinding wood pulp and bamboo pulp fibers serving as raw materials, wherein the diameter of the nano-cellulose is 10-500nm; the cationic starch is a quaternary ammonium salt modified starch derivative, and the cationic substitution degree is 0.02-0.05.
Further, the coupling agent is any one or a mixture of more than two of the following: silane coupling agent, titanate coupling agent or aluminate coupling agent.
Further, the lubricant is any one or a mixture of two or more of the following: calcium stearate, stearamide, oleamide, erucamide, zinc stearate, high molecular complex ester of metal soap, ethylene bis stearamide, polyethylene wax or silicone.
Further, the cellulose biocomposite is specifically a cellulose biocomposite model UPMFormi3D produced by finland and ohuiwa group.
Further, the toughening agent is any one or a mixture of more than two of the following components: styrene-butadiene-styrene block copolymers or hydrogenated styrene-butadiene-styrene block copolymers.
Further, the antioxidant is any one or a mixture of two or more of the following: 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, pentaerythritol tetrakis [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, octadecyl beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, dialkyl thiodipropionate or 2,6-di-tert-butyl-p-cresol.
The invention also provides a preparation method of the nano-cellulose modified pecan shell micro-powder/thermoplastic material composite 3D printing consumable material, which comprises the following steps:
s1, mixing the pecan shells and the talcum powder, adding the mixture into a ball mill, and performing ball milling by using alumina grinding balls to obtain pecan shell micro powder with the fineness of 300-800 meshes;
s2, adding the pecan micro powder into a nano cellulose aqueous solution, dropwise adding a cationic starch solution, stirring for 3-5 minutes after dropwise adding, dropwise adding an alkyl ketene dimer emulsion, stirring for 3-5 minutes after dropwise adding, and dropwise adding ammonia water to adjust the pH value to 7.5-8.5 to obtain a mixed solution of the pecan shell micro powder and the nano cellulose;
s3, drying the mixed solution of the pecan shell micro powder and the nano-cellulose in a vacuum drying oven, and performing surface coating modification and surface alkylation modification on the pecan shell micro powder to obtain the pecan shell micro powder with the water content of less than 1 percent, the surface of the nano-cellulose being coated and subjected to hydrophobic modification;
s4, mixing the pecan shell micro powder coated on the surface of the nano-cellulose and subjected to hydrophobic modification, a coupling agent and a lubricant, adding the mixture into a ball mill, and performing ball milling by using an alumina grinding ball, introducing terminal olefin into the surface of the nano-cellulose to obtain nano-cellulose modified pecan shell micro powder;
s5, drying materials: placing the nano-cellulose modified pecan shell micro-powder, polylactic acid particles, poly (butylene adipate/terephthalate) particles, cellulose biological composite material, toughening agent and antioxidant into an oven for drying;
s6, preparing materials: taking dried nano cellulose modified pecan shell micro powder, polylactic acid particles, poly adipic acid/butylene terephthalate particles, cellulose biological composite materials, toughening agents and antioxidants according to the formula;
s7, mixing materials: placing the prepared raw materials in a high-speed mixer to be uniformly mixed;
s8, granulation: adding the uniformly mixed raw materials into a single-screw or double-screw extruder for extrusion, air cooling, granulating and sieving to obtain new nano-cellulose modified pecan shell micro-powder/thermoplastic material composite particles;
s9, forming and rolling: and putting the nano-cellulose modified pecan shell micro-powder/thermoplastic material composite particles into a single-screw or double-screw extruder for extrusion and wire-drawing molding, and cooling and rolling to obtain the nano-cellulose modified pecan shell micro-powder/thermoplastic material composite 3D printing consumable.
Further, the drying temperature in the vacuum drying oven in the step S3 is 80-90 ℃, and the drying time is 5-10 hours.
Further, when a single-screw or double-screw extruder is used for granulation in the step S8, the temperature of the first temperature zone is 140-155 ℃, the temperature of the second temperature zone is 155-165 ℃, and the temperature of the third temperature zone is 165-175 ℃; the extrusion speed is 700-900rpm, and the traction speed is 300-500rpm; when a single-screw or double-screw extruder is used for extrusion, wire drawing and forming in the step S9, the temperature of the first temperature zone is 160-175 ℃, the temperature of the second temperature zone is 175-185 ℃, the temperature of the third temperature zone is 185-200 ℃, and the temperature of the water tank is 45-55 ℃; the extrusion speed is 700-900rpm, the traction speed is 400-600rpm, and the winding speed is 9.0-15.0rpm.
The invention has the beneficial effects that:
compared with common wood powder, the nano-cellulose modified pecan shell micro-powder provided by the invention has the advantages that since the pecan shell is hard, the properties of the manufactured 3D printing consumable, such as flexural modulus, thermal deformation temperature, cantilever beam notch impact and the like, are effectively improved after the surface of the nano-cellulose is enhanced. The nanocellulose is uniformly coated on the surface of the pecan micro powder, so that the nanocellulose is uniformly distributed in biodegradable plastic systems such as polylactic acid and the like, the risks of abrasion and blockage of a printer nozzle caused by agglomeration of the nanocellulose are reduced, and smooth printing is ensured. The density of the nano-cellulose modified pecan shell micro-powder is lighter than that of polylactic acid, and the nano-cellulose modified pecan shell micro-powder is not easy to absorb water and damp, so that the prepared cellulose biological composite material has obvious comparative advantages for 3D printing products with light weight, high strength, heat resistance and low shrinkage. The modified pecan shell micro powder 3D printing consumable containing the nano-cellulose can be directly used on a household or commercial desktop printer without special high-temperature equipment.
Detailed Description
The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
S1, mixing 400g of hickory shell and 50g of hydrated magnesium silicate talcum powder (the mesh number is 325 meshes), adding into a ball mill, and carrying out ball milling by using alumina grinding balls for 1-2 hours, and taking out to obtain the hickory shell micro powder;
s2, adding the pecan micro powder into 1800g of nano cellulose aqueous solution (2.5% solid content, diameter less than 500nm and length less than 100 microns), dropwise adding 10g of methacryloyloxyethyl trimethyl ammonium chloride grafted cationic starch solution (5% solid content), stirring for 3-5 minutes after dropwise adding, dropwise adding 4g of alkyl ketene dimer emulsion (12.5% solid content), stirring for 3-5 minutes after dropwise adding, dropwise adding ammonia water to adjust the pH value to 7.5-8.5, and obtaining a mixed solution of the pecan shell micro powder and the nano cellulose;
s3, drying the mixed solution of the pecan shell micro powder and the nano-cellulose in a vacuum drying oven at the temperature of 80 ℃ for 7 hours, and performing surface coating modification and surface alkylation modification on the pecan shell micro powder to obtain the pecan shell micro powder with the water content of less than 1 percent, the surface coating of the nano-cellulose and hydrophobic modification;
s4, mixing the pecan shell micro powder with the surface of the nano-cellulose coated and subjected to hydrophobic modification, 50g of methacryloxy trimethoxy silane coupling agent and 50g of calcium stearate lubricant, adding the mixture into a ball mill, performing ball milling by using alumina grinding balls for 1-2 hours, and introducing terminal olefin into the surface of the nano-cellulose to obtain the nano-cellulose modified pecan shell micro powder;
s5, drying materials: placing the nano-cellulose modified pecan shell micro powder, polylactic acid particles, polybutylene adipate/terephthalate particles, cellulose biological composite materials, styrene-butadiene-styrene block copolymers, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane in an oven at 60 ℃ for drying for 4 hours;
s6, preparing materials: taking 10g of dried nano-cellulose modified pecan shell micro powder, 64g of polylactic acid particles, 10g of poly adipic acid/butylene terephthalate particles, 10g of cellulose biological composite material, 5g of styrene-butadiene-styrene block copolymer and 1g of 1,1,3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane according to the formula;
s7, mixing materials: placing the prepared raw materials in a high-speed mixer with the rotating speed of 1000r/min for uniformly mixing for 3min;
s8, granulation: adding the uniformly mixed raw materials into a single-screw or double-screw extruder for extrusion, air cooling, granulating and sieving to obtain new nano-cellulose modified pecan shell micro-powder/thermoplastic material composite particles; wherein, when a single screw or double screw extruder is used for granulation, the temperature of the first temperature zone is 140 ℃, the temperature of the second temperature zone is 155 ℃, and the temperature of the third temperature zone is 165 ℃; the extrusion speed is 800rpm, and the traction speed is 350rpm;
s9, forming and rolling: putting the nano-cellulose modified pecan shell micro-powder/thermoplastic material composite particles into a single-screw or double-screw extruder for extrusion, wire-drawing and molding, cooling and rolling to obtain a nano-cellulose modified pecan shell micro-powder/thermoplastic material composite 3D printing consumable; wherein, when a single-screw extruder is used for extrusion wire-drawing forming, the temperature of the first temperature zone is 160 ℃, the temperature of the second temperature zone is 180 ℃, the temperature of the third temperature zone is 185 ℃, and the temperature of the water tank is 50 ℃; the extrusion speed was 800rpm, the drawing speed was 500rpm, and the take-up speed was 10rpm.
Example 2
S1, mixing 350g of hickory shell and 45g of hydrated magnesium silicate talcum powder (the mesh number is 325 meshes), adding into a ball mill, and carrying out ball milling by using alumina grinding balls for 1-2 hours, and taking out to obtain the hickory shell micro powder;
s2, adding the pecan micro powder into 1600g of nano-cellulose aqueous solution (2.5% solid content, diameter less than 500nm and length less than 100 microns), dropwise adding 16g of methacryloyloxyethyl trimethyl ammonium chloride grafted cationic starch solution (5% solid content), stirring for 3-5 minutes after dropwise adding, dropwise adding 6.4g of alkyl ketene dimer emulsion (12.5% solid content), stirring for 3-5 minutes after dropwise adding, dropwise adding ammonia water to adjust the pH value to 7.5-8.5, and obtaining a mixed solution of the pecan shell micro powder and the nano-cellulose;
s3, drying the mixed solution of the pecan shell micro powder and the nano-cellulose in a vacuum drying oven at the temperature of 85 ℃ for 6 hours, and performing surface coating modification and surface alkylation modification on the nano-cellulose to obtain the pecan shell micro powder with the water content of less than 1 percent, the surface of the nano-cellulose being coated and subjected to hydrophobization modification;
s4, mixing the pecan shell micro powder with the surface of the nano-cellulose coated and subjected to hydrophobic modification, 45g of methacryloxy trimethoxy silane coupling agent and 40g of stearamide lubricant, adding the mixture into a ball mill, performing ball milling by using an alumina grinding ball for 1-2 hours, and introducing terminal olefin into the surface of the nano-cellulose to obtain the nano-cellulose modified pecan shell micro powder;
s5, drying materials: placing the nano-cellulose modified pecan shell micro powder, polylactic acid particles, polybutylene adipate/terephthalate particles, cellulose biological composite materials, hydrogenated styrene-butadiene-styrene block copolymers and tetra [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) pentaerythritol propionate into an oven at 60 ℃ for drying for 4 hours;
s6, preparing materials: taking 16g of dried nano-cellulose modified pecan shell micro powder, 59g of polylactic acid particles, 10g of poly (butylene adipate)/terephthalate particles, 10g of cellulose biological composite material, 5g of hydrogenated styrene-butadiene-styrene block copolymer and 5g of tetra [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) pentaerythritol propionate according to the formula;
s7, mixing materials: placing the prepared raw materials in a high-speed mixer with the rotating speed of 1500r/min for uniformly mixing for 3min;
s8, granulation: adding the uniformly mixed raw materials into a single-screw or double-screw extruder for extrusion, air cooling, granulating and sieving to obtain new nano-cellulose modified pecan shell micro-powder/thermoplastic material composite particles; wherein, when a single screw or double screw extruder is used for granulation, the temperature of the first temperature zone is 145 ℃, the temperature of the second temperature zone is 157 ℃ and the temperature of the third temperature zone is 170 ℃; the extrusion speed is 750rpm, and the traction speed is 400rpm;
s9, forming and rolling: putting the nano-cellulose modified pecan shell micro-powder/thermoplastic material composite particles into a single-screw or double-screw extruder for extrusion, wire-drawing and molding, cooling and rolling to obtain a nano-cellulose modified pecan shell micro-powder/thermoplastic material composite 3D printing consumable; wherein, when a single screw extruder is used for extrusion wire drawing molding, the temperature of the first temperature zone is 165 ℃, the temperature of the second temperature zone is 175 ℃, the temperature of the third temperature zone is 190 ℃, and the temperature of the water tank is 45 ℃; the extrusion speed was 700rpm, the drawing speed was 400rpm, and the take-up speed was 9rpm.
Example 3
S1, mixing 300g of hickory shell and 25g of hydrated magnesium silicate talcum powder (the mesh number is 325 meshes), adding into a ball mill, and carrying out ball milling by using alumina grinding balls for 1-2 hours, and taking out to obtain the hickory shell micro powder;
s2, adding the pecan micro powder into 960g of nano cellulose aqueous solution (2.5% solid content, diameter less than 500 nanometers and length less than 100 micrometers), dropwise adding 50g of methacryloyloxyethyl trimethyl ammonium chloride grafted cationic starch solution (5% solid content), stirring for 3-5 minutes after dropwise adding, dropwise adding 20g of alkyl ketene dimer emulsion (12.5% solid content), stirring for 3-5 minutes after dropwise adding, dropwise adding ammonia water to adjust the pH value to 7.5-8.5, and obtaining mixed solution of the pecan shell micro powder and the nano cellulose;
s3, drying the mixed solution of the pecan shell micro powder and the nano-cellulose in a vacuum drying oven at the temperature of 80 ℃ for 5 hours, and performing surface coating modification and surface alkylation modification on the pecan shell micro powder to obtain the pecan shell micro powder with the water content of less than 1 percent, the surface coating of the nano-cellulose and the hydrophobic modification;
s4, mixing the pecan shell micro powder with the surface of the nano-cellulose coated and subjected to hydrophobic modification, 25g of methacryloxy trimethoxy silane coupling agent and 25g of oleamide lubricant, adding the mixture into a ball mill, performing ball milling by using alumina grinding balls for 1-2 hours, and introducing terminal olefin into the surface of the nano-cellulose to obtain the nano-cellulose modified pecan shell micro powder;
s5, drying materials: placing the nano-cellulose modified pecan shell micro powder, polylactic acid particles, polybutylene adipate/terephthalate particles, cellulose biological composite materials, hydrogenated styrene-butadiene-styrene block copolymers and beta- (3,5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate in an oven at 60 ℃ for drying for 4 hours;
s6, preparing materials: taking 22.5g of dried nano cellulose modified pecan shell micro powder, 54g of polylactic acid particles, 15g of polybutylene adipate/terephthalate particles, 15g of cellulose biological composite material, 3g of hydrogenated styrene-butadiene-styrene block copolymer and 3g of beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester according to the formula;
s7, mixing materials: placing the prepared raw materials in a high-speed mixer with the rotating speed of 2000r/min for uniformly mixing for 3min;
s8, granulation: adding the uniformly mixed raw materials into a single-screw or double-screw extruder for extrusion, air cooling, granulating and sieving to obtain new nano-cellulose modified pecan shell micro-powder/thermoplastic material composite particles; wherein, when a single screw or double screw extruder is used for granulation, the temperature of the first temperature zone is 155 ℃, the temperature of the second temperature zone is 165 ℃ and the temperature of the third temperature zone is 175 ℃; the extrusion speed is 900rpm, and the traction speed is 500rpm;
s9, forming and rolling: putting the nano-cellulose modified pecan shell micro-powder/thermoplastic material composite particles into a single-screw or double-screw extruder for extrusion, wire-drawing and molding, cooling and rolling to obtain a nano-cellulose modified pecan shell micro-powder/thermoplastic material composite 3D printing consumable; wherein, when a single-screw extruder is used for extrusion wire-drawing forming, the temperature of the first temperature zone is 175 ℃, the temperature of the second temperature zone is 185 ℃, the temperature of the third temperature zone is 200 ℃, and the temperature of the water tank is 55 ℃; the extrusion speed was 900rpm, the haul-off speed was 600rpm, and the take-up speed was 15.0rpm.
Example 4
S1, mixing 320g of hickory shell and 30g of hydrated magnesium silicate talcum powder (mesh number: 500 meshes), adding into a ball mill, and carrying out ball milling by using alumina grinding balls for 1-2 hours, and taking out to obtain the hickory shell micro powder;
s2, adding the pecan micro powder into 1200g of nano cellulose aqueous solution (the solid content is 2.5%, the diameter is less than 500 nanometers, and the length is less than 100 micrometers), dropwise adding 20g of acryloyloxyethyl trimethyl ammonium chloride grafted cationic starch solution (the solid content is 5%), stirring for 3-5 minutes after dripping is finished, dropwise adding 8g of alkyl ketene dimer emulsion (the solid content is 12.5%), stirring for 3-5 minutes after dripping is finished, dropwise adding ammonia water to adjust the pH value to 7.5-8.5, and obtaining a mixed solution of the pecan shell micro powder and the nano cellulose;
s3, drying the mixed solution of the pecan shell micro powder and the nano-cellulose in a vacuum drying oven at the temperature of 90 ℃ for 5 hours, and performing surface coating modification and surface alkylation modification on the pecan shell micro powder to obtain the pecan shell micro powder with the water content of less than 1 percent, the surface coating of the nano-cellulose and the hydrophobic modification;
s4, mixing the pecan shell micro powder with the surface of the nano-cellulose coated and subjected to hydrophobic modification, 40g of di (triethanolamine) diisopropyl titanate coupling agent and 28g of erucamide lubricant, adding the mixture into a ball mill, and performing ball milling for 1-2 hours by using an alumina grinding ball to introduce terminal olefin into the surface of the nano-cellulose to obtain nano-cellulose modified pecan shell micro powder;
s5, drying materials: drying the nano-cellulose modified pecan shell micro-powder, the polylactic acid particles, the poly (butylene adipate)/terephthalate) particles, the cellulose biological composite material, the hydrogenated styrene-butadiene-styrene block copolymer and the dialkyl thiodipropionate in an oven at 60 ℃ for 4 hours;
s6, preparing materials: taking 12g of dried nano-cellulose modified pecan shell micro powder, 50g of polylactic acid particles, 5g of polybutylene adipate/terephthalate particles, 20g of cellulose biological composite material, 1g of hydrogenated styrene-butadiene-styrene block copolymer and 5g of dialkyl thiodipropionate according to a formula;
s7, mixing materials: placing the prepared raw materials in a high-speed mixer with the rotating speed of 1500r/min for uniformly mixing for 3min;
s8, granulation: adding the uniformly mixed raw materials into a single-screw or double-screw extruder for extrusion, air cooling, granulating and sieving to obtain new nano-cellulose modified pecan shell micro-powder/thermoplastic material composite particles; wherein, when a single screw or double screw extruder is used for granulation, the temperature of the first temperature zone is 155 ℃, the temperature of the second temperature zone is 165 ℃, and the temperature of the third temperature zone is 175 ℃; the extrusion speed is 700rpm, and the traction speed is 500rpm;
s9, forming and rolling: putting the nano-cellulose modified pecan shell micro-powder/thermoplastic material composite particles into a single-screw or double-screw extruder for extrusion, wire-drawing and molding, cooling and rolling to obtain a nano-cellulose modified pecan shell micro-powder/thermoplastic material composite 3D printing consumable; wherein, when a single-screw extruder is used for extrusion wire-drawing forming, the temperature of the first temperature zone is 160 ℃, the temperature of the second temperature zone is 180 ℃, the temperature of the third temperature zone is 185 ℃, and the temperature of the water tank is 50 ℃; the extrusion speed was 800rpm, the drawing speed was 500rpm, and the take-up speed was 10rpm.
Example 5
S1, mixing 350g of hickory shell and 35g of hydrated magnesium silicate talcum powder (mesh number: 500 meshes), adding into a ball mill, and carrying out ball milling by using alumina grinding balls for 1-2 hours, and taking out to obtain the hickory shell micro powder;
s2, adding the pecan micro powder into 1280g of nano cellulose aqueous solution (2.5% solid content, diameter less than 500 nanometers and length less than 100 micrometers), dropwise adding 30g of acryloyloxyethyl trimethyl ammonium chloride grafted cationic starch solution (5% solid content), stirring for 3-5 minutes after dripping is finished, dropwise adding 12g of alkyl ketene dimer emulsion (12.5% solid content), stirring for 3-5 minutes after dripping is finished, dropwise adding ammonia water to adjust the pH value to 7.5-8.5, and obtaining mixed solution of the pecan shell micro powder and the nano cellulose;
s3, drying the mixed solution of the pecan shell micro powder and the nano-cellulose in a vacuum drying oven at the temperature of 80 ℃ for 10 hours, and performing surface coating modification and surface alkylation modification on the pecan shell micro powder to obtain the pecan shell micro powder with the water content of less than 1 percent, the surface coating of the nano-cellulose and the hydrophobic modification;
s4, mixing the pecan shell micro powder coated and subjected to hydrophobic property modification on the surface of the nano-cellulose, 30g of di (triethanolamine) diisopropyl titanate coupling agent and 30g of zinc stearate lubricant, adding the mixture into a ball mill, and performing ball milling for 1-2 hours by using an alumina grinding ball to introduce terminal olefin into the surface of the nano-cellulose to obtain nano-cellulose modified pecan shell micro powder;
s5, drying materials: placing the nano-cellulose modified pecan shell micro powder, polylactic acid particles, poly (butylene adipate/terephthalate) particles, cellulose biological composite materials, hydrogenated styrene-butadiene-styrene block copolymers and 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane into an oven at 60 ℃ for drying for 4 hours;
s6, preparing materials: taking 15g of dried nano cellulose modified pecan shell micro powder, 52g of polylactic acid particles, 20g of polybutylene adipate/terephthalate particles, 13g of cellulose biological composite material, 1g of hydrogenated styrene-butadiene-styrene block copolymer and 2g of 1,1,3-tri (2-methyl-4-hydroxy-5 tert-butylphenyl) butane according to the formula;
s7, mixing materials: placing the prepared raw materials in a high-speed mixer with the rotation speed of 1800r/min, and uniformly mixing for 3min;
s8, granulation: adding the uniformly mixed raw materials into a single-screw or double-screw extruder for extrusion, air cooling, granulating and sieving to obtain new nano-cellulose modified pecan shell micro-powder/thermoplastic material composite particles; wherein, when a single screw or double screw extruder is used for granulation, the temperature of the first temperature zone is 140 ℃, the temperature of the second temperature zone is 155 ℃, and the temperature of the third temperature zone is 165 ℃; the extrusion speed is 800rpm, and the traction speed is 350rpm;
s9, forming and rolling: putting the nano-cellulose modified pecan shell micro-powder/thermoplastic material composite particles into a single-screw or double-screw extruder for extrusion, wire-drawing and molding, cooling and rolling to obtain a nano-cellulose modified pecan shell micro-powder/thermoplastic material composite 3D printing consumable; wherein, when a single-screw extruder is used for extrusion wire-drawing forming, the temperature of the first temperature zone is 165 ℃, the temperature of the second temperature zone is 175 ℃, the temperature of the third temperature zone is 190 ℃, and the temperature of the water tank is 45 ℃; the extrusion speed was 700rpm, the drawing speed was 400rpm, and the take-up speed was 9rpm.
Example 6
S1, mixing 360g of hickory shell and 38g of hydrous magnesium silicate talcum powder (mesh number: 500 meshes), adding into a ball mill, and carrying out ball milling by using alumina grinding balls for 1-2 hours, and taking out to obtain the hickory shell micro powder;
s2, adding the pecan micro powder into 1520g of nano-cellulose aqueous solution (with the solid content of 2.5 percent, the diameter of less than 500 nanometers and the length of less than 100 micrometers), dropwise adding 36g of acryloyloxyethyl trimethyl ammonium chloride grafted cationic starch solution (with the solid content of 5 percent), stirring for 3-5 minutes after the dropwise adding is finished, dropwise adding 14.4g of alkyl ketene dimer emulsion (with the solid content of 12.5 percent), stirring for 3-5 minutes after the dropwise adding is finished, and dropwise adding ammonia water to adjust the pH value to 7.5-8.5 so as to obtain a mixed solution of the pecan shell micro powder and the nano-cellulose;
s3, drying the mixed solution of the pecan shell micro powder and the nano-cellulose in a vacuum drying oven at the temperature of 82 ℃ for 9 hours, and performing surface coating modification and surface alkylation modification on the pecan shell micro powder to obtain the pecan shell micro powder with the water content of less than 1 percent, the surface coating of the nano-cellulose and the hydrophobic modification;
s4, mixing the pecan shell micro powder coated and subjected to hydrophobic modification on the surface of the nano-cellulose, 36g of di (triethanolamine) diisopropyl titanate coupling agent and 35g of macromolecular composite ester lubricant of metal soap, adding the mixture into a ball mill, and ball-milling the mixture by using an alumina grinding ball for 1-2 hours to introduce terminal olefin into the surface of the nano-cellulose to obtain nano-cellulose modified pecan shell micro powder;
s5, drying materials: placing the nano-cellulose modified pecan shell micro powder, polylactic acid particles, polybutylene adipate/terephthalate particles, cellulose biological composite materials, hydrogenated styrene-butadiene-styrene block copolymers and tetra [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) pentaerythritol propionate into an oven at 60 ℃ for drying for 4 hours;
s6, preparing materials: taking 17g of dried nano-cellulose modified pecan shell micro powder, 60g of polylactic acid particles, 8g of poly (butylene adipate)/terephthalate particles, 16g of cellulose biological composite material, 1g of hydrogenated styrene-butadiene-styrene block copolymer and 2g of tetra [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) pentaerythritol propionate according to the formula;
s7, mixing materials: placing the prepared raw materials in a high-speed mixer with the rotating speed of 2000r/min for uniformly mixing for 3min;
s8, granulation: adding the uniformly mixed raw materials into a single-screw or double-screw extruder for extrusion, air cooling, granulating and sieving to obtain new nano-cellulose modified pecan shell micro-powder/thermoplastic material composite particles; wherein, when a single screw or double screw extruder is used for granulation, the temperature of the first temperature zone is 145 ℃, the temperature of the second temperature zone is 157 ℃ and the temperature of the third temperature zone is 170 ℃; the extrusion speed is 750rpm, and the traction speed is 400rpm;
s9, forming and rolling: putting the nano-cellulose modified pecan shell micro-powder/thermoplastic material composite particles into a single-screw or double-screw extruder for extrusion, wire drawing and molding, cooling and rolling to obtain a nano-cellulose modified pecan shell micro-powder/thermoplastic material composite 3D printing consumable; wherein, when a single screw extruder is used for extrusion wire drawing molding, the temperature of the first temperature zone is 175 ℃, the temperature of the second temperature zone is 185 ℃, the temperature of the third temperature zone is 200 ℃, and the temperature of the water tank is 55 ℃; the extrusion speed was 900rpm, the drawing speed was 600rpm, and the take-up speed was 15rpm.
Example 7
S1, mixing 310g of hickory shell and 47g of hydrous magnesium silicate talcum powder (mesh number: 800 meshes), adding into a ball mill, and carrying out ball milling by using alumina grinding balls for 1-2 hours, and taking out to obtain the hickory shell micro powder;
s2, adding the pecan micro powder into 1720g of nano-cellulose aqueous solution (2.5% solid content, the diameter of the pecan micro powder is less than 500 nanometers, and the length of the pecan micro powder is less than 100 micrometers), dropwise adding 40g of acryloyloxyethyl trimethyl ammonium chloride grafted cationic starch solution (5% solid content), stirring for 3-5 minutes after dropwise adding is finished, dropwise adding 16g of alkyl ketene dimer emulsion (12.5% solid content), stirring for 3-5 minutes after dropwise adding is finished, dropwise adding ammonia water to adjust the pH value to 7.5-8.5, and obtaining a mixed solution of the pecan shell micro powder and the nano-cellulose;
s3, drying the mixed solution of the pecan shell micro powder and the nano-cellulose in a vacuum drying oven at the temperature of 84 ℃ for 8 hours, and performing surface coating modification and surface alkylation modification on the pecan shell micro powder to obtain the pecan shell micro powder with the water content of less than 1 percent, the surface coating of the nano-cellulose and the hydrophobic modification;
s4, mixing the pecan shell micro powder coated and hydrophobized on the surface of the nano-cellulose, 42g of an aluminate coupling agent and 42g of an ethylene bis-stearamide lubricant, adding the mixture into a ball mill, and ball-milling the mixture by using alumina grinding balls for 1-2 hours to introduce terminal olefin into the surface of the nano-cellulose to obtain nano-cellulose modified pecan shell micro powder;
s5, drying materials: placing the nano-cellulose modified pecan shell micro powder, polylactic acid particles, polybutylene adipate/terephthalate particles, cellulose biological composite materials, styrene-butadiene-styrene block copolymers and beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl alcohol ester in an oven at 60 ℃ for drying for 4 hours;
s6, preparing materials: taking 23g of dried nano-cellulose modified pecan shell micro powder, 70g of polylactic acid particles, 12g of polybutylene adipate/terephthalate particles, 18g of cellulose biological composite material, 2g of styrene-butadiene-styrene block copolymer and 2g of beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester according to a formula;
s7, mixing materials: placing the prepared raw materials in a high-speed mixer with the rotating speed of 1200r/min, and uniformly mixing for 3min;
s8, granulation: adding the uniformly mixed raw materials into a single-screw or double-screw extruder for extrusion, air cooling, granulating and sieving to obtain new nano-cellulose modified pecan shell micro-powder/thermoplastic material composite particles; wherein, when a single screw or double screw extruder is used for granulation, the temperature of the first temperature zone is 155 ℃, the temperature of the second temperature zone is 165 ℃ and the temperature of the third temperature zone is 175 ℃; the extrusion speed is 900rpm, and the traction speed is 500rpm;
s9, forming and rolling: putting the nano-cellulose modified pecan shell micro-powder/thermoplastic material composite particles into a single-screw or double-screw extruder for extrusion, wire drawing and molding, cooling and rolling to obtain a nano-cellulose modified pecan shell micro-powder/thermoplastic material composite 3D printing consumable; wherein, when a single-screw extruder is used for extrusion wire-drawing forming, the temperature of the first temperature zone is 160 ℃, the temperature of the second temperature zone is 180 ℃, the temperature of the third temperature zone is 185 ℃, and the temperature of the water tank is 50 ℃; the extrusion speed was 800rpm, the drawing speed was 500rpm, and the take-up speed was 10rpm.
Example 8
S1, 370g of hickory shell and 42g of hydrated magnesium silicate talcum powder (mesh number: 800 meshes) are mixed and added into a ball mill, and are ball-milled by using alumina grinding balls for 1-2 hours, and then the mixture is taken out to obtain the hickory shell micro powder;
s2, adding the pecan micro powder into 1040g of nano cellulose aqueous solution (2.5% solid content, diameter less than 500nm and length less than 100 microns), dropwise adding 44g of acryloyloxyethyl trimethyl ammonium chloride grafted cationic starch solution (5% solid content), stirring for 3-5 minutes after dropwise adding, dropwise adding 17.6g of alkyl ketene dimer emulsion (12.5% solid content), stirring for 3-5 minutes after dropwise adding, dropwise adding ammonia water to adjust the pH value to 7.5-8.5, and obtaining a mixed solution of the pecan shell micro powder and the nano cellulose;
s3, drying the mixed solution of the pecan shell micro powder and the nano-cellulose in a vacuum drying oven at 86 ℃ for 7 hours, and performing surface coating modification and surface alkylation modification on the pecan shell micro powder to obtain the pecan shell micro powder with the water content of less than 1 percent, the surface coating of the nano-cellulose and the hydrophobization modification;
s4, mixing the pecan shell micro powder coated and subjected to hydrophobization modification on the surface of the nano-cellulose, 48g of aluminate coupling agent and 47g of polyethylene wax lubricant, adding the mixture into a ball mill, and ball-milling the mixture for 1-2 hours by using alumina grinding balls to obtain nano-cellulose modified pecan shell micro powder by introducing terminal olefin into the surface of the nano-cellulose;
s5, drying materials: placing the nano-cellulose modified pecan shell micro powder, polylactic acid particles, poly (butylene adipate)/terephthalate particles, cellulose biological composite materials, styrene-butadiene-styrene segmented copolymer, 2,6-di-tert-butyl-p-cresol in an oven at 60 ℃ for drying for 4 hours;
s6, preparing materials: taking 27g of dried nano-cellulose modified pecan shell micro powder, 75g of polylactic acid particles, 18g of poly (butylene adipate)/terephthalate particles, 12g of cellulose biological composite material, 4g of styrene-butadiene-styrene block copolymer and 4g of 2,6-di-tert-butyl-p-cresol according to a formula;
s7, mixing materials: placing the prepared raw materials in a high-speed mixer with the rotating speed of 2000r/min for uniformly mixing for 3min;
s8, granulation: adding the uniformly mixed raw materials into a single-screw or double-screw extruder for extrusion, air cooling, granulating and sieving to obtain new nano-cellulose modified pecan shell micro-powder/thermoplastic material composite particles; wherein, when a single screw or double screw extruder is used for granulation, the temperature of the first temperature zone is 155 ℃, the temperature of the second temperature zone is 165 ℃ and the temperature of the third temperature zone is 175 ℃; the extrusion speed is 700rpm, and the traction speed is 500rpm;
s9, forming and rolling: putting the nano-cellulose modified pecan shell micro-powder/thermoplastic material composite particles into a single-screw or double-screw extruder for extrusion, wire-drawing and molding, cooling and rolling to obtain a nano-cellulose modified pecan shell micro-powder/thermoplastic material composite 3D printing consumable; wherein, when a single-screw extruder is used for extrusion wire-drawing forming, the temperature of the first temperature zone is 165 ℃, the temperature of the second temperature zone is 175 ℃, the temperature of the third temperature zone is 190 ℃, and the temperature of the water tank is 45 ℃; the extrusion speed was 700rpm, the haul-off speed was 400rpm, and the take-up speed was 9rpm.
Example 9
S1, mixing 390g of pecan shells and 29g of hydrated magnesium silicate talcum powder (mesh number: 800 meshes), adding into a ball mill, and carrying out ball milling by using alumina grinding balls for 1-2 hours, and taking out to obtain pecan shell micro powder;
s2, adding the pecan micro powder into 1120g of nano cellulose aqueous solution (with the solid content of 2.5 percent, the diameter of less than 500 nanometers and the length of less than 100 micrometers), dropwise adding 48g of acryloyloxyethyl trimethyl ammonium chloride grafted cationic starch solution (with the solid content of 5 percent), stirring for 3-5 minutes after the dropwise adding is finished, dropwise adding 19.2g of alkyl ketene dimer emulsion (with the solid content of 12.5 percent), stirring for 3-5 minutes after the dropwise adding is finished, dropwise adding ammonia water to adjust the pH value to 7.5-8.5, and obtaining a mixed solution of the pecan shell micro powder and the nano cellulose;
s3, drying the mixed solution of the pecan shell micro powder and the nano-cellulose in a vacuum drying oven at the temperature of 88 ℃ for 6 hours, and performing surface coating modification and surface alkylation modification on the pecan shell micro powder to obtain the pecan shell micro powder with the water content of less than 1 percent, the surface coating of the nano-cellulose and the hydrophobic modification;
s4, mixing the pecan shell micro powder coated and hydrophobized and modified on the surface of the nano-cellulose, 27g of aluminate coupling agent and 38g of silicone lubricant, adding the mixture into a ball mill, and ball-milling the mixture by using alumina grinding balls for 1-2 hours to introduce terminal olefin into the surface of the nano-cellulose to obtain nano-cellulose modified pecan shell micro powder;
s5, drying materials: placing the nano-cellulose modified pecan shell micro-powder, polylactic acid particles, polybutylene adipate/terephthalate particles, cellulose biological composite materials, styrene-butadiene-styrene block copolymers and dialkyl thiodipropionate in an oven at 60 ℃ for drying for 4 hours;
s6, preparing materials: taking 28g of dried nano-cellulose modified pecan shell micro powder, 80g of polylactic acid particles, 16g of polybutylene adipate/terephthalate particles, 19g of cellulose biological composite material, 3g of styrene-butadiene-styrene segmented copolymer and 3g of dialkyl thiodipropionate according to a formula;
s7, mixing materials: placing the prepared raw materials in a high-speed mixer with the rotating speed of 1000r/min for uniformly mixing for 3min;
s8, granulation: adding the uniformly mixed raw materials into a single-screw or double-screw extruder for extrusion, air cooling, granulating and sieving to obtain new nano-cellulose modified pecan shell micro-powder/thermoplastic material composite particles; wherein, when a single screw or double screw extruder is used for granulation, the temperature of the first temperature zone is 155 ℃, the temperature of the second temperature zone is 165 ℃ and the temperature of the third temperature zone is 175 ℃; the extrusion speed is 900rpm, and the traction speed is 500rpm;
s9, forming and rolling: putting the nano-cellulose modified pecan shell micro-powder/thermoplastic material composite particles into a single-screw or double-screw extruder for extrusion, wire-drawing and molding, cooling and rolling to obtain a nano-cellulose modified pecan shell micro-powder/thermoplastic material composite 3D printing consumable; wherein, when a single-screw extruder is used for extrusion wire-drawing forming, the temperature of the first temperature zone is 175 ℃, the temperature of the second temperature zone is 185 ℃, the temperature of the third temperature zone is 200 ℃, and the temperature of the water tank is 55 ℃; the extrusion speed was 900rpm, the drawing speed was 600rpm, and the take-up speed was 15rpm.
Comparative example 1
Compared with the embodiment 1, the difference is that the surface of the modified pecan shell micro powder coated with the nanocellulose is not added, 64 parts of polylactic acid, 10 parts of cellulose biological composite material, 10 parts of poly (adipic acid)/butylene terephthalate, 5 parts of hydrogenated styrene-butadiene-styrene block copolymer and 1 part of 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, and the prepared 3D printing consumable material is a polylactic acid 3D printing consumable material.
The printed products of the above examples and comparative examples were tested for strength, the 3D printing consumables obtained by molding and winding were printed into sample strips, the printing temperature was set at 190 ℃, the soleplate temperature at 50 ℃, the printing speed at 90 mm/min, the layer thickness at 0.2 mm, and the fill factor at 100%; the tensile strength of the tensile sample strip is tested on a CMT4104 electronic universal testing machine according to the GB/T1040.2-2006 standard, and the tensile speed is 50 mm/min; the bending property is tested on a CMT4104 electronic universal tester according to the GB/T9341-2000 standard, the speed is 2 mm/min, and the displacement is 6 mm; testing the notched impact sample bars on a ZBC500 type pendulum impact tester according to the GB/T1043.1-2008 standard; the test results are shown in Table 1.
TABLE 1 results of mechanical Strength Properties measurements
| Tensile strength (Mpa) | Elongation at Break (%) | Flexural modulus (Mpa) | Notched Izod impact (KJ/m) 2 ) | Cantilever unnotched punchHit (KJ/m) 2 ) | Heat distortion temperature (. Degree. C.) | Density (kg/m) 2 ) | |
| Example 1 | 38.7 | 2.0 | 3989.2 | 5.6 | 14.1 | 129.3 | 1.33 |
| Example 2 | 41.5 | 2.1 | 4285.1 | 6.0 | 14.4 | 138.8 | 1.24 |
| Example 3 | 43.7 | 2.5 | 4520.4 | 6.3 | 15.6 | 146.5 | 1.21 |
| Example 4 | 40.1 | 2.0 | 4135.4 | 5.8 | 13.9 | 134.0 | 1.22 |
| Example 5 | 40.6 | 2.1 | 4192.4 | 5.9 | 14.1 | 135.9 | 1.23 |
| Example 6 | 42.3 | 2.2 | 4290.3 | 6.1 | 15.0 | 140.8 | 1.24 |
| Example 7 | 42.9 | 2.2 | 4385.1 | 6.2 | 15.1 | 142.1 | 1.22 |
| Example 8 | 43.4 | 2.4 | 4481.2 | 6.3 | 15.3 | 145.2 | 1.27 |
| Example 9 | 42.9 | 2.3 | 4431.3 | 6.2 | 15.2 | 143.5 | 1.31 |
| Comparative example 1 | 33.8 | 1.7 | 3499.3 | 4.9 | 12.8 | 113.4 | 1.17 |
Compared with the comparative example 1, the difference of the example 1 is that the surface of the nano-cellulose-coated modified pecan shell micro-powder is added, and according to the test result, all indexes of the mechanical strength performance are improved after the surface of the nano-cellulose-coated modified pecan shell micro-powder is added. And the comparison of the test results of examples 1-9 shows that the various indexes of mechanical strength performance are improved along with the increase of the dosage ratio of the nano-cellulose modified pecan shell micro-powder to the thermoplastic material.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A nanocellulose modified pecan shell micro powder/thermoplastic material composite 3D printing consumable material is characterized in that the nanocellulose modified pecan shell micro powder and thermoplastic material are mixed according to a mass ratio of 1:9-1:4;
the nano-cellulose modified pecan shell micro powder comprises the following components in parts by mass: 60-80 parts of pecan shell, 5-10 parts of talcum powder, 4.8-9 parts of nano-cellulose, 0.1-0.5 part of cationic starch, 0.1-0.5 part of alkyl ketene dimer, 5-10 parts of coupling agent and 5-10 parts of lubricating agent;
the preparation method of the nano-cellulose modified pecan shell micro powder comprises the following steps:
s1: mixing the pecan shells and the talcum powder, adding the mixture into a ball mill, and performing ball milling by using alumina grinding balls to obtain pecan shell micro powder with the fineness of 300-800 meshes;
s2: adding the pecan shell micro powder into a nano cellulose aqueous solution, dropwise adding a cationic starch solution, stirring for 3-5 minutes after dropwise adding, dropwise adding an alkyl ketene dimer emulsion, stirring for 3-5 minutes after dropwise adding, dropwise adding ammonia water to adjust the pH value to 7.5-8.5, and obtaining a mixed solution of the pecan shell micro powder and the nano cellulose;
s3: drying the mixed solution of the pecan shell micro powder and the nano-cellulose in a vacuum drying oven, and performing surface coating modification and surface alkylation modification on the pecan shell micro powder to obtain the pecan shell micro powder with the water content of less than 1 percent, and surface coating and hydrophobization modification on the nano-cellulose;
s4: mixing the pecan shell micro powder which is coated on the surface of the nano-cellulose and modified by hydrophobization, a coupling agent and a lubricant, adding the mixture into a ball mill, and ball milling the mixture by using an alumina grinding ball to introduce terminal olefin into the surface of the nano-cellulose to obtain nano-cellulose modified pecan shell micro powder;
the thermoplastic material comprises the following components in parts by mass: 50-80 parts of polylactic acid, 5-20 parts of poly (butylene adipate)/terephthalate, 10-20 parts of cellulose biological composite material, 1-5 parts of toughening agent and 1-5 parts of antioxidant;
the cellulose biological composite material is a cellulose biological composite material which is produced by Finland Finnish Ouhuichuan group and has a UPMFormi3D model.
2. The nanocellulose-modified pecan shell micropowder/thermoplastic material composite 3D printing consumable of claim 1, wherein the talc is a magnesium silicate mineral with a fineness of 325-800 mesh; the nano-cellulose is prepared by grinding wood pulp and bamboo pulp fibers serving as raw materials, wherein the diameter of the nano-cellulose is 10-500nm; the cationic starch is a quaternary ammonium salt modified starch derivative, and the cationic substitution degree is 0.02-0.05.
3. The nanocellulose-modified pecan shell micropowder/thermoplastic material composite 3D printing consumable of claim 1, wherein the coupling agent is any one or a mixture of two or more of: silane coupling agent, titanate coupling agent or aluminate coupling agent.
4. The nanocellulose-modified pecan shell micropowder/thermoplastic material composite 3D printing consumable of claim 1, wherein the lubricant is any one or a mixture of two or more of: calcium stearate, stearamide, oleamide, erucamide, zinc stearate, high-molecular composite ester of metal soap, ethylene bis stearamide, polyethylene wax or silicone.
5. The nanocellulose-modified pecan shell micropowder/thermoplastic material composite 3D printing consumable of claim 1, wherein the toughening agent is any one or a mixture of two or more of the following: styrene-butadiene-styrene block copolymers or hydrogenated styrene-butadiene-styrene block copolymers.
6. The nanocellulose-modified pecan shell micropowder/thermoplastic material composite 3D printing consumable of claim 1, wherein the antioxidant is any one or a mixture of two or more of the following: 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, pentaerythritol tetrakis [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, octadecyl beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, dialkyl thiodipropionate or 2,6-di-tert-butyl-p-cresol.
7. The preparation method of the nanocellulose modified pecan shell micropowder/thermoplastic material composite 3D printing consumable material of claim 1, comprising the following steps:
s1: mixing the hickory shell and the talcum powder, adding the mixture into a ball mill, and performing ball milling by using alumina grinding balls to obtain the hickory shell micro powder with the fineness of 300-800 meshes;
s2: adding the pecan shell micro powder into a nano cellulose aqueous solution, dropwise adding a cationic starch solution, stirring for 3-5 minutes after dropwise adding, dropwise adding an alkyl ketene dimer emulsion, stirring for 3-5 minutes after dropwise adding, dropwise adding ammonia water to adjust the pH value to 7.5-8.5, and obtaining a mixed solution of the pecan shell micro powder and the nano cellulose;
s3: drying the mixed solution of the pecan shell micro powder and the nano-cellulose in a vacuum drying oven, and performing surface coating modification and surface alkylation modification on the pecan shell micro powder to obtain the pecan shell micro powder with the water content of less than 1 percent, and surface coating and hydrophobization modification on the nano-cellulose;
s4: mixing the pecan shell micro powder coated and subjected to hydrophobization modification on the surface of the nano-cellulose, a coupling agent and a lubricant, adding the mixture into a ball mill, and performing ball milling by using an alumina grinding ball to introduce terminal olefin into the surface of the nano-cellulose to obtain nano-cellulose modified pecan shell micro powder;
s5: drying materials: placing the nano-cellulose modified pecan shell micro-powder, polylactic acid particles, poly (butylene adipate/terephthalate) particles, cellulose biological composite material, toughening agent and antioxidant into an oven for drying;
s6: preparing materials: taking dried nano cellulose modified pecan shell micro powder, polylactic acid particles, poly adipic acid/butylene terephthalate particles, cellulose biological composite materials, toughening agents and antioxidants according to the formula;
s7: mixing materials: placing the prepared raw materials in a high-speed mixer to be uniformly mixed;
s8: and (3) granulation: adding the uniformly mixed raw materials into a single-screw or double-screw extruder for extrusion, air cooling, granulating and sieving to obtain new nano-cellulose modified pecan shell micro-powder/thermoplastic material composite particles;
s9: molding and rolling: and putting the nano-cellulose modified pecan shell micro-powder/thermoplastic material composite particles into a single-screw or double-screw extruder for extrusion and wire-drawing molding, and cooling and rolling to obtain the nano-cellulose modified pecan shell micro-powder/thermoplastic material composite 3D printing consumable.
8. The method for preparing a nanocellulose modified pecan shell micropowder/thermoplastic material composite 3D printing consumable material according to claim 7, wherein the drying temperature in the vacuum drying oven in the step S3 is 80-90 ℃, and the drying time is 5-10 hours.
9. The method for preparing a nanocellulose modified pecan shell micropowder/thermoplastic material composite 3D printing consumable material of claim 7, wherein when a single screw or twin screw extruder is used for granulation in step S8, the temperature of the first temperature zone is 140-155 ℃, the temperature of the second temperature zone is 155-165 ℃, and the temperature of the third temperature zone is 165-175 ℃; the extrusion speed is 700-900rpm, and the traction speed is 300-500rpm; when a single-screw or double-screw extruder is used for extrusion, wire drawing and forming in the step S9, the temperature of the first temperature zone is 160-175 ℃, the temperature of the second temperature zone is 175-185 ℃, the temperature of the third temperature zone is 185-200 ℃, and the temperature of the water tank is 45-55 ℃; the extrusion speed is 700-900rpm, the traction speed is 400-600rpm, and the winding speed is 9.0-15.0rpm.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103302708A (en) * | 2013-05-08 | 2013-09-18 | 广东省宜华木业股份有限公司 | Preparation method of novel hydrophobic wood |
| CN106009566A (en) * | 2016-06-24 | 2016-10-12 | 苏州思创源博电子科技有限公司 | Preparation method of modified PLA (polylactide) and cellulose composite |
| CN106674936A (en) * | 2016-12-16 | 2017-05-17 | 华南协同创新研究院 | Glass fiber modified wood plastic composite material for 3D printing and preparation method thereof |
| WO2018045248A1 (en) * | 2016-09-01 | 2018-03-08 | Hs Manufacturing Group Llc | Methods for biobased derivatization of cellulosic surfaces |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103302708A (en) * | 2013-05-08 | 2013-09-18 | 广东省宜华木业股份有限公司 | Preparation method of novel hydrophobic wood |
| CN106009566A (en) * | 2016-06-24 | 2016-10-12 | 苏州思创源博电子科技有限公司 | Preparation method of modified PLA (polylactide) and cellulose composite |
| WO2018045248A1 (en) * | 2016-09-01 | 2018-03-08 | Hs Manufacturing Group Llc | Methods for biobased derivatization of cellulosic surfaces |
| CN106674936A (en) * | 2016-12-16 | 2017-05-17 | 华南协同创新研究院 | Glass fiber modified wood plastic composite material for 3D printing and preparation method thereof |
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