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CN107129699B - A kind of green non-poisonous 3D printing consumptive material and preparation method thereof - Google Patents

A kind of green non-poisonous 3D printing consumptive material and preparation method thereof Download PDF

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Publication number
CN107129699B
CN107129699B CN201710324335.2A CN201710324335A CN107129699B CN 107129699 B CN107129699 B CN 107129699B CN 201710324335 A CN201710324335 A CN 201710324335A CN 107129699 B CN107129699 B CN 107129699B
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straw powder
straw
preparation
printing
consumptive material
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CN107129699A (en
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万锕俊
周后璋
林贵娇
岳卫东
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Tongji University
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/02Ingredients treated with inorganic substances
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE 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
    • B33Y70/00Materials specially adapted for additive manufacturing
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/05Alcohols; Metal alcoholates
    • C08K5/053Polyhydroxylic alcohols

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Printing Methods (AREA)
  • Developing Agents For Electrophotography (AREA)

Abstract

本发明涉及一种绿色无毒3D打印耗材及其制备方法,属于新材料技术领域。本发明的新材料是以农作物废弃秸秆为主要原料,以硅藻壳为辅助原料,可用于3D打印。具体制备方法是将秸秆粉进行球磨预处理,用乙酸浸泡活化,然后将活化的秸秆粉和柠檬酸加热反应,反应结束后冷却至室温,调节pH至中性,加入乙醇,经离心、去离子水洗涤、烘干,得到改性秸秆粉,然后加入秸秆粉、活化硅藻壳、山梨糖醇,匀质混合至胶状混合物,经干燥得到绿色无毒3D打印耗材。采用本发明方法可以得到绿色无毒3D打印耗材,制备的耗材强度高,成型性能好,具有绿色、无毒、环保等特点。将废弃秸秆和硅藻壳变废为宝,有利于节约木材资源及其利用率,大大降低了成本,同时对环境保护具有重要意义;所述的制备方法,简化了制造工艺,降低了生产成本,且不会产生难处理的有毒废液。

The invention relates to a green non-toxic 3D printing consumable and a preparation method thereof, belonging to the technical field of new materials. The new material of the present invention uses crop waste straw as the main raw material and diatom frustules as the auxiliary raw material, and can be used for 3D printing. The specific preparation method is to pre-treat the straw powder by ball milling, soak it in acetic acid for activation, then heat the activated straw powder and citric acid to react, cool down to room temperature after the reaction, adjust the pH to neutrality, add ethanol, centrifuge, deionize Washing with water and drying to obtain modified straw powder, then adding straw powder, activated diatom frustules and sorbitol, homogeneously mixing to a colloidal mixture, and drying to obtain green non-toxic 3D printing consumables. By adopting the method of the invention, green and non-toxic 3D printing consumables can be obtained, and the prepared consumables have high strength, good molding performance, and are green, non-toxic, environmentally friendly, and the like. Turning waste straws and diatom frustules into treasures is conducive to saving wood resources and their utilization rate, greatly reducing costs, and at the same time having great significance for environmental protection; the preparation method simplifies the manufacturing process and reduces the production cost , and will not produce intractable toxic waste.

Description

A kind of green non-poisonous 3D printing consumptive material and preparation method thereof
Technical field
The invention belongs to new material technology field, it is related to a kind of green non-poisonous 3D printing consumptive material and preparation method thereof.
Background technique
3D printing is successively to increase material by 3D printing equipment to manufacture three-dimensional objects based on three-dimensional CAD model data Technology, also known as increasing material manufacturing, restrict at present 3D printing technique development factors first is that the research and development of printing consumables, 3D printing consumption Material is many kinds of, predominantly polymer, composite material etc., consumptive material meet efficiently, accurately forming requirements when, can bring toxic The problems such as substance, environmental pollution, therefore researching and developing green non-poisonous 3D printing consumptive material will be as the heat of the following 3D printing technique research Point.3D printing consumptive material of the invention is a kind of new material, green non-poisonous, functional, low in cost, is provided for 3D printing Environmentally protective material selection.
The yield of stalk and diatom test is big in agriculture field.Crops are the major products of agriculture field, annual inevitable A large amount of stalk by-product is generated, it is natural high molecular material, according to statistics, national stalk total output in 2011 is 7.51 × 108t.Microalgae is to refine bio-fuel-oil, the raw material with important energy source strategic reserves meaning, and diatom is that wherein oil content is higher One of microalgae, this necessarily leads to a large amount of diatom test by-product, and diatom test is unique biological form natural inorganic on the earth Material.Stalk and diatom test have the characteristic of green, environmental protection first is that natural material;Second is that stalk has certain toughness, and silicon Frustule has some strength, the mutual compound higher-strength and mouldable materials for being beneficial to obtain machinability.
The 3D printing consumptive material being mixed at present by stalk and thermal plastic high polymer is in the majority, and stalk is as obturator, increasing Strong composite materials property, but straw content is low, and the raising of consumptive material mechanical performance is not significant, and with straw base preparation 3D printing consumption The research of material is extremely short of.
China Patent Publication No. is that 103937278A discloses a kind of 3D printing wood plastic composite and preparation method thereof, Plant fiber is crushed and is modified after drying through processing aid, then uniformly mixes with polyolefin material grain, is squeezed with double screw extruder Composite finished product is made out, modified material has the processing characteristics of wooden appearance and Wood-plastic material, but plant fiber Content is low, and the mechanical performance raising of synthetic material is not significant, and material can release toxic gas in melting process, exist not The problems such as degradable, excessive use certainly will bring environmental problem, therefore can not large-scale promotion and application.
Summary of the invention
For the problems of above-mentioned prior art, the object of the present invention is to provide a kind of stalk and diatom test are compound, Cheap with certain intensity, low-carbon environment-friendly is green non-poisonous, and product has preferable physical mechanical property and processability The 3D printing consumptive material and preparation method thereof of energy.
In order to achieve the above objectives, the technical scheme adopted by the invention is that:
A kind of green non-poisonous 3D printing consumptive material proposed by the present invention, the consumptive material is by stalk, diatom test and D-sorbite group At the weight percent of raw material is as follows:
Stalk 50 ~ 80%,
Diatom test 1.5 ~ 2.5%,
Remaining is D-sorbite, and total weight meets 100%;
The stalk uses at least one of wheat straw, straw, corn stalk, cotton straw or the reed of 100~300 mesh.
The preparation method of green non-poisonous 3D printing consumptive material proposed by the present invention, the specific steps are as follows:
(1) stalk is pre-processed, obtains straw powder;
(2) pretreated straw powder, citric acid solution are carried out anti-as in acid-resistant container using magnetic stirring apparatus It answers;The mass ratio of pretreated straw powder and citric acid is 1:(3 ~ 5), citric acid solution concentration is 15% ~ 25wt%, and pH is 2.8-3.2, reaction time are 12 ~ 16h, and reaction temperature is 80 ~ 100 DEG C, and control magnetic stirring apparatus revolving speed is 600 ~ 800r/min;
(3) it is cooled to room temperature, by ethyl alcohol and step (2) products therefrom as in centrifuge, adjusting solution PH to neutrality is heavy Multiple centrifugation three times, obtains sediment, and product is washed with deionized, and drying obtains modified straw powder;Straw powder that treated with The mass ratio of ethyl alcohol is 1:(4 ~ 8), centrifuge speed is 3000 ~ 5000r/min, and the time is 20 ~ 30min;
(4) by diatom test as being activated in sodium hydroxide solution;
(5) modified straw powder, the activation diatom test, D-sorbite obtained straw powder that step (1) obtains, step (3) As for mixing in ultrasonic wave homogenizer, colloidal mixture is obtained, it is dry, obtain green non-poisonous 3D printing consumptive material.
In the present invention, in step (1), pre-process as at least one of mechanical ball mill, acetic acid immersion or NaOH immersion.
In the present invention, in step (3), the mass ratio of straw powder that treated and ethyl alcohol is 1:(4 ~ 8), centrifuge speed is 3000 ~ 5000r/min, time are 20 ~ 30min.
In the present invention, in step (5), incorporation time is 3 ~ 6h, and mixing temperature is 70 ~ 80 DEG C, and drying temperature is 60 ~ 70 DEG C, drying time be 20 ~ for 24 hours.
The beneficial effects of the present invention are: prepared 3D printing consumptive material has green non-poisonous environmental protection characteristic.In consumptive material system It is added to diatom test in standby, compared with the material for being not added with diatom test, intensity is higher, and corrosion resistance is stronger, improves simultaneously Wearability, improves the finish of material surface, and material is made to have waterproof, anti-aging property;Timber is replaced with waste straw, Turn waste into wealth, is conducive to save timber resources, greatly reduces cost, while being of great significance to environmental protection;Diatom test Use, improve the utilization rate of resource, also greatly improve the performance of material, reach win-win, the preparation method simplifies Manufacturing process, reduces production cost.With good practicability.
Detailed description of the invention
Fig. 1 is the flow chart of green non-poisonous 3D printing consumptive material preparation method provided in an embodiment of the present invention.
Specific embodiment
It elaborates below to the embodiment of the present invention, the present embodiment carries out under the premise of the technical scheme of the present invention Implement, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to following implementation Example.
Embodiment 1
(1) wheat straw for weighing 5g100 mesh is put into ball milling 60min in ball mill;
(2) wheat straw after ball milling is placed in a beaker, 25g acetic acid is added, 5h is impregnated in sealing at room temperature, filters out extra second Acid;
(3) by after immersion wheat straw and 100ml concentration be 15wt% citric acid solution be placed in the three-neck flask equipped with condenser pipe In, 12h is reacted in 80 DEG C, 600r/min heat-collecting magnetic stirring device;
(4) product that step (3) obtains is cooled to room temperature, adjusts pH to neutrality, by its be 95% with 30ml concentration second Alcohol, which is placed in the centrifuge that revolving speed is 3000r/min, is centrifuged 30min, and three times, gained precipitating is washed with deionized repeated centrifugation, It finally dries, crush;
(5) it weighs 0.1g diatom test to be placed in a beaker, the NaOH solution that 5ml concentration is 6wt% is added, sealing is soaked at room temperature Steep 5h;
(6) product, 0.5g100 mesh wheat straw, 1g D-sorbite and the 100ml distilled water obtained step (4), step (5) It is placed in a beaker, in the stirring of ultrasonic wave homogenizer until gluey, temperature is 70 DEG C, and finally dry 20h in 60 DEG C of baking ovens to obtain the final product Green non-poisonous 3D printing consumptive material.
By the consumptive material in 120 DEG C of progress 3D printings, the density of material is 0.89g/cm3 after molding, and tensile strength is 20.5MPa, bending modulus 2.1GPa, shrinking percentage 0.93%.
Embodiment 2
(1) straw for weighing 5g150 mesh is put into ball milling 60min in ball mill;
(2) straw after ball milling is placed in a beaker, 30g acetic acid is added, 4h is impregnated in sealing at room temperature, filters out extra second Acid;
(3) by after immersion straw and 100ml concentration be 20wt% citric acid solution be placed in the three-neck flask equipped with condenser pipe In, 15h is reacted in 90 DEG C, 650r/min heat-collecting magnetic stirring device;
(4) product that step (3) obtains is cooled to room temperature, adjusts pH to neutrality, by its be 95% with 40ml concentration second Alcohol, which is placed in the centrifuge that revolving speed is 3500r/min, is centrifuged 25min, and three times, gained precipitating is washed with deionized repeated centrifugation, It finally dries, crush;
(5) it weighs 0.12g diatom test to be placed in a beaker, the NaOH solution that 6ml concentration is 6wt% is added, seals, at room temperature Impregnate 5h;
(6) product, 0.4g150 mesh straw, 1.5g D-sorbite and the 100ml distillation obtained step (4), step (5) Water is placed in a beaker, and in the stirring of ultrasonic wave homogenizer until gluey, temperature is 70 DEG C, and finally dry 22h is in 60 DEG C of baking ovens Obtain green non-poisonous 3D printing consumptive material.
By the consumptive material in 110 DEG C of progress 3D printings, the density of material is 0.78g/cm3 after molding, and tensile strength is 19.6MPa, bending modulus 1.82GPa, shrinking percentage 1.33%.
Embodiment 3
(1) corn stalk for weighing 5g200 mesh is put into ball milling 55min in ball mill;
(2) corn stalk after ball milling is placed in a beaker, 30g acetic acid is added, 4h is impregnated in sealing at room temperature, and it is extra to filter out Acetic acid;
(3) by after immersion corn stalk and 100ml concentration be 20wt% citric acid solution be placed in three necks equipped with condenser pipe burn In bottle, 15h is reacted in 90 DEG C, 750r/min heat-collecting magnetic stirring device;
(4) product that step (3) obtains is cooled to room temperature, adjusts pH to neutrality, by its be 95% with 40ml concentration second Alcohol, which is placed in the centrifuge that revolving speed is 4500r/min, is centrifuged 25min, and three times, gained precipitating is washed with deionized repeated centrifugation, It finally dries, crush;
(5) it weighs 0.13g diatom test to be placed in a beaker, the NaOH solution that 8ml concentration is 6wt% is added, seals, at room temperature Impregnate 6h;
(6) product, 0.35g200 mesh corn stalk, 2g D-sorbite and the 150ml distillation obtained step (4), step (5) Water is placed in a beaker, and in the stirring of ultrasonic wave homogenizer until gluey, temperature is 75 DEG C, and finally dry 23h is in 65 DEG C of baking ovens Obtain green non-poisonous 3D printing consumptive material.
By the consumptive material in 130 DEG C of progress 3D printings, the density of material is 1.02g/cm3 after molding, and tensile strength is 21.2MPa, bending modulus 1.79GPa, shrinking percentage 0.99%.
Embodiment 4
(1) the cotton straw for weighing 5g250 mesh, are put into ball milling 55min in ball mill;
(2) the cotton straw after ball milling are placed in a beaker, 35g acetic acid is added, 5h is impregnated in sealing at room temperature, and it is extra to filter out Acetic acid;
(3) by after immersion cotton straw and 100ml concentration be 25wt% citric acid solution be placed in three necks equipped with condenser pipe burn In bottle, 15h is reacted in 95 DEG C, 750r/min heat-collecting magnetic stirring device;
(4) product that step (3) obtains is cooled to room temperature, adjusts pH to neutrality, by its be 95% with 45ml concentration second Alcohol, which is placed in the centrifuge that revolving speed is 4500r/min, is centrifuged 20min, and three times, gained precipitating is washed with deionized repeated centrifugation, It finally dries, crush;
(5) it weighs 0.15g diatom test to be placed in a beaker, the NaOH solution that 5ml concentration is 6wt% is added, seals, at room temperature Impregnate 5h;
(6) product, 0.5g250 mesh cotton straw, 2g D-sorbite and the 200ml distillation obtained step (4), step (5) Water is placed in a beaker, and in the stirring of ultrasonic wave homogenizer until gluey, temperature is 70 DEG C, and finally dry 23h is in 60 DEG C of baking ovens Obtain green non-poisonous 3D printing consumptive material.
By the consumptive material in 100 DEG C of progress 3D printings, the density of material is 1.1g/cm3 after molding, and tensile strength is 22.1MPa, bending modulus 1.89GPa, shrinking percentage 0.91%.
Embodiment 5
(1) reed for weighing 5g300 mesh is put into ball milling 50min in ball mill;
(2) reed after ball milling is placed in a beaker, 40g acetic acid is added, 3h is impregnated in sealing at room temperature, filters out extra second Acid;
(3) by after immersion reed and 100ml concentration be 25wt% citric acid solution be placed in the three-neck flask equipped with condenser pipe In, 16h is reacted in 100 DEG C, 800r/min heat-collecting magnetic stirring device;
(4) product that step (3) obtains is cooled to room temperature, adjusts pH to neutrality, by its be 95% with 50ml concentration second Alcohol, which is placed in the centrifuge that revolving speed is 5000r/min, is centrifuged 20min, and three times, gained precipitating is washed with deionized repeated centrifugation, It finally dries, crush;
(5) it weighs 0.15g diatom test to be placed in a beaker, the NaOH solution that 10ml concentration is 6wt% is added, seals, at room temperature Impregnate 8h;
(6) product, 0.3g300 mesh reed, 2.5g D-sorbite and the 200ml distillation obtained step (4), step (5) Water is placed in a beaker, and in the stirring of ultrasonic wave homogenizer until gluey, temperature is 80 DEG C, and finally drying is for 24 hours in 70 DEG C of baking ovens Obtain green non-poisonous 3D printing consumptive material.
By the consumptive material in 125 DEG C of progress 3D printings, the density of material is 0.94g/cm3 after molding, and tensile strength is 20.1MPa, bending modulus 2.3GPa, shrinking percentage 0.91%.

Claims (3)

1. a kind of preparation method of green non-poisonous 3D printing consumptive material, it is characterised in that: the consumptive material is by stalk, diatom test and sorb Sugar alcohol composition, the weight percent of raw material are as follows:
Stalk 50 ~ 80%,
Diatom test 1.5 ~ 2.5%,
Remaining is D-sorbite, and total weight meets 100%;
The stalk uses at least one of wheat straw, straw, corn stalk, cotton straw or the reed of 100~300 mesh;
The preparation method of the green non-poisonous 3D printing consumptive material, the specific steps are as follows:
(1) stalk is pre-processed, obtains straw powder;
(2) pretreated straw powder, citric acid solution are placed in acid-resistant container, are reacted using magnetic stirring apparatus;In advance The mass ratio of straw powder that treated and citric acid is 1:(3 ~ 5), citric acid solution concentration is 15% ~ 25wt%, pH value 2.8- 3.2, the reaction time is 12 ~ 16h, and reaction temperature is 80 ~ 100 DEG C, and control magnetic stirring apparatus revolving speed is 600 ~ 800r/min;
(3) it is cooled to room temperature, ethyl alcohol and step (2) products therefrom is placed in a centrifuge, adjust solution ph to neutrality, weight Multiple centrifugation three times, obtains sediment, and product is washed with deionized, and drying obtains modified straw powder;Straw powder that treated with The mass ratio of ethyl alcohol is 1:(4 ~ 8), centrifuge speed is 3000 ~ 5000r/min, and the time is 20 ~ 30min;
(4) diatom test is placed in sodium hydroxide solution and is activated;
(5) modified straw powder, activation diatom test, D-sorbite that straw powder that step (1) obtains, step (3) obtain are placed in It is mixed in ultrasonic wave homogenizer, obtains colloidal mixture, it is dry, obtain green non-poisonous 3D printing consumptive material.
2. preparation method according to claim 1, which is characterized in that in step (1), pre-process as mechanical ball mill, acetic acid At least one of immersion or NaOH immersion.
3. preparation method according to claim 1, which is characterized in that in step (5), incorporation time is 3 ~ 6h, mixing temperature Degree be 70 ~ 80 DEG C, drying temperature be 60 ~ 70 DEG C, drying time be 20 ~ for 24 hours.
CN201710324335.2A 2017-05-10 2017-05-10 A kind of green non-poisonous 3D printing consumptive material and preparation method thereof Expired - Fee Related CN107129699B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108034273A (en) * 2017-11-27 2018-05-15 安徽拓宝增材制造科技有限公司 A kind of 3D printing consumptive material and preparation method thereof
CN109603920B (en) * 2018-12-18 2020-04-07 同济大学 Visible light excited cellulose-TiO2Composite photocatalyst
CN110330805A (en) * 2019-07-17 2019-10-15 东北农业大学 A kind of crop branch fiber base special type agricultural mulching and its manufacturing method based on 3D printing technique
CN111548617B (en) * 2020-06-24 2022-11-04 南方科技大学 Biodegradable polylactic acid material and preparation method and application thereof

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CN104312119A (en) * 2014-11-06 2015-01-28 芜湖瀚博电子科技有限公司 Straw 3D printing consumable and preparation method thereof
CN104926272A (en) * 2015-06-14 2015-09-23 卞洪锋 3D printing material, preparation method, application method and application
CN106267370A (en) * 2016-08-16 2017-01-04 东华大学 Fibroin albumen/cellulose 3D marking ink
CN106398265A (en) * 2016-12-15 2017-02-15 广西筑梦三体科技有限公司 3D printing material of rape straw with high flexural modulus

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Publication number Priority date Publication date Assignee Title
JP2015501332A (en) * 2011-04-06 2015-01-15 オーエムエス・インヴェストメンツ・インコーポレイティッド Multipurpose lignin-carbohydrate binding system
CN104312119A (en) * 2014-11-06 2015-01-28 芜湖瀚博电子科技有限公司 Straw 3D printing consumable and preparation method thereof
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CN106267370A (en) * 2016-08-16 2017-01-04 东华大学 Fibroin albumen/cellulose 3D marking ink
CN106398265A (en) * 2016-12-15 2017-02-15 广西筑梦三体科技有限公司 3D printing material of rape straw with high flexural modulus

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