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 PDFInfo
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- 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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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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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
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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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
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Abstract
The present invention relates to a kind of green non-poisonous 3D printing consumptive materials and preparation method thereof, belong to new material technology field.New material of the invention is, using diatom test as auxiliary material, to can be used for 3D printing using crop waste stalk as primary raw material.Specific preparation method is that straw powder is carried out ball milling pretreatment, it is impregnated and is activated with acetic acid, then it by the straw powder of activation and citric acid heating reaction, is cooled to room temperature after reaction, adjusts pH to neutrality, ethyl alcohol is added, through centrifugation, deionized water washing, drying, modified straw powder is obtained, straw powder, activation diatom test, D-sorbite is then added, it is homogeneous to mix to colloidal mixture, it is dried to obtain green non-poisonous 3D printing consumptive material.Using the available green non-poisonous 3D printing consumptive material of the method for the present invention, the consumptive material intensity of preparation is high, and processability is good, has the characteristics that green, nontoxic, environmentally friendly.Waste straw and diatom test are turned waste into wealth, is conducive to save timber resources and its utilization rate, greatly reduces cost, while being of great significance to environmental protection；The preparation method, simplifies manufacturing process, reduces production cost, and will not generate intractable toxic waste liquid.
Description
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.
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| 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 |
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| 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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