CN107129699A - 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
- Publication number
- CN107129699A CN107129699A CN201710324335.2A CN201710324335A CN107129699A CN 107129699 A CN107129699 A CN 107129699A CN 201710324335 A CN201710324335 A CN 201710324335A CN 107129699 A CN107129699 A CN 107129699A
- Authority
- CN
- China
- Prior art keywords
- straw
- powder
- consumptive material
- preparation
- poisonous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- 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
Abstract
The present invention relates to a kind of green non-poisonous 3D printing consumptive material and preparation method thereof, belong to new material technology field.The new material of the present invention is using crop waste stalk as primary raw material, using diatom test as auxiliary material, available for 3D printing.Specific preparation method is that powder of straw is carried out into ball milling pretreatment, soaked and activated with acetic acid, then by the powder of straw of activation and citric acid heating response, reaction is cooled to room temperature, regulation pH to neutrality after terminating, add ethanol, through centrifugation, deionized water washing, drying, modified straw powder is obtained, powder of straw, activation diatom test, D-sorbite is then added, it is homogeneous to mix to colloidal mixture, through being dried to obtain green non-poisonous 3D printing consumptive material.Green non-poisonous 3D printing consumptive material can be obtained using the inventive method, the consumptive material intensity of preparation is high, and processability is good, with it is green, nontoxic, environmentally friendly the features such as.Waste straw and diatom test are turned waste into wealth, is conducive to saving timber resources and its utilization rate, cost is greatly reduced, while significant to environmental protection；Described preparation method, simplifies manufacturing process, reduces production cost, and will not produce 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 technology
3D printing is to be based on three-dimensional CAD model data, successively increases material to manufacture three-dimensional objects by 3D printing equipment
Technology, also known as increasing material manufacturing, restriction one of 3D printing technique development factors are the research and development of printing consumables, 3D printing consumption at present
Assortment class is various, predominantly polymer, composite etc., consumptive material meet efficiently, accurately forming requirements when, can bring poisonous
The problems such as material, environmental pollution, therefore green non-poisonous 3D printing consumptive material is researched and developed by the heat as following 3D printing technique research
Point.The 3D printing consumptive material of the present invention is a kind of new material, and its is green non-poisonous, functional, with low cost, is provided for 3D printing
The material selection of environmental protection.
The yield of stalk and diatom test is big in agriculture field.Crops are the major products of agriculture field, annual inevitable
Substantial amounts of stalk accessory substance being produced, it is natural high polymer 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 substantial amounts of diatom test accessory substance, and diatom test is unique biological form natural inorganic on the earth
Material.Stalk and diatom test one are natural materials, the characteristic with green, environmental protection；Two be that stalk has certain toughness, and silicon
Frustule has some strength, the mutually compound higher-strength and mouldable materials for being beneficial to obtain machinability.
The 3D printing consumptive material being mixed with present by stalk and thermal plastic high polymer is in the majority, and stalk is used as obturator, increasing
Strong composite materials property, but straw content is low, and consumptive material mechanical performance improves not notable, and prepares 3D printing consumption with straw base
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, its
It is modified after string is crushed into drying through processing aid, then uniformly mixes, squeezed with double screw extruder with polyolefin material grain
Go out obtained composite finished product, modified material possesses the processing characteristics of wooden outward appearance and Wood-plastic material, but string
Content is low, and the mechanical performance of synthetic material improves not notable, and material can discharge toxic gas in melting process, exist not
Degradable the problems such as, excessive use certainly will bring environmental problem, therefore can not large-scale promotion and application.
The content of the invention
For the problems of above-mentioned prior art, it is combined it is an object of the invention to provide a kind of stalk and diatom test,
Cheap with certain intensity, low-carbon environment-friendly is green non-poisonous, and product has preferable physical and mechanical properties and processability
3D printing consumptive material of energy and preparation method thereof.
To reach above-mentioned purpose, the technical solution adopted in the present invention is：
A kind of green non-poisonous 3D printing consumptive material proposed by the present invention, the consumptive material is made up of stalk, diatom test and D-sorbite, former
The percentage by weight of material is as follows：
Stalk 50 ~ 80%,
Diatom test 1.5 ~ 2.5%,
Remaining is D-sorbite, and its gross weight meets 100%；
The stalk is using at least one of wheat straw, straw, corn stalk, cotton straw or reed of 100~300 mesh.
The preparation method of green non-poisonous 3D printing consumptive material proposed by the present invention, is comprised the following steps that：
（1）Stalk is pre-processed, powder of straw is obtained；
（2）By pretreated powder of straw, citric acid solution as in acid-resistant container, reacted using magnetic stirring apparatus；In advance
The mass ratio of powder of straw and citric acid after processing is 1:(3 ~ 5), citric acid solution concentration is 15% ~ 25wt%, and pH is 2.8-
3.2, the reaction time is 12 ~ 16h, and reaction temperature is 80 ~ 100 DEG C, and it is 600 ~ 800r/min to control magnetic stirring apparatus rotating speed；
（3）Room temperature is cooled to, by ethanol and step（2）Products therefrom is as in centrifuge, regulation solution PH to neutrality, repeat from
The heart three times, obtains sediment, and product is washed with deionized, and drying obtains modified straw powder；Powder of straw and ethanol after processing
Mass ratio be 1:（4~8）, centrifuge speed is 3000 ~ 5000r/min, and the time is 20 ~ 30min；
（4）By diatom test as carrying out activation process in sodium hydroxide solution；
（5）By step（1）Obtained powder of straw, step（3）Obtained modified straw powder, activation diatom test, D-sorbite as
Mixed in ultrasonic wave homogenizer, obtain colloidal mixture, dried, obtain green non-poisonous 3D printing consumptive material.
In the present invention, step（1）In, pre-process as at least one of mechanical ball mill, acetic acid immersion or NaOH immersions.
In the present invention, step（3）In, the mass ratio of powder of straw and ethanol after processing is 1:（4~8）, centrifuge speed is
3000 ~ 5000r/min, the time is 20 ~ 30min.
In the present invention, step（5）In, incorporation time is 3 ~ 6h, and mixing temperature is 70 ~ 80 DEG C, and drying temperature is 60 ~ 70
DEG C, drying time is 20 ~ 24h.
The beneficial effects of the present invention are：Prepared 3D printing consumptive material has green non-poisonous environmental protection characteristic.In consumptive material system
Diatom test is with the addition of in standby, compared with the material for being not added with diatom test, its intensity is higher, and corrosion resistance is stronger, improved simultaneously
Wearability, improves the finish of material surface, material is had waterproof, ageing resistace；Timber is replaced with waste straw,
Turn waste into wealth, be conducive to saving timber resources, cost greatly reduced, while significant to environmental protection；Diatom test
Use, improve the utilization rate of resource, also greatly improve the performance of material, reach win-win, described preparation method simplifies
Manufacturing process, reduces production cost.With good practicality.
Brief description of the drawings
Fig. 1 is the flow chart of green non-poisonous 3D printing consumptive material preparation method provided in an embodiment of the present invention.
Embodiment
Embodiments of the invention are elaborated below, the present embodiment is carried out lower premised on technical solution of the present invention
Implement, give detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following implementations
Example.
Embodiment 1
（1）The wheat straw of 5g100 mesh is weighed, ball milling 60min in ball mill is put into；
（2）Wheat straw after ball milling is placed in beaker, 25g acetic acid is added, seals, soak 5h at room temperature, filter out excess acetic acid；
（3）It is that 15wt% citric acid solutions are placed in the three-neck flask equipped with condenser pipe by the wheat straw after immersion and 100ml concentration,
12h is reacted in 80 DEG C, 600r/min heat-collecting magnetic stirring devices；
（4）By step（3）Obtained product is cooled to room temperature, and regulation pH to neutrality puts it with 30ml concentration for 95% ethanol
30min is centrifuged in rotating speed is 3000r/min centrifuge, repeated centrifugation three times, gained precipitation is washed with deionized, finally
Drying, crushing；
（5）Weigh 0.1g diatom tests to be placed in beaker, add the NaOH solution that 5ml concentration is 6wt%, seal, soak at room temperature
5h；
（6）By step（4）, step（5）Obtained product, 0.5g100 mesh wheat straw, 1g D-sorbites and 100ml distilled water is placed in
In beaker, in the stirring of ultrasonic wave homogenizer until gluey, temperature is 70 DEG C, and 20h is finally dried in 60 DEG C of baking ovens produces green
Nontoxic 3D printing consumptive material.
The consumptive material is subjected to 3D printing at 120 DEG C, the density of material is 0.89g/cm3 after shaping, and tensile strength is
20.5MPa, bending modulus is 2.1GPa, and shrinkage factor is 0.93%.
Embodiment 2
（1）The straw of 5g150 mesh is weighed, ball milling 60min in ball mill is put into；
（2）Straw after ball milling is placed in beaker, 30g acetic acid is added, seals, soak 4h at room temperature, filter out excess acetic acid；
（3）It is that 20wt% citric acid solutions are placed in the three-neck flask equipped with condenser pipe by the straw after immersion and 100ml concentration,
15h is reacted in 90 DEG C, 650r/min heat-collecting magnetic stirring devices；
（4）By step（3）Obtained product is cooled to room temperature, and regulation pH to neutrality puts it with 40ml concentration for 95% ethanol
25min is centrifuged in rotating speed is 3500r/min centrifuge, repeated centrifugation three times, gained precipitation is washed with deionized, finally
Drying, crushing；
（5）Weigh 0.12g diatom tests to be placed in beaker, add the NaOH solution that 6ml concentration is 6wt%, seal, soak at room temperature
5h；
（6）By step（4）, step（5）Obtained product, 0.4g150 mesh straw, 1.5g D-sorbites and 100ml distilled water is put
In beaker, in the stirring of ultrasonic wave homogenizer until gluey, temperature is 70 DEG C, finally dried in 60 DEG C of baking ovens 22h produce it is green
The nontoxic 3D printing consumptive material of color.
The consumptive material is subjected to 3D printing at 110 DEG C, the density of material is 0.78g/cm3 after shaping, and tensile strength is
19.6MPa, bending modulus is 1.82GPa, and shrinkage factor is 1.33%.
Embodiment 3
（1）The corn stalk of 5g200 mesh is weighed, ball milling 55min in ball mill is put into；
（2）Corn stalk after ball milling is placed in beaker, 30g acetic acid is added, seals, soak 4h at room temperature, filter out excess acetic acid；
（3）It is that 20wt% citric acid solutions are placed in the three-neck flask equipped with condenser pipe by the corn stalk after immersion and 100ml concentration
In, react 15h in 90 DEG C, 750r/min heat-collecting magnetic stirring devices；
（4）By step（3）Obtained product is cooled to room temperature, and regulation pH to neutrality puts it with 40ml concentration for 95% ethanol
25min is centrifuged in rotating speed is 4500r/min centrifuge, repeated centrifugation three times, gained precipitation is washed with deionized, finally
Drying, crushing；
（5）Weigh 0.13g diatom tests to be placed in beaker, add the NaOH solution that 8ml concentration is 6wt%, seal, soak at room temperature
6h；
（6）By step（4）, step（5）Obtained product, 0.35g200 mesh corn stalk, 2g D-sorbites and 150ml distilled water is put
In beaker, in the stirring of ultrasonic wave homogenizer until gluey, temperature is 75 DEG C, finally dried in 65 DEG C of baking ovens 23h produce it is green
The nontoxic 3D printing consumptive material of color.
The consumptive material is subjected to 3D printing at 130 DEG C, the density of material is 1.02g/cm3 after shaping, and tensile strength is
21.2MPa, bending modulus is 1.79GPa, and shrinkage factor is 0.99%.
Embodiment 4
（1）The cotton straw of 5g250 mesh are weighed, ball milling 55min in ball mill is put into；
（2）Cotton straw after ball milling are placed in beaker, 35g acetic acid is added, seals, soak 5h at room temperature, filter out excess acetic acid；
（3）It is that 25wt% citric acid solutions are placed in the three-neck flask equipped with condenser pipe by the cotton straw and 100ml concentration after immersion
In, react 15h in 95 DEG C, 750r/min heat-collecting magnetic stirring devices；
（4）By step（3）Obtained product is cooled to room temperature, and regulation pH to neutrality puts it with 45ml concentration for 95% ethanol
20min is centrifuged in rotating speed is 4500r/min centrifuge, repeated centrifugation three times, gained precipitation is washed with deionized, finally
Drying, crushing；
（5）Weigh 0.15g diatom tests to be placed in beaker, add the NaOH solution that 5ml concentration is 6wt%, seal, soak at room temperature
5h；
（6）By step（4）, step（5）Obtained product, 0.5g250 mesh cottons straw, 2g D-sorbites and 200ml distilled water is put
In beaker, in the stirring of ultrasonic wave homogenizer until gluey, temperature is 70 DEG C, finally dried in 60 DEG C of baking ovens 23h produce it is green
The nontoxic 3D printing consumptive material of color.
The consumptive material is subjected to 3D printing at 100 DEG C, the density of material is 1.1g/cm3 after shaping, and tensile strength is
22.1MPa, bending modulus is 1.89GPa, and shrinkage factor is 0.91%.
Embodiment 5
（1）The reed of 5g300 mesh is weighed, ball milling 50min in ball mill is put into；
（2）Reed after ball milling is placed in beaker, 40g acetic acid is added, seals, soak 3h at room temperature, filter out excess acetic acid；
（3）It is that 25wt% citric acid solutions are placed in the three-neck flask equipped with condenser pipe by the reed after immersion and 100ml concentration,
16h is reacted in 100 DEG C, 800r/min heat-collecting magnetic stirring devices；
（4）By step（3）Obtained product is cooled to room temperature, and regulation pH to neutrality puts it with 50ml concentration for 95% ethanol
20min is centrifuged in rotating speed is 5000r/min centrifuge, repeated centrifugation three times, gained precipitation is washed with deionized, finally
Drying, crushing；
（5）Weigh 0.15g diatom tests to be placed in beaker, add the NaOH solution that 10ml concentration is 6wt%, seal, soak at room temperature
8h；
（6）By step（4）, step（5）Obtained product, 0.3g300 mesh reed, 2.5g D-sorbites and 200ml distilled water is put
In beaker, in the stirring of ultrasonic wave homogenizer until gluey, temperature is 80 DEG C, finally dried in 70 DEG C of baking ovens 24h produce it is green
The nontoxic 3D printing consumptive material of color.
The consumptive material is subjected to 3D printing at 125 DEG C, the density of material is 0.94g/cm3 after shaping, and tensile strength is
20.1MPa, bending modulus is 2.3GPa, and shrinkage factor is 0.91%.
Claims (5)
1. a kind of green non-poisonous 3D printing consumptive material, it is characterised in that：The consumptive material is made up of stalk, diatom test and D-sorbite,
The percentage by weight of raw material is as follows：
Stalk 50 ~ 80%,
Diatom test 1.5 ~ 2.5%,
Remaining is D-sorbite, and its gross weight meets 100%；
The stalk is using at least one of wheat straw, straw, corn stalk, cotton straw or reed of 100~300 mesh.
2. a kind of preparation method of green non-poisonous 3D printing consumptive material as claimed in claim 1, it is characterised in that：Specific steps are such as
Under：
（1）Stalk is pre-processed, powder of straw is obtained；
（2）By pretreated powder of straw, citric acid solution as in acid-resistant container, reacted using magnetic stirring apparatus；In advance
The mass ratio of powder of straw and citric acid after processing is 1:(3 ~ 5), citric acid solution concentration is 15% ~ 25wt%, and pH value is 2.8-
3.2, the reaction time is 12 ~ 16h, and reaction temperature is 80 ~ 100 DEG C, and it is 600 ~ 800r/min to control magnetic stirring apparatus rotating speed；
（3）Room temperature is cooled to, by ethanol and step（2）Products therefrom is as in centrifuge, and regulation solution ph to neutrality is repeated
Centrifugation three times, obtains sediment, and product is washed with deionized, and drying obtains modified straw powder；Powder of straw and second after processing
The mass ratio of alcohol is 1:（4~8）, centrifuge speed is 3000 ~ 5000r/min, and the time is 20 ~ 30min；
（4）By diatom test as carrying out activation process in sodium hydroxide solution；
（5）By step（1）Obtained powder of straw, step（3）Obtained modified straw powder, activation diatom test, D-sorbite as
Mixed in ultrasonic wave homogenizer, obtain colloidal mixture, dried, obtain green non-poisonous 3D printing consumptive material.
3. preparation method according to claim 1, it is characterised in that step（1）In, pre-process as mechanical ball mill, acetic acid
At least one of immersion or NaOH immersions.
4. preparation method according to claim 1, it is characterised in that step（3）In, powder of straw and ethanol after processing
Mass ratio is 1:（4~8）, centrifuge speed is 3000 ~ 5000r/min, and the time is 20 ~ 30min.
5. preparation method according to claim 1, it is characterised in that step（5）In, incorporation time is 3 ~ 6h, mixing temperature
Spend for 70 ~ 80 DEG C, drying temperature is 60 ~ 70 DEG C, drying time is 20 ~ 24h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710324335.2A CN107129699B (en) | 2017-05-10 | 2017-05-10 | A kind of green non-poisonous 3D printing consumptive material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710324335.2A CN107129699B (en) | 2017-05-10 | 2017-05-10 | A kind of green non-poisonous 3D printing consumptive material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107129699A true CN107129699A (en) | 2017-09-05 |
| CN107129699B CN107129699B (en) | 2019-05-14 |
Family
ID=59732329
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710324335.2A Expired - Fee Related CN107129699B (en) | 2017-05-10 | 2017-05-10 | A kind of green non-poisonous 3D printing consumptive material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107129699B (en) |
Cited By (4)
| 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 |
| CN109603920A (en) * | 2018-12-18 | 2019-04-12 | 同济大学 | Cellulose-the TiO of excited by visible light2Composite photo-catalyst |
| 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 |
| CN111548617A (en) * | 2020-06-24 | 2020-08-18 | 南方科技大学 | Biodegradable polylactic acid material and preparation method and application thereof |
Citations (5)
| 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 |
| 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 |
-
2017
- 2017-05-10 CN CN201710324335.2A patent/CN107129699B/en not_active Expired - Fee Related
Patent Citations (5)
| 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 |
| 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 |
Cited By (5)
| 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 |
| CN109603920A (en) * | 2018-12-18 | 2019-04-12 | 同济大学 | Cellulose-the TiO of excited by visible light2Composite photo-catalyst |
| 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 |
| CN111548617A (en) * | 2020-06-24 | 2020-08-18 | 南方科技大学 | Biodegradable polylactic acid material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107129699B (en) | 2019-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107129699A (en) | A kind of green non-poisonous 3D printing consumptive material and preparation method thereof | |
| CN104086785A (en) | Method for preparing composite hydrogel through modifying bamboo shoot leftovers and application of composite hydrogel | |
| CN103223687B (en) | A kind of acetylize modification processing method of Poplar Powder | |
| CN102226030B (en) | Preparation method of crop straw based high power water absorbent | |
| CN107522812A (en) | It is a kind of can slow-release nutrient bone meal Quito function water-loss reducer preparation method | |
| CN109624017A (en) | A kind of fiberboard and preparation method thereof based on fungi | |
| CN103627033B (en) | A kind of Alcohol-soluble protein-starch-baseddegradable degradable composite film and preparation method thereof | |
| CN107082685A (en) | A kind of preparation method of hydro-thermal carbon-base slow release nitrogenous fertilizer | |
| CN110128800A (en) | The biomass-based Wholly-degradable material of powdered rice hulls/PBAT and preparation method | |
| CN103319738B (en) | The method that agricultural crop straw prepares regenerated cellulose composite film | |
| CN103819615A (en) | Method of preparing starch-base highly-water-absorbent material by radiation | |
| CN104497609B (en) | A kind of preparation method of Whole fiber degradable composite material | |
| CN110078940A (en) | A kind of preparation method of BIOLOGICAL CALCIUM composite high-water-absorptivresin resin | |
| CN107383815B (en) | A kind of bamboo fibre lactic acid composite material and preparation method | |
| CN103627035B (en) | The method of mechanical activation strengthening manioc waste thermoplastification modification | |
| CN109251278A (en) | A kind of preparation method of mushroom bran base high water-absorption resin | |
| CN107141513A (en) | A kind of degradable liquid ground film solution of bamboo fiber-based water conservation and preparation method thereof | |
| CN104193500A (en) | Organic fertilizer capable of promoting absorption of strawberries to minerals and preparation method of organic fertilizer | |
| CN102838880A (en) | Method for producing an environmentally-friendly type wood-plastic composite material by utilizing renewable resources | |
| CN102504349B (en) | Phosphate starch biodegradable film and preparation method thereof | |
| CN105985156A (en) | Biomass char adsorbing fertilizer for mulberry and production method thereof | |
| CN109220831A (en) | A kind of dustless type cat litter of green and preparation method thereof | |
| CN109181253A (en) | A kind of degradable foaming biomass fiber composite material and preparation method | |
| CN108048105A (en) | A kind of water-loss reducer of soil and preparation method thereof | |
| CN107619503A (en) | A kind of preparation method of biodegradable plastic material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190514 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |