CN115160059B - Formula and production method of fertilizer carrier capable of being subjected to extrusion type 3D printing - Google Patents
Formula and production method of fertilizer carrier capable of being subjected to extrusion type 3D printing Download PDFInfo
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- CN115160059B CN115160059B CN202210735636.5A CN202210735636A CN115160059B CN 115160059 B CN115160059 B CN 115160059B CN 202210735636 A CN202210735636 A CN 202210735636A CN 115160059 B CN115160059 B CN 115160059B
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- 238000001125 extrusion Methods 0.000 title claims abstract description 49
- 239000003337 fertilizer Substances 0.000 title claims abstract description 49
- 238000010146 3D printing Methods 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 238000009472 formulation Methods 0.000 title claims description 39
- 238000007639 printing Methods 0.000 claims abstract description 68
- 239000000463 material Substances 0.000 claims abstract description 29
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 20
- 239000000661 sodium alginate Substances 0.000 claims abstract description 20
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000230 xanthan gum Substances 0.000 claims abstract description 16
- 235000010493 xanthan gum Nutrition 0.000 claims abstract description 16
- 229920001285 xanthan gum Polymers 0.000 claims abstract description 16
- 229940082509 xanthan gum Drugs 0.000 claims abstract description 16
- 239000000919 ceramic Substances 0.000 claims abstract description 14
- 238000013270 controlled release Methods 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims description 46
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 25
- 239000004202 carbamide Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 16
- 229930195725 Mannitol Natural products 0.000 claims description 16
- 239000000594 mannitol Substances 0.000 claims description 16
- 235000010355 mannitol Nutrition 0.000 claims description 16
- 239000004113 Sepiolite Substances 0.000 claims description 13
- 235000019355 sepiolite Nutrition 0.000 claims description 13
- 229910052624 sepiolite Inorganic materials 0.000 claims description 13
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical group [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000005507 spraying Methods 0.000 claims description 12
- 238000005516 engineering process Methods 0.000 claims description 11
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 8
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 8
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 8
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 8
- 239000001103 potassium chloride Chemical group 0.000 claims description 6
- 235000011164 potassium chloride Nutrition 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010907 mechanical stirring Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical group [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910021538 borax Inorganic materials 0.000 claims description 3
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 3
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 3
- 239000011591 potassium Chemical group 0.000 claims description 3
- 229910052700 potassium Chemical group 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000004328 sodium tetraborate Chemical group 0.000 claims description 3
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 3
- 239000005909 Kieselgur Substances 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical group [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 2
- 235000007686 potassium Nutrition 0.000 claims description 2
- 239000001341 hydroxy propyl starch Substances 0.000 claims 1
- 235000013828 hydroxypropyl starch Nutrition 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- 235000015097 nutrients Nutrition 0.000 abstract description 33
- 230000000694 effects Effects 0.000 abstract description 12
- 229920006237 degradable polymer Polymers 0.000 abstract description 4
- 238000013461 design Methods 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 4
- 229920005615 natural polymer Polymers 0.000 abstract description 4
- 235000016709 nutrition Nutrition 0.000 abstract description 4
- 230000035764 nutrition Effects 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 239000000945 filler Substances 0.000 abstract description 3
- 238000005457 optimization Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 241000196324 Embryophyta Species 0.000 description 8
- 239000004576 sand Substances 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- BGNGWHSBYQYVRX-UHFFFAOYSA-N 4-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C=C1 BGNGWHSBYQYVRX-UHFFFAOYSA-N 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000002035 prolonged effect Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 235000013877 carbamide Nutrition 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004737 colorimetric analysis Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 238000010413 gardening Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000003049 inorganic solvent Substances 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- VFTKIWJJPDJBKD-UHFFFAOYSA-N OCCC[Na] Chemical compound OCCC[Na] VFTKIWJJPDJBKD-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 229910001867 inorganic solvent Inorganic materials 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- -1 roen) Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229940080313 sodium starch Drugs 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- WYWFMUBFNXLFJK-UHFFFAOYSA-N [Mo].[Sb] Chemical compound [Mo].[Sb] WYWFMUBFNXLFJK-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000005048 flame photometry Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000021048 nutrient requirements Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 230000001863 plant nutrition Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229940032147 starch Drugs 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
-
- 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
- B33Y10/00—Processes of additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C9/00—Fertilisers containing urea or urea compounds
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/40—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting fertiliser dosage or release rate; for affecting solubility
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G5/00—Fertilisers characterised by their form
- C05G5/10—Solid or semi-solid fertilisers, e.g. powders
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
- Y02P60/20—Reduction of greenhouse gas [GHG] emissions in agriculture, e.g. CO2
- Y02P60/21—Dinitrogen oxide [N2O], e.g. using aquaponics, hydroponics or efficiency measures
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Structural Engineering (AREA)
- Fertilizers (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a fertilizer carrier formula capable of performing extrusion type 3D printing and a production method thereof. The fertilizer modules produced by printing can be degraded step by step and release the needed nutrients according to the nutrition requirements of specific plants. The invention utilizes natural or synthetic degradable polymer and natural nanometer/micrometer ceramic filler to prepare the formula required by printing, and does not produce harmful residues and cause environmental pollution while achieving customization and controlling fertilizer release. The invention covers the design and production of fertilizer modules by utilizing a multi-material extrusion type 3D printing platform, the release of nutrients is controlled by controlling the spatial distribution of target nutrients in the product, and the controlled release and the slow release of different components and the optimization of printing effects are realized by utilizing natural polymers such as sodium alginate, diatomite, xanthan gum and the like, so that the aim of designing the release of different nutrients according to the requirements of users is fulfilled.
Description
Technical Field
The invention relates to the field of customized production of fertilizers by an extrusion type 3D printing technology, in particular to a formula of a fertilizer carrier capable of performing extrusion type 3D printing and a production method.
Background
The 3D printing technology has cost and production cycle advantages which are incomparable with the traditional processing technology in the direction of product customization according to the user requirements. Because the special printing mode does not need to be developed on a mould or a production line, the printing method is particularly suitable for customizing and producing small-batch products. In the plant nutrition supply direction, different plant varieties, different growth periods, even different geographic positions and environments can cause the change of the plant on the nutrition demand. The existing scheme is to use a general chemical fertilizer to meet the target requirement, and the situation can cause environmental problems such as fertilizer loss, water eutrophication and the like, and also has negative effects on plant growth. Therefore, a 3D printing technology is introduced, and corresponding fertilizer schemes are customized according to the nutrition characteristics and the planting environment requirements of plants, especially household gardening plants with higher economic added values, so as to meet the growth requirements to the greatest extent. No precedent has been found to customize fertilizer modules using 3D printing techniques.
Disclosure of Invention
The invention aims to provide a fertilizer carrier formula capable of performing extrusion type 3D printing and a production method thereof, and the fertilizer can be produced in a small batch in a customized manner.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a fertilizer carrier formula capable of performing extrusion type 3D printing, which comprises the following components in parts by mass:
preferably, the formula comprises the following components in parts by mass:
preferably, the carrier may include one or more of natural organic colloids such as sodium alginate and xanthan gum.
Preferably, the urea can be replaced by compounds such as monopotassium phosphate, potassium chloride, ammonium chloride, borax, potassium fulvate and the like.
Preferably, the natural ceramic powdery material is diatomite or sepiolite, so that the slow release period of the printing product is further improved, and the slow release period is further prolonged by adding the natural ceramic powdery material.
A technology for customizing and producing a controlled release fertilizer by utilizing a multi-nozzle multi-material extrusion type 3D printing technology.
The target printer may have a plurality of independent heads and each head has an independent feed system; or a plurality of feeding systems share one spray head and are mixed in real time during printing, and the two schemes realize the production of the customized fertilizer module containing various functional materials.
The raw material meeting the requirements of the target printer can be fluidity required by printing through a high-temperature melting technology or meet the printing requirement through a method of increasing the fluidity of the material by introducing an inorganic/organic solvent.
The raw materials can be the product molding in a physical mode by a material cooling method and an organic/inorganic solvent volatilizing method, and can also be the product molding in a chemical mode by triggering chemical polymerization reaction by introducing an external energy source of ultraviolet/infrared light.
The printing formula comprises one or more of the following components:
(1) The slow release carrier is natural polymer such as sodium alginate, xanthan gum, etc., or water-soluble degradable polymer artificially synthesized by polyvinyl alcohol, polylactic mannitol, etc.
(2) The target nutrient substances include urea, borax, potassium fulvate and other compounds containing main elements required by plants.
(3) The release rate is regulated by using natural ceramic powdery materials such as diatomite, sepiolite and the like.
(4) Using organic or inorganic solvents such as: the fluidity of the formulation and the physical initiation curing rate are adjusted by water, ethanol and the like.
(5) Chemical initiated cure rate adjustment is achieved using a synthetic material containing chemically reactive end groups.
The invention also provides a method of making further release profile adjustments to a printed product:
(1) In order to further improve the slow release period of the printing product, the slow release period is further prolonged by adding the natural ceramic powdery material. On the basis of the original preparation of the formula, the diatomite or sepiolite with different contents is added on the surface of the formula before stirring and cooling after the mixture is mixed, sealed and heated for 2 hours according to a fixed proportion, and then the mixture is mechanically stirred until the ink is completely cooled, and then the mixture is ground in a grinder for 15 minutes to the required particle size and then stored for printing. After printing, a sand column leaching experiment was performed to determine and compare release curves at different levels of diatomaceous earth or sepiolite.
(2) In order to further improve the slow release period of the printing product, the slow release period of the formula is prolonged by spraying aqueous solutions of materials with different concentrations to cause the materials to form compact chemical bonds to crosslink to form a coating layer or form a indissolvable hydrophobic coating layer to isolate water erosion. After the normal formulation is prepared, after the printing of the sample is finished, forming a cross-linked structure by immediately spraying the formulations of calcium chloride solutions with different contents and sodium alginate until the block-shaped structure is solidified and shaped; and spraying different contents of hydroxypropyl methylcellulose solution or hydroxypropyl sodium starch and other insoluble water solution on the surface of the cured printed sample until the surface of the block structure is finally shaped into a structure with fixed thickness.
A method of producing an extruded 3D printed fertilizer carrier comprising the steps of:
(1) Mixing mannitol, sodium alginate/xanthan gum, urea, ethanol and water, sealing the mixture in an oven at 55-65 ℃ for heating for 0.5-3 hours, then optionally adding natural ceramic powdery materials into the mixed formula, stirring and cooling the mixture under mechanical stirring, and finally further grinding the mixture in a grinding instrument to obtain a fertilizer carrier formula capable of performing extrusion type 3D printing, and waiting for equipment printing;
(2) And (3) carrying out controlled release fertilizer production on the formula of the fertilizer carrier capable of being subjected to extrusion type 3D printing by utilizing a multi-nozzle multi-material extrusion type 3D printing technology.
After printing production, the slow release period of the formula is prolonged by spraying aqueous solutions of materials with different concentrations to cause the materials to form compact chemical bonds to crosslink with each other to form a coating layer or form a indissolvable hydrophobic coating layer to isolate water erosion. After the normal formulation is prepared, after the printing of the sample is finished, forming a cross-linked structure by immediately spraying the formulations of calcium chloride solutions with different contents and sodium alginate until the block-shaped structure is solidified and shaped; and spraying different contents of hydroxypropyl methylcellulose solution or hydroxypropyl sodium starch and other insoluble water solution on the surface of the cured printed sample until the surface of the block structure is finally shaped into a structure with fixed thickness.
Preferably, the diatomite content is 5-50%;
the specific parameters during printing are that the printing speed is 200mm/min, the extrusion speed is 0.02mm/s, the nozzle height is 1mm, and the nozzle diameter is 1mm;
preferably, the coating film is formed from a material and a solvent in an amount of 1 to 10%
The specific parameters are 1-10mm when the film is coated;
the invention also discloses a mode for realizing release of various nutrients or release of one nutrient by stages by carrying out compound printing on formulas with different contents and different fertilizer types and different binder concentrations, which comprises the following specific embodiments:
(1) The formula of single nutrient substances is printed by a single spray head in an experiment, and the quick release and the slow release of the nutrient substances can be realized by adjusting the types, the concentrations and the contents of different binders of the fertilizer, so that the requirements of garden crops with different nutrient requirement periods are respectively met; in addition, the staged release of the same nutrient substance can be further realized by the mode of adjusting different slow release curves, the nutrient demand characteristics of crops are further matched, and the nutrient demands of the crops in different periods are met as far as possible.
(2) Through can possess a plurality of independent shower nozzles and every shower nozzle has independent feed system's printer, assemble different concentration and type nutrient substance and release matrix respectively, through the spatial distribution (such as sandwich structure) of control different nutrient substance and release matrix to obtain different substances and release step by step, further match the nutrient demand characteristic of crop, accomplish the nutrient demand that satisfies the crop in different periods as far as possible.
Compared with the prior art, the invention has the following advantages:
the invention adopts a multi-nozzle multi-material extrusion type 3D printing technology to customize the technology for producing the fertilizer module. The fertilizer modules produced by printing can be degraded step by step and release the needed nutrients according to the nutrition requirements of specific plants. The invention utilizes natural or synthetic degradable polymer and natural nanometer/micrometer ceramic filler to prepare the formula required by printing, and does not produce harmful residues and cause environmental pollution while achieving customization and controlling fertilizer release. The invention covers the design and production of fertilizer modules by utilizing a multi-material extrusion type 3D printing platform, the release of nutrients is controlled by controlling the spatial distribution of target nutrients in the product, and the controlled release and the slow release of different components and the optimization of printing effects are realized by utilizing natural polymers such as sodium alginate, diatomite, xanthan gum and the like, so that the aim of designing the release of different nutrients according to the requirements of users is fulfilled.
Drawings
FIG. 1 is a flow chart of the recipe configuration in the present invention;
FIG. 2 is a release profile of sodium alginate formulation;
FIG. 3 is a release profile of a xanthan gum formulation;
FIG. 4 is a release profile of a sepiolite formulation;
FIG. 5 is an SEM image of formulations 1-6 and formulations 2-5 after spraying with a calcium chloride solution and a hydroxypropyl methylcellulose solution, respectively;
fig. 6 is a block diagram of a printer, wherein the printer comprises a 1 extrusion controller, a 2 extrusion motor, a 3 detachable extrusion screw, a 4 extrusion table (holder), a 5 syringe (storage device), a 6 liftable printing platform (Z-axis regulator), a 7 printing nozzle, an 8 main body support frame, a 9 main body base, a 10 conveyor motor, a 11 conveyor (embedded), and a 12 computer control device (adjusting X/Y/Z axis and printing path).
Detailed Description
The following is a detailed description of the present invention with reference to examples, but they should not be construed as limiting the scope of the invention.
The extrusion type 3D printer in the embodiment of the invention is an extrusion type printer, and the printing path is controlled by a repeater Host software. The method specifically adopts screw extrusion type printing, realizes the design of paths and shapes through g-code codes, controls the moving speed and the Z-axis height of the screw, and adjusts and controls the extrusion speed through an external device. In addition, the printer can be matched with a plurality of printing nozzles at the same time so as to realize the simultaneous printing of a plurality of nozzles.
As shown in fig. 6, the printer includes: extrusion controller 1, extrusion motor 2, detachable extrusion screw 3, extrusion table (holder) 4, injector (storage device) 5, liftable print platform (Z-axis adjuster) 6, print head 7, main body support 8, main body base 9, conveyor motor 10, conveyor (embedded) 11, computer control device (adjust X/Y/Z axis and print path) 12.
Working principle:
the test is carried out in a device built in a laboratory shown in the figure, and the printing path and the position of the X/Y/Z axis are adjusted and the printing speed is adjusted by encoding G-Code in the computer control device 12, so that the printing is also started and stopped; the extrusion speed is regulated by the extrusion controller 1, and test formal printing is started after the test pre-extrusion keeps stable; the printing ink is loaded into the injector (storage device) 5 after the configuration is completed, and the printing ink is removed in the middle of printing or is freely replaced after printing, so that printing is continued; the whole device of the detachable extrusion type screw 3 and the extrusion table 4 can be detached and changed into a double-nozzle injector for printing; a glass plate is placed on the liftable printing platform 6 for ink extrusion, so that the post-treatment of the printing structure is facilitated after the printing is finished;
the printing process comprises the following steps: after the printing ink and the printing spray head are installed in the test, G-code codes are imported through the computer control device 12, initial parameters are adjusted, then the X/Y/Z axis is adjusted to a fixed position and zeroed, the extrusion controller is opened first, then the computer controller is clicked synchronously, a section of ink is pre-extruded, after the printing is stable, the required structure is formally printed, and after the printing is finished, the printing device is adjusted to return to the initial position. The single-material extrusion printing or the multi-material extrusion printing can be realized by changing the spray head or removing the ink halfway, and the printing of various structures such as a core-shell structure or a sandwich structure is finished; after printing, the printing structure can be post-processed, and the test platform can be cleaned to continue printing until printing is completed.
The material in the embodiment of the invention is purchased from a Zhejiang university material and chemical purchasing platform, and specifically, part of reagent information is as follows: mannitol (C) 6 H 14 O 6 Purity is more than or equal to 99%, and the purity is higher than or equal toButyl), xanthan gum (USP grade reagent, roen), sodium alginate ((C) 6 H 7 O 6 Na) n Viscosity of 200+ -20 mpa.s, allatin), urea (CH 4 N 2 O, 99% purity, rohn), potassium chloride (99.5% purity, source foliar organisms, china), sepiolite (400 mesh, rohn), hydroxypropyl methylcellulose (2% viscosity: 6 mpa.s; methoxy: 28-30%; hydroxypropyl: 7.0-12%, aladine), sodium hydroxymethyl cellulose (BR, source leaf organism), calcium chloride (analytically pure, shanghai test), potassium dihydrogen phosphate (purity 99%, source leaf organism), p-dimethylaminobenzaldehyde (CAS: 100-10-7, analytically pure, aledine), solvents (ethanol and water), and other corresponding reagents are analytically pure.
In the experimental embodiment and the comparative example, the content of urea in the eluent is measured by adopting a p-dimethylaminobenzaldehyde colorimetric method, so that the accumulated release rate of nitrogen is calculated; the cumulative release rate of phosphorus in the leacheate was determined using flame photometry and the cumulative release rate of phosphorus was determined using molybdenum antimony anti-colorimetry.
The release curve in the embodiment of the invention is determined by adopting a sand column leaching mode to simulate the release condition of the fertilizer blocks. Specifically, nutrient release conditions of the formulation were studied by designing a sand column (sand core with a height of 15cm, an inner diameter of 4.5cm, and a bottom of 0.1mm, and a piston provided at the upper end thereof, so as to collect the leacheate by an extrusion device such as an ear ball). The release of nutrients under the leaching of the sand column can be simulated in a preliminary way, so that the release of the nutrients can be monitored for a long time. About 0.5g of block fertilizer with different formulations and conventional urea (as a control) are added at the position of 3cm at the top of the sand column, the nitrogen content is kept consistent, 50 milliliters of distilled water (the volume water content of the column under the saturation condition) is added into each sand column, the filtrate is collected at different times of 1, 3, 5, 7, 10, 15, 28 and 30 days, after the eluent is collected, the urea content in the eluent is measured through a p-dimethylaminobenzaldehyde colorimetric method, and the accumulated release rate of nitrogen is calculated, so that a time-dependent change curve of the nitrogen release amount under different formulations is drawn.
Example 1
Taking 18g of mannitol to dissolve in a mixed solvent of 6ml of ethanol and 4ml of water, dissolving 0.2g of sodium alginate and 5g of urea in 10ml of water (one printable formulation, other feasible formulation details are shown in table 1 below), respectively sealing the two in an oven at 60 ℃ for heating for 1 hour, mixing and heating for 15 minutes after the two are dissolved, stirring and cooling the mixed formulation to normal temperature under mechanical stirring, and finally grinding the ink in a grinding instrument for 15 minutes and waiting for equipment printing. (details of the configuration flow are shown in FIG. 1)
Table 1 sodium alginate experimental formulation
( And (3) injection: the urea in the formula can be changed into other various nutrient substances such as potassium chloride, and the quantity of mannitol, sodium alginate and urea can also be changed )
After the configuration is completed, the different formulations of ink need to be loaded into a 5ml syringe and the printer used in the invention is equipped with the ink to be printed. The printing parameters are debugged, the size of the spray head is finally determined to be not lower than 1mm, and 1mm is adopted in the experiment; the printing speed can be between 250 and 100mm/min, and the experiment adopts 200mm/min; the extrusion speed is 0.01-0.05mm/s, and the experimental use is 0.02mm/s; the print height was set to 1mm. The block fertilizer required by the invention is printed under the guidance of the g-code, and can be printed according to any shape required by the code, thereby playing the roles of decoration, beautiful appearance and the like to meet the personalized demands of gardening lovers.
The release curves of different formulations are obviously different, and mainly change due to the content of nutrient elements, the content of binders and other factors. The specific details are shown in figure 2, the sodium alginate-containing formulation has good release effect, long release period and no difference in 14-40 days. When the mannitol content is 1-6, the release period of the formula can be up to about 40 days at the highest, and when the mannitol content is 1-2, the release period of the formula is reduced to 14 days; the slow release period is between 17g mannitol and 30 days.
Example 2
Taking 18g of mannitol to dissolve in 6ml of ethanol and 4ml of water solvent, then dissolving 1g of xanthan gum and 10g of urea in 10ml of water (one of the formulations, other feasible formulation details are shown in the following table 2), respectively sealing the two in an oven at 60 ℃ and heating for 1 hour, mixing and heating for 15 minutes after the two are dissolved, stirring the mixed formulation to normal temperature under mechanical stirring, and finally grinding the ink in a grinder for 15 minutes to wait for equipment to print. (details of the configuration flow are shown in FIG. 1)
Table 2 xanthan gum experimental formulation
( And (3) injection: the urea in the formula can be changed into other various nutrient substances such as potassium chloride, and the quantity of mannitol, sodium alginate and urea can also be changed )
The release curves of different formulations are obviously different, and mainly change due to the content of nutrient elements, the content of binders and other factors. In particular, as shown in fig. 3, the release effect of the xanthan gum-containing formulation is generally short, and the release period is not uniform within 3-7 days. The release period was 7 days when the mannitol content was 18g and the urea content was 5g, whereas the release period was further reduced with increasing urea content, and was 5 days when the urea content was 10g and only 3 days when the urea content was 15 g. It follows that too much urea content has a greater effect on the formulation and can reduce the release cycle of the formulation.
Example 3
Taking 18g of mannitol to dissolve in 6ml of ethanol and 4ml of water solvent, then dissolving 1g of xanthan gum and 10g of urea in 10ml of water (one of the formulations, other feasible formulation details are shown in the following table 3), respectively sealing the two in an oven at 60 ℃ for heating for 1 hour, mixing and heating for 15 minutes after all the two are dissolved, adding 2g of sepiolite into the mixed formulation, then sealing and stirring to normal temperature under mechanical stirring, and finally grinding the ink in a grinder for 15 minutes to wait for equipment printing. (details of the configuration flow are shown in FIG. 1)
Table 3 sepiolite experimental formulation
( And (3) injection: the urea in the formula can be replaced by other nutrients such as potassium chloride, the amount of mannitol, sodium alginate and urea can also be changed, and sepiolite can be replaced by other ceramic-based materials such as diatomite )
The release curves of different formulations are obviously different, and mainly change due to the content of nutrient elements, the content of binders and other factors. The details are shown in the following figure 4, the sepiolite-containing formula has a remarkable prolonging effect relative to the slow release period of the initial formula, the release effect is good, the release period is long, and the maximum time can reach about 40 days. Specifically, 2g of sepiolite is added to the original formulation containing xanthan gum, and the release period of the formulation is improved by 7 days, up to 14 days, relative to the original formulation; and 2g of sepiolite is added to the original formula containing sodium alginate, the release period of the formula is improved by 10 days, up to 40 days, the slow release period is obviously improved, the fertilizer requirement characteristic of gardening crops for a long period is met, and the effect of the ceramic matrix material on adjusting the release curve is obvious from the side surface.
EXAMPLE 4 spray Effect study of post-treatments
After the formula configuration and printing are carried out in a conventional manner, the surface of the 3D printing controlled release fertilizer extruded by the material can be obviously improved by spraying a calcium chloride solution in the range of 2% -10% (w/v) or coating a hydroxypropyl methylcellulose or a hydroxymethyl starch sodium aqueous solution on the surface layer (see the SEM image of figure 5 for details), the surface of the block fertilizer is more compact after the calcium chloride solution is sprayed, and the surface of the block fertilizer is smoother after the hydroxypropyl methylcellulose is sprayed. The release period of the two is obviously different, the longest release period can reach 50 days after spraying the calcium chloride solution, but the release period after spraying the hydroxypropyl methylcellulose solution is not obviously enhanced, which indicates that the crosslinking capability is better than the effect of common coating, and the method provides a new idea for researching and developing the massive fertilizer and is more beneficial to customizing the plant fertilizer.
From the above examples, the present invention provides a technique for custom manufacturing fertilizer modules using multi-jet multi-material extrusion 3D printing techniques. The fertilizer modules produced by printing can be degraded step by step and release the needed nutrients according to the specific plant requirements. The invention utilizes natural or synthetic degradable polymer and natural nanometer/micrometer ceramic filler to prepare the formula required by printing, and the invention realizes customization, controls fertilizer release, produces no harmful residue and does not cause environmental pollution. The invention covers the design and production of fertilizer modules by utilizing a multi-material extrusion type 3D printing platform, the release of nutrients is controlled by controlling the spatial distribution of target nutrients in the product, and the controlled release and the slow release of different components and the optimization of printing effects are realized by utilizing natural polymers such as sodium alginate, diatomite, xanthan gum and the like, so that the aim of designing the release of different nutrients according to the requirements of users is fulfilled.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (4)
1. The production method of the customized modular controlled release fertilizer based on the extrusion type 3D printing is characterized by adopting a fertilizer carrier formula capable of performing the extrusion type 3D printing, and the production method comprises the following components in parts by mass:
10-30 parts of mannitol;
sodium alginate or/and xanthan gum 0.1-2 parts;
3-20 parts of urea;
3-10 parts of ethanol;
7-20 parts of water;
0-5 parts of natural ceramic powdery material;
the production method comprises the following steps:
(1) Mixing mannitol, sodium alginate or/and xanthan gum, urea, ethanol and water, sealing the mixture in an oven at 55-65 ℃ for heating for 0.5-3 hours, then optionally adding natural ceramic powdery materials into the mixed formula, stirring and cooling the mixture under mechanical stirring, and finally further grinding the mixture in a grinding instrument to obtain a fertilizer carrier formula capable of performing extrusion type 3D printing, and waiting for equipment printing;
(2) The formula of the fertilizer carrier capable of being subjected to extrusion type 3D printing is subjected to controlled release fertilizer production by utilizing a multi-nozzle multi-material extrusion type 3D printing technology;
after printing production, forming a cross-linked structure by immediately spraying calcium chloride solutions with different contents until the block structure is solidified and shaped, so as to obtain the customized modular controlled release fertilizer based on extrusion type 3D printing;
or after the printing production, spraying hydroxypropyl methyl cellulose water solutions or hydroxypropyl starch sodium water solutions with different contents on the surface of the block structure until the block structure is finally shaped into a structure with fixed thickness, so as to obtain the customized modular controlled release fertilizer based on the extrusion type 3D printing.
2. The method for producing a customized modular controlled release fertilizer based on extrusion 3D printing according to claim 1, wherein the fertilizer carrier formulation capable of extrusion 3D printing comprises the following components in parts by mass:
12-18 parts of mannitol;
sodium alginate or/and xanthan gum 0.5-1 part;
5-15 parts of urea;
4-8 parts of ethanol;
8-16 parts of water;
2-4 parts of natural ceramic powdery material.
3. The method according to claim 1, wherein the urea is replaced with potassium dihydrogen phosphate, potassium chloride, ammonium chloride, borax or potassium fulvate.
4. The method according to claim 1, wherein the natural ceramic powder material is diatomaceous earth or sepiolite.
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