CN115073245A - Rapid 3D printing and forming method for photo-thermal composite curing of butylated hydroxytoluene solid propellant - Google Patents
Rapid 3D printing and forming method for photo-thermal composite curing of butylated hydroxytoluene solid propellant Download PDFInfo
- Publication number
- CN115073245A CN115073245A CN202110261593.7A CN202110261593A CN115073245A CN 115073245 A CN115073245 A CN 115073245A CN 202110261593 A CN202110261593 A CN 202110261593A CN 115073245 A CN115073245 A CN 115073245A
- Authority
- CN
- China
- Prior art keywords
- printing
- curing
- solid propellant
- rapid
- photo
- 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.)
- Pending
Links
- 239000004449 solid propellant Substances 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000010146 3D printing Methods 0.000 title claims abstract description 24
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 239000004322 Butylated hydroxytoluene Substances 0.000 title claims description 8
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 title claims description 8
- 229940095259 butylated hydroxytoluene Drugs 0.000 title claims description 8
- 235000010354 butylated hydroxytoluene Nutrition 0.000 title claims description 8
- 239000000463 material Substances 0.000 claims abstract description 52
- 238000007639 printing Methods 0.000 claims abstract description 49
- 239000007921 spray Substances 0.000 claims abstract description 20
- 238000011417 postcuring Methods 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 16
- 238000001125 extrusion Methods 0.000 claims abstract description 15
- 239000007800 oxidant agent Substances 0.000 claims abstract description 15
- 230000001590 oxidative effect Effects 0.000 claims abstract description 14
- 239000000853 adhesive Substances 0.000 claims abstract description 13
- 230000001070 adhesive effect Effects 0.000 claims abstract description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 9
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- BDAHDQGVJHDLHQ-UHFFFAOYSA-N [2-(1-hydroxycyclohexyl)phenyl]-phenylmethanone Chemical compound C=1C=CC=C(C(=O)C=2C=CC=CC=2)C=1C1(O)CCCCC1 BDAHDQGVJHDLHQ-UHFFFAOYSA-N 0.000 claims description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 4
- UOQACRNTVQWTFF-UHFFFAOYSA-N decane-1,10-dithiol Chemical compound SCCCCCCCCCCS UOQACRNTVQWTFF-UHFFFAOYSA-N 0.000 claims description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 4
- 239000013307 optical fiber Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 claims description 3
- -1 4-methylthiophenyl Chemical group 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 2
- XTFIVUDBNACUBN-UHFFFAOYSA-N 1,3,5-trinitro-1,3,5-triazinane Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)C1 XTFIVUDBNACUBN-UHFFFAOYSA-N 0.000 claims description 2
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000838 Al alloy Inorganic materials 0.000 claims description 2
- 239000000028 HMX Substances 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- 244000028419 Styrax benzoin Species 0.000 claims description 2
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 2
- PXJIGLODKBGIFU-UHFFFAOYSA-N [PH3]=O.CC1NC1.CC1NC1.CC1NC1 Chemical compound [PH3]=O.CC1NC1.CC1NC1.CC1NC1 PXJIGLODKBGIFU-UHFFFAOYSA-N 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 2
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 2
- FJMNNXLGOUYVHO-UHFFFAOYSA-N aluminum zinc Chemical compound [Al].[Zn] FJMNNXLGOUYVHO-UHFFFAOYSA-N 0.000 claims description 2
- 229960002130 benzoin Drugs 0.000 claims description 2
- 238000009529 body temperature measurement Methods 0.000 claims description 2
- FUHQFAMVYDIUKL-UHFFFAOYSA-N fox-7 Chemical compound NC(N)=C([N+]([O-])=O)[N+]([O-])=O FUHQFAMVYDIUKL-UHFFFAOYSA-N 0.000 claims description 2
- 235000019382 gum benzoic Nutrition 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- UZGLIIJVICEWHF-UHFFFAOYSA-N octogen Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)CN([N+]([O-])=O)C1 UZGLIIJVICEWHF-UHFFFAOYSA-N 0.000 claims description 2
- 239000003570 air Substances 0.000 claims 3
- 239000012080 ambient air Substances 0.000 claims 1
- 238000009413 insulation Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 239000012752 auxiliary agent Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 33
- 239000003380 propellant Substances 0.000 description 16
- 230000001276 controlling effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000009864 tensile test Methods 0.000 description 4
- 239000013022 formulation composition Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000009826 distribution Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
- C06B21/0033—Shaping the mixture
- C06B21/005—By a process involving melting at least part of the ingredients
-
- 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
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/007—Ballistic modifiers, burning rate catalysts, burning rate depressing agents, e.g. for gas generating
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B33/00—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide
- C06B33/04—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide the material being an inorganic nitrogen-oxygen salt
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B33/00—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide
- C06B33/06—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide the material being an inorganic oxygen-halogen salt
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B33/00—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide
- C06B33/08—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide with a nitrated organic compound
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Structural Engineering (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The invention discloses a rapid 3D printing and forming method for photo-thermal composite curing of a hydroxyl-terminated solid propellant, which is characterized in that a small amount of photoinitiator, thermal initiator and curing catalyst are introduced into a hydroxyl-terminated solid propellant system with adhesive, solid fuel and oxidant as main raw materials, the mixed materials are conveyed to a fixed spray head, the movement of a printing platform and the extrusion of the materials at the spray head are controlled, the extruded materials to be cured are simultaneously heated and irradiated by ultraviolet light, so that the pre-curing speed and effect are improved, and finally, a printing and forming sample is subjected to post-curing in a constant temperature box. The method is characterized in that a small amount of curing auxiliary agent is directly introduced into the butylated hydroxyl adhesive system, so that the pre-curing speed and effect are improved, the post-curing time is shortened, and the integral printing and forming speed is improved.
Description
Technical Field
The invention relates to a forming processing method of a solid propellant, in particular to a rapid 3D printing forming method of a hydroxyl-terminated polybutadiene solid propellant through photo-thermal composite curing.
Background
The butyl hydroxy compound solid propellant has the characteristics of moderate energy level, good mechanical property, excellent process property, aging resistance and low cost, and is widely applied.
The traditional mechanical pouring and charging process has limitations in manufacturing propellant grains with complex structures, the production period is long due to multiple working procedures and long curing time, and the application of a 3D printing technology in the field of energetic materials is beneficial to realizing the manufacturing of propellants with complex structures. The curing method in the propellant 3D printing process mainly comprises thermal curing and photo-curing. The production period is prolonged because longer curing time is needed for thermosetting, and Chinese patent document CN109438149A discloses a preparation method of a thermosetting composite propellant, wherein a spray head and the ambient temperature are changed to control the curing speed, but the curing time still needs 120-168 h, so that the aim of rapid printing cannot be fulfilled; the photo-curing is realized mainly by introducing photosensitive resin to partially replace the binder of the original system. Chinese patent document CN107283826A discloses a 3D printing and forming method of a solid propellant based on ultraviolet light curing, wherein 2-20% of photosensitive resin is introduced, and ultraviolet light irradiates along with a material extrusion head to enable the material to be cured and formed in time.
Disclosure of Invention
In order to overcome the defects of the prior art and improve the curing speed of the solid propellant with the hydroxyl groups in the 3D printing process, the invention provides a rapid 3D printing and forming method for photo-thermal composite curing of the solid propellant with the hydroxyl groups, wherein an initiator and a curing catalyst with the total mass not more than 6 percent are introduced into the formula of the solid propellant with the hydroxyl groups, so that the requirements of the rapid 3D printing and forming of the solid propellant with the hydroxyl groups on the curing speed and the curing effect can be met.
The technical scheme of the invention is as follows:
a rapid 3D printing and forming method of hydroxyl-terminated solid propellant photo-thermal composite curing is characterized in that an adhesive and a solid fuel are uniformly mixed under the heating condition, then an oxidant, a photoinitiator, a thermal initiator and a curing catalyst are uniformly mixed, and slurry is conveyed to a fixed spray head for continuous extrusion through vacuum defoaming. Controlling the stacking molding of the extruded materials, simultaneously adopting an ultraviolet irradiation and heating mode to pre-cure the extruded materials, and adjusting the heating power and the ultraviolet light intensity in real time according to the material temperature to ensure the safety. And after printing, placing the sample in a water bath thermostat for post-curing, and obtaining a finished product of the solid propellant after post-curing.
The method comprises the following specific steps:
step 1, uniformly mixing an adhesive and solid fuel under a heating condition, uniformly mixing an oxidant, a photoinitiator, a thermal initiator and a curing catalyst, and then carrying out vacuum defoaming to obtain solid propellant slurry;
step 2, conveying the slurry uniformly mixed in the step 1 to an extrusion nozzle for continuous extrusion, performing point irradiation on the material at the nozzle by adopting ultraviolet light, and preheating the material by using an oil bath circulating heating nozzle;
step 3, controlling the printing platform to perform three-dimensional movement and extruding and stacking slurry at the fixed spray nozzle, simultaneously performing surface irradiation on stacked materials by using an annular ultraviolet light source which synchronously moves along with the printing platform, and heating the stacked materials by using an oil bath circulating heating printing platform; heating the printing environment by using hot air; after each layer of material is piled up and precured, the printing platform descends one layer thickness to obtain a precured solid propellant printing body;
and 4, placing the pre-cured solid propellant printing body obtained by printing in the step 3 into a constant-temperature oven for post-curing, and obtaining a solid propellant finished product after curing is completed.
Compared with the prior art, the invention has the following remarkable advantages: 1) a small amount of initiator and catalyst are used for replacing a large amount of introduced photosensitive resin, so that the influences on the formula and the energy performance of the butylated hydroxytoluene solid propellant are small; 2) the ultraviolet irradiation mode is improved, and two processing methods of point irradiation and surface irradiation are adopted for the nozzle and the stacking material; 3) a light and heat dual-initiation curing system is adopted, so that the curing reaction and curing of the system are accelerated, the speed and the degree of pre-curing are improved, and the time required by post-curing is reduced; 4) the whole material conveying system is fixed with the spray head pipeline, so that the stability and reliability of feeding are ensured.
Detailed Description
A rapid 3D printing and forming method for photo-thermal composite curing of a hydroxyl-terminated polybutadiene solid propellant comprises the following specific embodiments:
step 1, continuously mixing an adhesive and solid fuel under the heating condition of 30-40 ℃, stopping heating after the adhesive is fully soaked in the solid fuel, mixing an oxidant, a photoinitiator, a thermal initiator and a curing catalyst, and uniformly kneading under the vacuum condition. The adhesive is hydroxyl-terminated polybutadiene; the solid fuel is one or a mixture of more than one of aluminum powder, titanium powder, magnesium aluminum alloy powder and aluminum zinc alloy powder; the oxidant is one or a mixture of more than one of ammonium perchlorate, ammonium nitrate, hexogen, octogen and FOX-7; the photoinitiator is one or a mixture of more than two of benzoin dimethyl ether, 1-hydroxycyclohexyl benzophenone, tripropylene glycol diacrylate, isobornyl acrylate and 2-methyl-1- (4-methylthiophenyl) -2-morpholine-1-acetone; the thermal initiator is one or a mixture of more than two of isophorone diisocyanate, toluene diisocyanate, tris (2-methyl aziridine) phosphine oxide and hexamethylene diisocyanate; the curing catalyst is one or a mixture of more than two of 1, 10-decanedithiol and dibutyltin dilaurate.
The average molecular weight of the hydroxyl-terminated polybutadiene is 2500-4500 g/mol;
the diameter of the solid fuel particles is 1-50 mu m, and the diameter of the oxidant particles is 10-120 mu m;
the using amount of the adhesive accounts for 10-20% of the total mass of the propellant;
the solid fuel accounts for 0-20% of the total mass of the propellant;
the using amount of the oxidant accounts for 50-85% of the total mass of the propellant;
the content of the photoinitiator accounts for 0.4-2.5% of the total mass of the material;
the content of the thermal initiator accounts for 0.4-2.5% of the total mass of the material;
the content of the curing catalyst accounts for 0.2-1% of the total mass of the material.
And 2, conveying the slurry uniformly mixed in the step 1 to an extrusion nozzle by adopting a screw rod type to perform continuous extrusion.
And 3, controlling the printing platform to perform three-dimensional motion and continuously extruding propellant slurry by the nozzle by the 3D printing control software according to the sliced propellant three-dimensional model. For the materials at the nozzle, the optical fiber fixed relative to the nozzle is used for transmitting ultraviolet light for point irradiation, and the oil bath circulating heating nozzle is used for heating the materials; performing surface irradiation on the piled materials by using an annular ultraviolet light source which synchronously moves along with the printing platform, and heating the materials by using an oil bath circulating heating printing platform; the curing environment is heated with hot air. And regulating and controlling heating power according to the material temperature monitored by infrared temperature measurement. And after each layer of material is built, the printing platform descends by one layer thickness, and the layers are built and cured layer by layer to obtain the pre-cured solid propellant printing body.
The intensity of ultraviolet light output by the optical fiber interface is 1-30 mW/cm 2 The wavelength range is 200-420 nm, and the intensity of the ultraviolet light output by the annular ultraviolet light source is 0.5-20 mW/cm 2 The wavelength range is 250-420 nm;
the heating temperature of the spray head and the printing platform is 50-70 ℃, and the hot air temperature is 50-100 ℃;
the thickness of the layer is 0.05-1.0 mm, the horizontal movement speed of the extrusion nozzle is less than 200mm/s, and the diameter of a nozzle of the extrusion nozzle is 0.3-3.0 mm.
And 4, placing the solid propellant obtained by printing in the step 3 into a constant-temperature oven for post-curing, and obtaining a finished product of the solid propellant after curing is completed.
The post-curing temperature is 50-70 ℃, and the time required by post-curing is 5-24 h.
The invention is further illustrated, but not limited, by the following examples.
Examples 1 to 4:
hydroxyl-terminated polybutadiene with the average molecular weight of 2500 is used as an adhesive, ammonium perchlorate with the particle size distribution of 100-120 mu m is used as an oxidant, 1-hydroxycyclohexyl benzophenone is used as a photoinitiator, toluene diisocyanate is used as a thermal initiator, and 1, 10-decanedithiol and dibutyltin dilaurate are used as curing catalysts. The components and contents are shown in the following table 1. The materials are uniformly mixed under the condition of heating at 30 ℃, and are conveyed to a spray head by a screw extruder for continuous extrusion. The diameter of the nozzle is 3mm, the propellant model is sliced and planned by slicing software, the 3D printing software reads a slice file to control the movement of the printing platform and the extrusion speed of the spray head, and extruded materials are orderly stacked on the printing platform. And respectively irradiating the discharge port and the stacking material by adopting point and surface ultraviolet light, and heating the material by utilizing hot air, a spray head and the temperature of a printing platform for precuring. Wherein the ultraviolet irradiation intensity at the nozzle is 1mW/cm 2 The ultraviolet irradiation intensity of the stacking material is 0.5mW/cm 2 The ultraviolet wavelength is 420nm, and the heating temperature of the nozzle and the printing platform is 50 ℃. The horizontal movement speed of the printing platform is 200mm/s, the descending layer thickness of the printing platform is 1mm after each layer of material is built, and the printing platform is built, cured and molded layer by layer. And (3) placing the formed sample into a constant-temperature oven at 50 ℃ for post-curing for 5h to obtain a finished solid propellant, standing for 7d without deformation, and carrying out tensile test on the propellant according to a GJB770B-2005 method 413.1, wherein the formula and the corresponding elongation at break of the solid propellant are shown in Table 1.
TABLE 1 examples 1-4 propellant formulation compositions and elongation at break
Examples 5 to 7:
hydroxyl-terminated polybutadiene with average molecular weight of 2500 as adhesiveAmmonium perchlorate with the diameter distribution of 100-120 mu m is used as an oxidant, aluminum powder with the average particle diameter of 1 mu m is used as solid fuel, 1-hydroxycyclohexyl benzophenone is used as a photoinitiator, toluene diisocyanate is used as a thermal initiator, and 1, 10-decanedithiol and dibutyltin dilaurate are used as curing catalysts. The components and contents are shown in the following table 1. The solid fuel and the adhesive are heated and mixed, then the oxidant, the photoinitiator, the thermal initiator and the curing catalyst are mixed, and the mixture is conveyed to a nozzle by a screw extruder for continuous extrusion. The diameter of a nozzle is 1mm, a propellant model is sliced and planned by slicing software, a 3D printing software reads a slice file to control the movement of a printing platform and the extrusion speed of a spray head, and extruded materials are orderly stacked on the printing platform. And respectively irradiating the discharge port and the stacking material by adopting point and surface ultraviolet light, and heating the material by utilizing hot air, a spray head and the temperature of a printing platform for precuring. Wherein the ultraviolet irradiation intensity at the nozzle is 30mW/cm 2 The ultraviolet irradiation intensity of the stacking material is 20mW/cm 2 The ultraviolet wavelength is 310nm, and the heating temperature of the spray head and the printing platform is 60 ℃. The horizontal movement speed of the printing platform is 200mm/s, the descending layer thickness of the printing platform is 0.5mm after each layer of material is built, and the printing platform is built, cured and molded layer by layer. And (3) placing the molded sample into a constant-temperature oven at 50 ℃ for post-curing for 8h to obtain a solid propellant finished product, standing for 7d without deformation, and performing tensile test on the obtained solid propellant, wherein the formula and the elongation at break are shown in Table 2.
TABLE 2 examples 5-7 propellant formulation compositions and elongation at break
Compared with the embodiments 1-4, the metal fuel is added in the formula of the embodiments 5-7, the light transmittance of the system is influenced, and the good curing effect can still be achieved by changing the ultraviolet parameters and the post-curing time.
Examples 8 to 13:
the average molecular weight of the adhesive, the type and the amount of the oxidant and the type and the amount of the solid fuel are changed to carry out a comparison test, the other conditions of the diameter of a nozzle, the wavelength and the irradiation intensity of ultraviolet light, the heating temperature of a spray head, the falling layer thickness of a printing platform, the post-curing temperature and the like are the same as those of the embodiment 5-7, the solid propellant finished product is obtained by post-curing for 10-24 hours at 50 ℃, standing for 7 days without deformation, the obtained solid propellant is subjected to a tensile test, and the formula and the elongation at break are shown in the table 3.
TABLE 3 propellant formulation compositions and elongations at break of examples 8-13
From examples 8 to 13, it can be seen that solid propellants with good curing effects can be obtained by selecting different initiators and catalysts, introducing a butylated hydroxy system propellant, and performing short-time post-curing.
Examples 14 to 18:
the formula same as that of the embodiment 8 is adopted, the process parameters such as printer parameters, ultraviolet wavelength and intensity, heating temperature and the like are changed to carry out a comparison test, after post-curing for 10-15 hours, a solid propellant finished product is obtained, standing is carried out for 7 days without deformation, the obtained solid propellant is subjected to a tensile test, and the process parameters and the elongation at break are shown in the table 4.
TABLE 4 examples 14 to 18 Process parameters conditions and elongation at break
The embodiment shows that the method disclosed by the invention is adopted for 3D printing of the hydroxyl-terminated solid propellant, a small amount of initiator and catalyst are directly introduced into the hydroxyl-terminated solid propellant, the precuring speed in the printing process is increased by a photo-thermal composite curing method, the time required by post curing is shortened, and the forming speed of 3D printing of the hydroxyl-terminated solid propellant is finally increased.
Claims (10)
1. A rapid 3D printing and forming method for photo-thermal composite curing of a hydroxyl-terminated polybutadiene solid propellant is characterized by comprising the following steps:
step 1, uniformly mixing an adhesive and solid fuel under a heating condition, uniformly mixing an oxidant, a photoinitiator, a thermal initiator and a curing catalyst, and then carrying out vacuum defoamation to obtain solid propellant slurry;
step 2, conveying the slurry uniformly mixed in the step 1 to a fixed spray head for continuous extrusion;
step 3, controlling the printing platform to perform three-dimensional motion and control slurry stacking at the fixed spray nozzle by computer software, simultaneously performing precuring on the freshly extruded material and the stacked material in an ultraviolet irradiation and heating mode, and adjusting heating power in real time according to the temperature of the material below the spray nozzle, which is monitored by infrared temperature measurement; after each layer of material is piled up and precured, the printing platform descends one layer thickness to obtain a precured solid propellant printing body;
and 4, placing the pre-cured solid propellant printing body obtained by printing in the step 3 in a constant-temperature oven for post-curing to obtain a solid propellant finished product.
2. The method for rapid 3D printing and forming through the photothermal composite curing of the hydroxyl solid propellant according to claim 1, wherein the adhesive in the step 1 is hydroxyl-terminated polybutadiene (hydroxyl), and the average molecular weight is 2500-4500 g/mol;
the solid fuel is one or a mixture of more than two of aluminum powder, titanium powder, magnesium-aluminum alloy powder and aluminum-zinc alloy powder;
the oxidant is one or a mixture of more than two of ammonium perchlorate, ammonium nitrate, hexogen, octogen and FOX-7;
the photoinitiator is one or a mixture of more than two of benzoin dimethyl ether, 1-hydroxycyclohexyl benzophenone, tripropylene glycol diacrylate, isobornyl acrylate and 2-methyl-1- (4-methylthiophenyl) -2-morpholine-1-acetone;
the thermal initiator is one or a mixture of more than two of isophorone diisocyanate, toluene diisocyanate, tris (2-methyl aziridine) phosphine oxide and hexamethylene diisocyanate;
the curing catalyst is a mixture of 1, 10-decanedithiol and dibutyltin dilaurate.
3. The method for rapid 3D printing and forming through photo-thermal composite curing of the butylated hydroxyl solid propellant as claimed in claim 1, wherein the content of the binder accounts for 10-20% of the total mass of the material, the content of the oxidant accounts for 50-85% of the total mass of the material, the content of the solid fuel accounts for 0-20% of the total mass of the material, the content of the photoinitiator accounts for 0.4-2.5% of the total mass of the material, the content of the thermal initiator accounts for 0.4-2.5% of the total mass of the material, and the content of the curing catalyst accounts for 0.2-1% of the total mass of the material.
4. The method for rapid 3D printing and forming through photo-thermal composite curing of the butylated hydroxytoluene solid propellant as claimed in claim 1, wherein the heating condition for mixing the binder and the solid fuel in step 1 is 30-40 ℃.
5. The method for rapid 3D printing and forming through photo-thermal composite curing of the butylated hydroxytoluene solid propellant as claimed in claim 1, wherein the particle diameter of the solid fuel is 1-50 μm, and the particle diameter of the oxidizer is 10-120 μm.
6. The method for rapid 3D printing and forming through photo-thermal composite curing of the butylated hydroxytoluene solid propellant as claimed in claim 1, wherein the materials uniformly mixed in the step 2 are conveyed by a screw type conveying mode or a piston type conveying mode.
7. The method for rapid 3D printing and forming through photo-thermal composite curing of the butylated hydroxytoluene solid propellant as claimed in claim 1, wherein the distance of each layer of descending of the printing platform in step 3 is 0.05-1.0 mm, the horizontal movement speed of the printing platform is 50-200 mm/s, and the diameter of the nozzle of the extrusion nozzle is 0.3-3.0 mm.
8. The hydroxyl-terminated solid propellant photo-thermal composite curing rapid 3D printing and forming method as claimed in claim 1, wherein the irradiation manner of the ultraviolet light in step 3 includes point irradiation on the material at the nozzle and surface irradiation on the piled material, wherein the point irradiation requires 3 optical fibers for transmitting the ultraviolet light, the light outlet synchronously moves along with the fixed nozzle to irradiate the freshly extruded material, and the output ultraviolet light intensity of the optical fiber light outlet is 1-30 mW/cm 2 The wavelength range is 250-420 nm; ultraviolet light required by surface irradiation is provided by an annular ultraviolet light source, the annular ultraviolet light source synchronously moves along with the printing platform, and the intensity of the output ultraviolet light is 0.5-20 mW/cm 2 The wavelength range is 250-420 nm.
9. The method for rapid 3D printing and forming through photo-thermal composite curing of the butylated hydroxytoluene solid propellant as claimed in claim 1, wherein the manner of heating the pre-cured material in step 3 comprises heating a sprayer and a printing platform in an oil bath and heating ambient air with hot air.
10. The method for heating the pre-cured material according to claim 10, wherein the heating of the spray head and the printing platform in the step 3 is realized by an oil bath circulation system, the heat insulation is realized between the spray head and the air and between the printing platform and a moving platform below the printing platform, and the temperature of the spray head and the printing platform is 50-70 ℃; the hot air temperature is 50-100 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110261593.7A CN115073245A (en) | 2021-03-10 | 2021-03-10 | Rapid 3D printing and forming method for photo-thermal composite curing of butylated hydroxytoluene solid propellant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110261593.7A CN115073245A (en) | 2021-03-10 | 2021-03-10 | Rapid 3D printing and forming method for photo-thermal composite curing of butylated hydroxytoluene solid propellant |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115073245A true CN115073245A (en) | 2022-09-20 |
Family
ID=83241356
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110261593.7A Pending CN115073245A (en) | 2021-03-10 | 2021-03-10 | Rapid 3D printing and forming method for photo-thermal composite curing of butylated hydroxytoluene solid propellant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115073245A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107283826A (en) * | 2017-06-28 | 2017-10-24 | 南京理工大学 | A kind of solid propellant 3D printing forming method solidified based on ultraviolet light |
| CN109438149A (en) * | 2018-12-05 | 2019-03-08 | 湖北航天化学技术研究所 | A kind of thermosetting property composite solidpropellant and preparation method thereof |
| WO2020212785A1 (en) * | 2019-04-15 | 2020-10-22 | Politecnico Di Torino | Composite propellant manufacturing process based on deposition and light-activated polymerization for solid rocket motors |
-
2021
- 2021-03-10 CN CN202110261593.7A patent/CN115073245A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107283826A (en) * | 2017-06-28 | 2017-10-24 | 南京理工大学 | A kind of solid propellant 3D printing forming method solidified based on ultraviolet light |
| CN109438149A (en) * | 2018-12-05 | 2019-03-08 | 湖北航天化学技术研究所 | A kind of thermosetting property composite solidpropellant and preparation method thereof |
| WO2020212785A1 (en) * | 2019-04-15 | 2020-10-22 | Politecnico Di Torino | Composite propellant manufacturing process based on deposition and light-activated polymerization for solid rocket motors |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109438149B (en) | Thermosetting composite solid propellant and preparation method thereof | |
| CN107283826A (en) | A kind of solid propellant 3D printing forming method solidified based on ultraviolet light | |
| CN111559948B (en) | Formula of 3D printing solid propellant/heat insulating layer and integrated preparation method thereof | |
| CN113461427B (en) | Photocuring 4D printing ceramic-based precursor slurry, ceramic part and preparation method | |
| CN1191548A (en) | Application of polymer backing onto glass substrate | |
| CN113683473B (en) | Polyether-based composite solid propellant 3D printing ink and preparation method thereof | |
| US20220342305A1 (en) | Dual-cure phase-separation type photosensitive resin composition for continuous 3d printing with high precision | |
| CN104774312A (en) | Resin with mixing and solidification functions and synthetic method thereof | |
| CN105542628A (en) | 3D (three dimensional) print light-cured resin composition and preparation method thereof | |
| CN115073245A (en) | Rapid 3D printing and forming method for photo-thermal composite curing of butylated hydroxytoluene solid propellant | |
| CN110628194A (en) | Glass fiber reinforced plastic pultrusion section for cooling tower and preparation method thereof | |
| CN113548897A (en) | Ceramic 3D printing paste with high curing capacity and preparation method thereof | |
| CN112408993A (en) | Titanium dioxide photosensitive resin ceramic slurry and preparation method and application thereof | |
| US20030190472A1 (en) | Thermoplastic polymer filled pastes | |
| CN111808259B (en) | 3D printing silicone rubber and preparation method and application thereof | |
| WO1982000649A1 (en) | Methods and apparatus for producing foamed thermoplastics materials and articles | |
| CN113968738A (en) | Ceramic precursor slurry for additive manufacturing and additive manufacturing process | |
| CN111808525B (en) | Multiphase structure UV (ultraviolet) photocuring powder coating resin and preparation method thereof | |
| CN116063064A (en) | Photocuring additive manufacturing method of ceramic | |
| CN112094164B (en) | Photocuring propellant and preparation method thereof | |
| Seo et al. | Ceramic bodies without warping using epoxide–acrylate hybrid ceramic slurry for photopolymerization‐based 3D printing | |
| CN114014654A (en) | Photocuring additive manufacturing method of active filler reinforced precursor ceramic composite material | |
| CN108115928A (en) | A kind of manufacturing method of polymer three-dimensional product | |
| CN110885253A (en) | Laser scanning ceramic printing process | |
| WO2019204074A2 (en) | Additive manufacturing method and apparatus |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220920 |