A kind of nylon composite powder material for selective laser sintering
Technical field
The present invention relates to a kind of polymer composite, particularly relate to a kind of nylon composite powder material for selective laser sintering.
Background technology
At selective laser sintering (SelectiveLaserSintering, be called for short SLS) in technique, powdered material is the key factor affecting part performance, current macromolecule nylon powdered material is that SLS manufactures the most widely used starting material in field, its product density is high, mechanical property good, can be widely used in the fields such as Aerospace Engineering, defence and military product, building engineering model, machinofacture, artwork making.But simple nylon powder material has certain limitation in performance, and price comparison is expensive.Industrial conventional glass fibre carries out enhancing modified to macromolecular material, as patent CN101348609 carries out modification by adding the components such as glass fibre to nylon powder material, improve the flexural strength of nylon composite materials moulding, modulus in flexure and resistance to elevated temperatures etc., but research only relates to nylon composite materials moulding, and the nylon composite materials adding glass fibre spreads mealiness energy and SLS processability is all very bad, is not suitable for SLS technique.Patent CN1379061 carries out modification by adding the fillers such as talcum powder, glass sphere, nano silicon, polystyrene to SLS nylon powder material, its SLS product is made to have good processability, intensity and toughness, but its filling kind used is many, and technique is comparatively complicated, and cost is high.Glass microballon is a kind of silicates material, it has the advantages such as high compression-strength, stable chemical performance, lower thermal conductivity and Thermal Contraction Coefficient, its spherical surface is smooth, filling capacity is high, good fluidity, has excellent processing characteristics using it as the matrix material of filler; The stress concentration of glass microballon spheroidal particle is little, glass microballon particulate is filled in material and can causes a large amount of tiny crazing and not cause destructive crackle, spherical surface is more conducive to by suffered external force Transmit evenly to surrounding matrix simultaneously, thus improves the mechanical property of matrix material.Glass microballon is good as polymer modification agent performance, price is low, there is higher using value, as patent CN101597425 with the addition of solid glass micro-bead in polycarbonate powder material, improve the processability of material, improve the rigidity of its SLS product, physical strength, wear resistance, dimensional stability etc.; Patent CN101724258, while employing glass fibre carries out enhancing modified to nylon, adds hollow glass micropearl as filler, reduces the warpage degree of material, improves moulding outward appearance, achieve good effect.But above-mentioned research does not all relate to the report about the glass microballon modified nylon materials based on SLS technology, the prior art drawbacks limit application development of SLS technology.
Summary of the invention
The object of the present invention is to provide a kind of nylon composite powder material for selective laser sintering, this nylon composite powder material has excellent SLS processability, its SLS product mechanical property is good, rigidity is high, good stability of the dimension, material preparation process is simple, environment friendly and pollution-free simultaneously, and SLS product cost is significantly reduced.
A kind of nylon composite powder material for selective laser sintering provided by the invention is composed of the following components: nylon resin powder, solid glass micro-bead, coupling agent, light absorber, flow promotor, oxidation inhibitor; Each component is by following portions by weight proportioning:
Nylon resin 35-65
Solid glass micro-bead 35-65
Coupling agent 0.2-2
Flow promotor 0.1-1
Light absorber 0.1-1
Oxidation inhibitor 0.5-1
Above-mentioned nylon resin is selected from PA6, one or several in PA66, PA1010, PA11, PA12.
Above-mentioned solid glass micro-bead particle diameter is 20 ~ 50 μm.
Above-mentioned coupling agent is silane coupling agent, is preferably one or more in γ-aminopropyl triethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane.
Above-mentioned flow promotor is one or more in nano carborundum powder, nano silicon, nano aluminium oxide and nano-titanium oxide.
Above-mentioned light absorber is one or more in benzophenone class, benzotriazole category, group-substituted acrylonitrile, triazines and hindered amines light absorber; Wherein benzophenone class light absorber is preferably 2,4-dihydroxy benaophenonel, ESCALOL 567, benzotriazole category light absorber be preferably 2-(2 '-hydroxyl-3 ', 5 '-two tertiary phenyl)-5-chlorination benzotriazole etc., triazines light absorber is preferably 2,4,6-tri-(2 '-n-butoxyphenyl)-1,3,5-triazine, hindered amines is preferably two (2,2,6,6-tetramethyl--4-piperidyl (sebate, two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate.
Above-mentioned antioxidant is the composite antioxidant of Hinered phenols antioxidant and phosphite ester kind antioxidant composition, wherein Hinered phenols antioxidant is preferably 1, 3, 5-trimethylammonium-2, 4, 6-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl) benzene, 2, 6-di-t-butyl-4-methyl-phenol, N, N '-two (3, 5-di-tert-butyl-hydroxy phenyl propionic acid amide), 2, 2 '-bis-(4-methyl-6-tert butyl-phenol) methane, 2, one or more in 2 '-bis-(4-ethyl-6-t-butyl-phenol) methane, its consumption is the 60-80% of composite antioxidant gross weight, wherein phosphite ester kind antioxidant is preferably 2,2 '-ethylenebis (4,6-di-tert-butyl-phenyl) fluorophosphite, four (2,4-di-tert-butyl-phenyl)-4, one or more in 4 '-xenyl bis-phosphite, its consumption is the 20-40% of composite antioxidant gross weight.
Described a kind of nylon composite powder material for selective laser sintering is prepared by the following method according to said components and proportioning:
First coupling agent is dissolved in the solution that ethanol/water the solvent mixture is mixed with mass concentration 3%, then adds solid glass micro-bead and be mixed evenly, dry, ball milling, crosses 250 mesh sieves, obtains the solid glass micro-bead of surface organic process; Get appropriate above-mentioned glass microballon to add in mechanical stirrer, then add nylon resin powder, flow promotor, light absorber, oxidation inhibitor in agitator, stir, cross 150 mesh sieves, obtain required nylon composite powder material.
Gained nylon composite powder material is used for SLS molding device shaping, gained profiled member carries out performance test by ASTM standard.
In aforesaid operations used reinforced, stir, dry, sieve and method that SLS forming method is known to the skilled person.Those skilled in the art are according to content disclosed by the invention, and the technique means adopting other alternative to realize the object of the invention all belongs to the scope of the invention.
Nylon composite powder material provided by the invention has excellent mechanical property and SLS molding effect, gained SLS profiled member good stability of the dimension, its tensile strength and flexural strength rise all to some extent, especially modulus in flexure improves 60 ~ 70%, material cost reduces by more than 30% simultaneously, material preparation process is simple, environment friendly and pollution-free, is a kind of high-performance, low cost, free of contamination novel nylon composite powder material of being applicable to SLS, effectively facilitates the application development of SLS technology in each field.
Embodiment
Embodiment 1
Get 300 grams of γ-aminopropyl triethoxysilanes, be dissolved in 9700 grams of ethanol/waters (mass ratio 95: 2) the solvent mixture, obtain the solution of mass concentration 2%; Get solid glass micro-bead 4000 grams, add in above-mentioned solution, be mixed evenly, at room temperature dry 2 days, then at 65 DEG C dry 2 hours, ball milling, crosses 250 mesh sieves, obtains the solid glass micro-bead of surface organic process;
Get above-mentioned glass microballon 1750 grams to add in mechanical stirrer, then in agitator, add nylon 12 powder 3250 grams, flow promotor 40 grams, light absorber 40 grams, 40 grams, oxidation inhibitor, stir, cross 150 mesh sieves, obtain nylon composite powder material.
Shaping above-mentioned gained nylon composite powder material on SLS equipment, preparation technology parameter is: laser power 12W, sweep velocity 2000mm/s, sintering spacing 0.1mm, sintered layer thickness 0.1mm, preheating temperature 170 DEG C; Gained SLS profiled member is carried out performance test by ASTM standard, the results are shown in Table 1.
Embodiment 2
Get 300 grams of γ-aminopropyl triethoxysilanes, be dissolved in 9700 grams of ethanol/waters (mass ratio 95: 2) the solvent mixture, obtain the solution of mass concentration 3%; Get solid glass micro-bead 4000 grams, add in above-mentioned solution, be mixed evenly, at room temperature dry 2 days, then at 65 DEG C dry 2 hours, ball milling, crosses 250 mesh sieves, obtains the solid glass micro-bead of surface organic process;
Get above-mentioned glass microballon 2250 grams to add in mechanical stirrer, then in agitator, add nylon 12 powder 2750 grams, flow promotor 45 grams, light absorber 45 grams, 45 grams, oxidation inhibitor, stir, cross 150 mesh sieves, obtain nylon composite powder material.
Shaping above-mentioned gained nylon composite powder material on SLS equipment, preparation technology parameter is: laser power 12W, sweep velocity 2000mm/s, sintering spacing 0.1mm, sintered layer thickness 0.1mm, preheating temperature 170 DEG C; Gained SLS profiled member is carried out performance test by ASTM standard, the results are shown in Table 1.
Embodiment 3
Get 300 grams of γ-aminopropyl triethoxysilanes, be dissolved in 9700 grams of ethanol/waters (mass ratio 95: 2) the solvent mixture, obtain the solution of mass concentration 3%; Get solid glass micro-bead 4000 grams, add in above-mentioned solution, be mixed evenly, at room temperature dry 2 days, then at 65 DEG C dry 2 hours, ball milling, crosses 250 mesh sieves, obtains the solid glass micro-bead of surface organic process;
Get above-mentioned glass microballon 2750 grams to add in mechanical stirrer, then in agitator, add nylon 12 powder 2250 grams, flow promotor 45 grams, light absorber 45 grams, 45 grams, oxidation inhibitor, stir, cross 150 mesh sieves, obtain nylon composite powder material.
Shaping above-mentioned gained nylon composite powder material on SLS equipment, preparation technology parameter is: laser power 12W, sweep velocity 2000mm/s, sintering spacing 0.1mm, sintered layer thickness 0.1mm, preheating temperature 170 DEG C; Gained SLS profiled member is carried out performance test by ASTM standard, the results are shown in Table 1.
Comparative example
Feedstock nylon 12 powder is directly shaping on SLS equipment, and preparation technology parameter is: laser power 12W, sweep velocity 2000mm/s, sintering spacing 0.1mm, sintered layer thickness 0.1mm, preheating temperature 170 DEG C; Gained SLS profiled member is carried out performance test by ASTM standard, the results are shown in Table 1.
The performance test of table 1SLS profiled member