CN103951971B - A kind of carbon fiber-reinforced resin dusty material for selective laser sintering - Google Patents
A kind of carbon fiber-reinforced resin dusty material for selective laser sintering Download PDFInfo
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Abstract
A kind of carbon fiber-reinforced resin dusty material for selective laser sintering, this dusty material includes toner, carbon fiber, antioxidant, flow promortor and dispersant, when this reinforcing material mass fraction is 100 parts, toner mass fraction is 48-88 part, carbon fiber mass fraction is 10-50 part, flow promortor mass fraction is 0.2-1 part, antioxidant mass fraction is 0.5-1.2 part, dispersant mass fraction is 0.2-0.6 part, each component is obtained the carbon fiber-reinforced resin dusty material for selective laser sintering according to the configuration of certain process sequence, the SLS profiled member of this material has a distinct increment in intensity and modulus compared to the SLS profiled member of base resin material, the mechanical property requirements that profiled member uses can be better met directly as end product.
Description
Technical field
The present invention relates to Material Field, be specifically related to a kind of carbon fiber-reinforced resin dusty material for selective laser sintering.
Background technology
At Selective Laser Sintering (SelectiveLaserSintering, it is called for short SLS) it is a kind of rapid shaping technique being widely used at present, its moulding process principle is: initially set up the electronic 3-D model of target part, then by delamination software, threedimensional model is carried out slicing treatment, obtain the data message of each processing aspect, under the control of the computer, according to slicing layer surface information, utilize laser beam to the dusty material of hot melt can successively scan sintering, be finally completed the processing and manufacturing of target part.The non-constant width of the applicable material ranges of SLS technology, including polymer, metal and pottery etc..
In selective laser sintering technique, dusty material is the key factor affecting part performance.Owing to polymeric material is compared with metal and ceramic material, there is the advantages such as forming temperature is low, sintering power is little, thus becoming the SLS material that application is maximum at present.Nylon-based resin material is a kind of semi-crystalline polymer, has good sintering character and relatively low melt viscosity, can, mechanical property good function part higher by SLS straight forming consistency, become one of SLS moulding material of being most widely used at present.But such strength of materials and rigidity are relatively low, some profiled member measuring mechanical property requirement or the performance requirement used directly as final products can not be met by SLS technology institute shaped article.
For meeting the mechanical property requirements that resin SLS product directly uses as end product, occur in that multiple Enhancement Method at present, as resin-based materials is strengthened by glass fibre, mineral fibres, but mechanical property and the surface topography problem due to glass fibre and mineral fibres itself, it is not especially desirable for making reinforced effects, it is impossible to well meet the application demand of some SLS profiled member.Carbon fiber has the features such as light weight, intensity is high, wear-resistant, and through carbon fiber reinforced resin material, its SLS profiled member has a distinct increment in intensity and modulus compared to the SLS profiled member of base resin material, improves the range of application of SLS profiled member.
Summary of the invention
The invention provides a kind of carbon fiber-reinforced resin dusty material for selective laser sintering, this material SLS profiled member has a distinct increment in intensity and modulus compared to the SLS profiled member of base resin material, can more meet the performance requirement that SLS profiled member directly uses as end product.
The present invention relates to a kind of carbon fiber-reinforced resin dusty material for selective laser sintering, this material includes toner, carbon fiber, antioxidant, flow promortor and dispersant.Wherein the mass percent of each component is: when this reinforcing material mass fraction is 100 parts, toner mass fraction is 48-88 part, carbon fiber mass fraction is 10-50 part, flow promortor mass fraction is 0.2-1 part, antioxidant mass fraction 0.2-1.2 part, dispersant mass fraction is 0.1-0.6 part.
For in the carbon fiber reinforced resin material of selective laser sintering, along with the raising strengthening phase component carbon fibers content, its profiled member intensity is substantially in rising trend, but during component carbon fibers too high levels, in profiled member, the contact surface between carbon fiber and carbon fiber will increase, and this contact is weak contact, can reduce profiled member intensity when running up to a certain amount of on the contrary, therefore, when component carbon fibers content is beyond a certain value, its profiled member intensity presents and does not rise the anti-phenomenon dropped.Flow promortor can improve the mobile performance of material, dispersant can make carbon fiber dispersion be more uniformly distributed, but in the SLS technical process using carbon dioxide laser as energy source, it is different from resin material absorption laser energy and realizes melting adhered process, flow promortor and dispersant all exist with solid forms in this process, and both therefore, constituent content is too high also can reduce molten state component adhesive effect.Antioxidant can prevent powder oxidized in SLS sintering process, but when antioxidant addition exceedes certain value, antioxidant effect will not strengthen along with increasing of addition again, and antioxidant can produce volatile matter in sintering process in addition, is unfavorable for maintenance and the maintenance of former.
Toner available in the present invention can be nylon 11, nylon 12, nylon 1212, nylon 6, nylon66 fiber, polypropylene one of which or several.In SLS technical process, powder diameter distribution influence spreads powder process and surface of shaped parts quality.When powder diameter is too small, the frictional force between powder body increases, and adhesion strength becomes big, and mobility is deteriorated, and is unfavorable for paving powder；When powder diameter is excessive, paving powder process can produce scratch, and surface of shaped parts is coarse.Experiments show that, powder diameter is distributed in 20-150 micron, it is preferable that particle size range 30-100 micron, in normal distribution and pattern is substantially spherically-shaped or the toner of elliposoidal has good mobility, is conducive to paving powder and sintering.
In the present invention, preferred carbon fiber diameter is 7-10 micron, and length is 201-350 micron.Usual carbon fiber is more long, and reinforced effects is more good, but carbon fiber itself has certain flexibility, and oversize being susceptible to of carbon fiber is reunited, and forms floccule, reduces adhesion strength.The too short then reinforced effects of carbon fiber draw ratio is inconspicuous, affects the elongation at break of profiled member on the contrary.
After the method for chemical oxidation or graft processes, average diameter is 7-10 micron, and the carbon fiber that distribution of lengths is 50-200 micron also meets enhancing demand.It is generally: at 50-80 DEG C carbon fiber is soaked 1-2 hour in the concentrated nitric acid solution that concentration is 60-70%, its surface is aoxidized the method for surface treatment of carbon fibers in this length range；Or use Silane coupling agent KH550 or KH560, in toluene solvant, it is carried out graft reaction.
In the present invention, the interpolation of flow promortor can increase the processing fluidity of dusty material, improving the surface smoothness of plastic product, flow promortor can be one or more in aerosil, gaseous oxidation aluminum, gas-phase silica, nano-titanium oxide, nano carborundum powder.
In the present invention, antioxidant is Hinered phenols antioxidant and phosphite ester kind antioxidant.Preferred antioxidant is obtained by mixing with irgasfos 168 3:1 in mass ratio by antioxidant 1010.
In the present invention, carbon fiber dispersant can be one or more in powdered graphite, ethylene group bis-stearamides (EBS), glycerol monostearate (GMS), glyceryl tristearate (HTG), barium stearate (BaSt) or microcrystalline wax.
A kind of carbon fiber-reinforced resin dusty material disclosed by the invention can obtain through following steps:
(1) according to design component ratio take each component material, wherein carbon fiber mass fraction 10-50 part, toner mass fraction 48-88 part, antioxidant mass fraction 0.5-1.2 part, flow promortor mass fraction 0.2-1.0 part, dispersant mass fraction 0.2-0.6 part；
(2) part toner being mixed to get draw powder with flow promortor, antioxidant and dispersant high-speed stirred, this whipping process contributes to being dispersed in resin material flow promortor, antioxidant and dispersant；
(3) carbon fiber is sieved with 80 mesh sieves, the part reunited in carbon fiber and impurity are screened out；
(4) put into stirring mixing in V-type agitating device by drawing powder, sieved carbon fiber and residual resin powder, stir 40-60 minute and can obtain target material.
Carbon fiber-reinforced resin dusty material SLS technological forming effect prepared by the present invention is better, profiled member is lightweight, intensity and modulus higher, can be widely applied to the direct manufacture of the test of structure function part in the fields such as machinery, electric, space flight and aviation, military project, transportation or terminal part.
Detailed description of the invention
Embodiment 1
Hereinafter, the embodiment of the present invention is described, but the present invention is not limited to this:
(1) going out each component according to data below precise: carbon fiber, 1Kg, its average diameter is 7 microns, length range 201-300 micron；Nylon 12 powder, 8.8Kg, its particle size range 20-100 micron；Aerosil, 100g；Dispersant powdered graphite, 20g；Antioxidant 1098,80g；
(2) with the high speed agitator of 2.5L, the aerosil of caking is smashed；
(3) mixing with the stirring of the aerosil smashed, antioxidant 1098 and powdered graphite with about 1Kg nylon 12 powder, obtain drawing powder, mixing point carries out for 3 times；
(4) carbon fiber is sieved with 80 mesh sieves, the part reunited in carbon fiber and impurity are screened out；
(5) drawing powder, sieved carbon fiber and residue nylon 12 powder and put into stirring mixing in V-type agitating device, mixing time is 40-60 minute；
(6) material being stirred in step (5) and target material.
Embodiment 2
(1) going out each component according to data below precise: carbon fiber, 2Kg, its average diameter is 7 microns, length range 201-300 micron；Nylon 12 powder, 7.8Kg, its particle size range 20-100 micron；Aerosil, 90g；Dispersant powdered graphite, 30g；Antioxidant 1098,80g；
(2) with the high speed agitator of 2.5L, the aerosil of caking is smashed；
(3) mixing with the stirring of the aerosil smashed, antioxidant 1098 and powdered graphite with about 1Kg nylon 12 powder, obtain drawing powder, mixing point carries out for 3 times；
(4) carbon fiber is sieved with 80 mesh sieves, the part reunited in carbon fiber and impurity are screened out；
(5) drawing powder, sieved carbon fiber and residue nylon 12 powder and put into stirring mixing in V-type agitating device, mixing time is 40-60 minute；
(6) material being stirred in step (5) and target material.
Embodiment 3
(1) going out each component according to data below precise: carbon fiber, 3Kg, its average diameter is 7 microns, length range 250-350 micron；Nylon 12 powder, 6.8Kg, its particle size range 25-120 micron；Gaseous oxidation aluminum, 80g；Dispersant EBS powder, 50g；Antioxidant 9228,70g；
(2) mixing with the stirring of gaseous oxidation aluminum, antioxidant 9228 and EBS powder with about 1Kg nylon 12 powder, obtain drawing powder, mixing point carries out for 3 times；
(3) carbon fiber is sieved with 80 mesh sieves, the part reunited in carbon fiber and impurity are screened out；
(4) drawing powder, sieved carbon fiber and residue nylon 12 powder and put into stirring mixing in V-type agitating device, mixing time is 40-60 minute；
(5) material being stirred in step (4) and target material.
Embodiment 4
(1) going out each component according to data below precise: carbon fiber, 3.5Kg, its average diameter is 7 microns, length range 201-350 micron；Nylon 1212 poweder, 6.3Kg, its particle size range 30-150 micron；Gas-phase silica, 90g；Dispersant barium stearate, 60g；Antioxidant 3026,50g；
(2) mixing with the stirring of gas-phase silica, antioxidant 3026 and barium stearate powder with about 1Kg nylon 1212 poweder, obtain drawing powder, mixing point carries out for 3 times；
(3) carbon fiber is sieved with 80 mesh sieves, the part reunited in carbon fiber and impurity are screened out；
(4) drawing powder, sieved carbon fiber and residue nylon 1212 poweder and put into stirring mixing in V-type agitating device, mixing time is 40-60 minute；
(5) material being stirred in step (4) and target material.
Embodiment 5
(1) going out each component according to data below precise: carbon fiber, 4.0Kg, its average diameter is 7 microns, length range 201-350 micron；Nylon 1212 poweder, 5.8Kg, its particle size range 30-150 micron；Gas-phase silica, 85g；Dispersant barium stearate, 55g；Antioxidant 3026,60g；
(2) mixing with the stirring of gas-phase silica, antioxidant 3026 and barium stearate powder with about 1Kg nylon 1212 poweder, obtain drawing powder, mixing point carries out for 3 times；
(3) carbon fiber is sieved with 80 mesh sieves, the part reunited in carbon fiber and impurity are screened out；
(4) drawing powder, sieved carbon fiber and residue nylon 1212 poweder and put into stirring mixing in V-type agitating device, mixing time is 40-60 minute；
(5) material being stirred in step (4) and target material.
Embodiment 6
(1) going out each component according to data below precise: carbon fiber, 4.5Kg, its average diameter is 7 microns, length range 201-300 micron；Nylon 1212 poweder, 5.3Kg, its particle size range 25-100 micron；Nano oxidized silica flour, 40g；Dispersant glyceryl tristearate, 50g；Antioxidant 1010,82.5g, irgasfos 168,27.5g；
(2) mixing with the stirring of nano oxidized silica flour, antioxidant 1010, irgasfos 168 and glyceryl tristearate powder with about 1Kg nylon 1212 poweder, obtain drawing powder, mixing point carries out for 3 times；
(3) carbon fiber is sieved with 80 mesh sieves, the part reunited in carbon fiber and impurity are screened out；
(4) drawing powder, sieved carbon fiber and residue nylon 1212 poweder and put into stirring mixing in V-type agitating device, mixing time is 40-60 minute；
(5) material being stirred in step (4) and target material.
Embodiment 7
(1) going out each component according to data below precise: carbon fiber, 5.0Kg, its average diameter is 7 microns, length range 201-300 micron；Nylon 1212 poweder, 4.8Kg, its particle size range 25-100 micron；Nano oxidized silica flour, 20g；Dispersant glyceryl tristearate, 60g；Antioxidant 1010,90g, irgasfos 168,30g；
(2) mixing with the stirring of nano oxidized silica flour, antioxidant 1010, irgasfos 168 and glyceryl tristearate powder with about 1Kg nylon 1212 poweder, obtain drawing powder, mixing point carries out for 3 times；
(3) carbon fiber is sieved with 80 mesh sieves, the part reunited in carbon fiber and impurity are screened out；
(4) drawing powder, sieved carbon fiber and residue nylon 1212 poweder and put into stirring mixing in V-type agitating device, mixing time is 40-60 minute；
(5) material being stirred in step (4) and target material.
Embodiment 8
(1) going out each component according to data below precise: carbon fiber, 2.5Kg, its average diameter is 7 microns, length range 50-200 micron；The concentration prepared is the concentrated nitric acid 500ml of 60%；Nylon 12 powder, 7.3Kg, its particle size range 25-120 micron；Gaseous oxidation aluminum, 90g；Dispersant EBS, 40g；Antioxidant 9228,70g；Separately need distilled water some, heating platform one, infrared radiation thermometer one, three, 1L beaker；
(2) concentrated nitric acid that 500ml concentration is 60% is loaded in 1L beaker, take 0.5Kg carbon fiber and put into beaker, beaker is placed on heating platform and heats, heating and temperature control is at 50-60 DEG C, use infrared radiation thermometer detection temperature, soak 1 hour, then take out to be placed on by carbon fiber and clean equipped with in the beaker of distilled water, repeatedly clean 5 times, finally carbon fiber is put in drying baker and dry.Repeat aforesaid operations 5 times, 2.5Kg carbon fiber is all carried out surface oxidation treatment；
(3) carbon fiber of all drying is sieved with 80 mesh sieves, the part reunited in carbon fiber and impurity are screened out；
(4) mixing with the stirring of gaseous oxidation aluminum, antioxidant 9228 and EBS powder with about 1Kg nylon 12 powder, obtain drawing powder, mixing point carries out for 3 times；
(5) drawing powder, sieved carbon fiber and residue nylon 12 powder and put into stirring mixing in V-type agitating device, mixing time is 40-60 minute；
(6) material being stirred in step (5) and target material.
Following table is nylon 12SLS profiled member, nylon 1212 SLS profiled member and the intensity of SLS profiled member after fibre reinforced and modulus versus:
Claims (5)
1. the carbon fiber-reinforced resin dusty material for selective laser sintering, it is characterized in that: this dusty material includes toner, carbon fiber, antioxidant, flow promortor and dispersant, when this reinforcing material mass fraction is 100 parts, toner mass fraction is 48-88 part, carbon fiber mass fraction is 10-50 part, flow promortor mass fraction is 0.2-1 part, and antioxidant mass fraction is 0.5-1.2 part, and dispersant mass fraction is 0.2-0.6 part；
The diameter of described carbon fiber is 7-10 micron, and length is 201-350 micron.
2. carbon fiber-reinforced resin dusty material according to claim 1, it is characterized in that described toner is nylon 11, nylon 12, nylon 1212, nylon 6, nylon66 fiber, polypropylene one of which or several, its particle size distribution range is 20-150 micron, in normal distribution, pattern is ganoid spherical or ellipsoidal particle.
3. carbon fiber-reinforced resin dusty material according to claim 1, it is characterised in that described flow promortor is one or more in aerosil, gaseous oxidation aluminum, nano-titanium oxide, nano carborundum powder.
4. carbon fiber-reinforced resin dusty material according to claim 1, it is characterised in that described antioxidant is Hinered phenols antioxidant and phosphite ester kind antioxidant.
5. carbon fiber-reinforced resin dusty material according to claim 1, it is characterised in that described dispersant is one or more in powdered graphite, ethylene group bis-stearamides, glycerol monostearate, glyceryl tristearate, barium stearate, microcrystalline wax.
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