CN104448805A - High-strength nylon-based composite material for 3D printing and preparation method of high-strength nylon-based composite material for 3D printing - Google Patents
High-strength nylon-based composite material for 3D printing and preparation method of high-strength nylon-based composite material for 3D printing Download PDFInfo
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- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
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Abstract
The invention provides a high-strength nylon-based composite material for 3D printing. The high-strength nylon-based composite material for 3D printing is prepared from the following raw materials in parts by weight: 60-95 parts of nylon resin, 5-40 parts of alkali-free glass fibers, 0.2-1 part of an antioxidant, 0.3-2 parts of a coupling agent and 0.2-1 part of a nucleating agent. The glass fibers have very high modulus and strength which are further higher than those of the nylon resin matrix; the glass fibers and the nylon resin interface are combined very well, and the force borne on the material can be conducted to the glass fibers, so that the mechanical strength of the composite material is improved. Moreover, the raw materials interact with one another, so that the strength and the modulus of the composite material are also improved.
Description
Technical field
The invention belongs to 3D printing technique field, be specifically related to a kind of high-strength nylon based composites for 3D printing and preparation method thereof.
Background technology
It is the popular appellation increasing material manufacturing technology that 3D prints, and is superposed by continuous print physical layer, successively increases the technology that 3D solid produced by material.Different from traditional removal materials processing technology, 3D printing technique is without the need to proembryo and mould, just can directly according to computer graphics data, the object of any shape is produced by the method increasing material, effectively can simplify the manufacturing course of product, shorten the lead time of product, raise the efficiency and reduce costs.3D printing technique is the field such as widespread use and product prototype, Making mold, artistic creation, jewelry-making, biotechnology and medicine, building, clothes.Fused glass pellet (FDM) is a kind of 3D printing type common in the market, and the innovation and development of its machine is very fast, but its consumptive material development that can use is limited.
The consumptive material for 3D printing common in the market has poly(lactic acid) (PLA), acrylonitrile-butadiene-styrene copolymer (ABS) and polyvinyl alcohol (PVA) etc.But the mechanical property of PLA is poor, and non-refractory; ABS print procedure has peculiar smell, and mechanical property is general, also non-refractory; PVA is commonly used to as a kind of propping material, but non-refractory.Therefore, the shortcoming that above-mentioned consumptive material also exists limits their range of application.
Nylon (PA) be develop the earliest, most widely used thermoplastic engineering plastic, there is the performance that high-strength, high temperature resistant, wear-resisting, shock-resistant, corrosion-resistant, antifatigue, oil resistant, self-lubricating etc. are excellent, being widely used in the fields such as trolley part, electronic apparatus, petrochemical complex, aerospace, is the macromolecular material that in five large-engineering plastics, output is maximum, purposes is the widest, kind is maximum.The mechanical property of pure PA is better, but the tensile strength (injection moulding) of pure PA is the highest at about 60MPa simultaneously, and tensile strength shaping reluctantly after being printed by 3D only has about 20MPa, can not meet the actual needs that 3D prints.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of high-strength nylon based composites for 3D printing and preparation method thereof, and the high-strength nylon based composites that 3D provided by the present invention prints has higher mechanical strength and modulus.
The invention provides a kind of high-strength nylon based composites printed for 3D, comprise the raw material of following weight part:
The nylon resin of 60 ~ 95 weight parts;
The alkali free glass fibre of 5 ~ 40 weight parts;
The oxidation inhibitor of 0.2 ~ 1 weight part;
The coupling agent of 0.3 ~ 2 weight part;
The nucleator of 0.2 ~ 1 weight part.
Preferably, described nylon resin to be selected from PA6, PA66, PA11, PA12 and PA1010 one or more.
Preferably, described alkali free glass fibre is that alkali-free short glass fiber and/or alkali-free length cut glass fibre.
Preferably, described oxidation inhibitor is selected from 3,5-di-t-butyl-4-hydroxybenzene propionyl-hexanediamine (oxidation inhibitor 1098), tricresyl phosphite (2,4-di-tert-butyl phenolic ester) (irgasfos 168), four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), copper halide, potassiumiodide, 1,3,5-trimethylammonium-2, one or more in 4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene, 2 '-bis-(4-methyl-6-tert butyl-phenol) methane.
Preferably, described coupling agent is silane coupling agent.
Preferably, described nucleator is selected from one or more in talcum powder, nano silicon, nano aluminium oxide, adipamide dimer, organic hypophosphite, nano calcium oxide.
Present invention also offers a kind of preparation method of the high-strength nylon based composites for 3D printing, comprise the following steps:
Nylon resin, alkali free glass fibre, oxidation inhibitor, coupling agent and nucleator mix and blend are obtained mixture; By described mixture successively through melt extruding the flame-proof composite material obtaining with wire-drawing shape printing for 3D.
Preferably, before described mix and blend, also comprise nylon resin dry.
Preferably, the rotating speed of described mix and blend is 1000 ~ 2000r/min, and the mix and blend time is 3 ~ 10min.
Preferably, the 6 sections of temperature melt extruded described in are respectively 160 ~ 240 DEG C, 180 ~ 250 DEG C, 190 ~ 270 DEG C, 200 ~ 275 DEG C, 220 ~ 280 DEG C, 230 ~ 280 DEG C.
Compared with prior art, the invention provides a kind of high-strength nylon based composites printed for 3D, comprise the raw material of following weight part: the nylon resin of 60 ~ 95 weight parts; The alkali free glass fibre of 5 ~ 40 weight parts; The oxidation inhibitor of 0.2 ~ 1 weight part; The coupling agent of 0.3 ~ 2 weight part and the nucleator of 0.2 ~ 1 weight part.Glass fibre of the present invention has very high modulus and intensity, and far above nylon resin matrix, glass fibre and nylon resin interface good combination, the power suffered by material can be transmitted on glass fibre, improves the mechanical strength of matrix material.Further, the interaction between raw material, also improves intensity and the modulus of matrix material.
Result shows, the tensile strength >=84.5MPa of high-strength nylon based composites provided by the present invention, Young's modulus >=1862.2MPa, flexural strength >=117.6MPa, modulus in flexure >=3265.5MPa, shock strength is 47.1 ~ 79.8J/m, and fracture rate elongation is 5.3 ~ 30.9%.
Embodiment
The invention provides a kind of high-strength nylon based composites printed for 3D, comprise the raw material of following weight part:
The nylon resin of 60 ~ 95 weight parts;
The alkali free glass fibre of 5 ~ 40 weight parts;
The oxidation inhibitor of 0.2 ~ 1 weight part;
The coupling agent of 0.3 ~ 2 weight part;
The nucleator of 0.2 ~ 1 weight part.
Matrix material provided by the invention comprises nylon resin, and nylon is the one in engineering plastics, and have the characteristics such as intensity is high, wear-resisting, self-lubricating, its mechanical property is apparently higher than the mechanical property of ABS and PLA printed for 3D.Described nylon resin to be selected from PA6, PA66, PA11, PA12 and PA1010 one or more.In described matrix material, the content of nylon resin is 60 ~ 95 weight parts, is preferably 75 ~ 90 weight parts, is more preferably 80 ~ 85 weight parts.
In the present invention, described matrix material also comprises alkali free glass fibre, and described alkali free glass fibre is a kind of borosilicate fiberglass, and be also E glass fibre, wherein alkali metal oxide content is less than 0.5%.Glass fibre has very high modulus and intensity, far above resin matrix.Due to glass fibre and resin boundary surface good combination, the power suffered by material can be transmitted on glass fibre, plays the object of resin tooth, makes the mechanical strength of matrix material be better than virgin resin material.Further, glass fibre add water-absorbent and the dimensional stability that significantly can improve nylon.Filament diameter 10 ~ the 20um of described alkali free glass fibre, described alkali free glass fibre is selected from alkali-free short glass fiber and/or alkali-free length cuts glass fibre.In described matrix material, the content of described alkali free glass fibre is 5 ~ 40 weight parts, is preferably 10 ~ 35 weight parts, is more preferably 15 ~ 30 weight parts.
Described matrix material also comprises oxidation inhibitor, described oxidation inhibitor is selected from 3,5-di-t-butyl-4-hydroxybenzene propionyl-hexanediamine (oxidation inhibitor 1098), tricresyl phosphite (2,4-di-tert-butyl phenolic ester) (irgasfos 168), four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), copper halide, potassiumiodide, 1,3,5-trimethylammonium-2,4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene, one or more in 2 '-bis-(4-methyl-6-tert butyl-phenol) methane.Wherein, the content of oxidation inhibitor is 0.2 ~ 1 weight part, is preferably 0.4 ~ 0.8 weight part, is more preferably 0.5 ~ 0.7 weight part.
Matrix material provided by the invention also comprises coupling agent, coupling agent effect be in the composite it can with the radical reaction of fiberglass surfacing, can react with matrix resin again, an interfacial layer is formed between glass fibre and resin matrix, interfacial layer can transmit stress, thus enhance bond strength between glass fibre and resin, improve the mechanical property of matrix material.In the present invention, the preferred silane coupling agent of described coupling agent, being more preferably model is one or more in the silane coupling agent of KH550, KH560, KH570, KH792, DL602 and DL171.The addition of described coupling agent is 0.3 ~ 2 weight part, is preferably 0.5 ~ 1.5 weight part, is more preferably 0.7 ~ 1.2 weight part.
Matrix material provided by the invention also comprises nucleator, nucleator add the crystallization that can promote nylon resin, physical strength and the dimensional stability of goods can be improved, the shrinking percentage of moulded products can be reduced, ensure that 3D prints goods mechanical strength and dimensional stability, improve the precision of goods.Nucleator of the present invention is selected from one or more in talcum powder, nano silicon, nano aluminium oxide, adipamide dimer, organic hypophosphite, nano calcium oxide.The addition of described nucleator is 0.2 ~ 1 weight part, is preferably 0.4 ~ 0.8 weight part.
Present invention also offers a kind of preparation method of the high-strength nylon based composites for 3D printing, comprise the following steps:
Nylon resin, alkali free glass fibre, oxidation inhibitor, coupling agent and nucleator mix and blend are obtained mixture; By described mixture successively through melt extruding the flame-proof composite material obtaining with wire-drawing shape printing for 3D.
First the raw material preparing matrix material is carried out mix and blend by the present invention, and before mix and blend, also comprise and nylon resin is carried out drying, concrete grammar is:
Nylon resin is placed in loft drier and carries out drying, wherein, drying temperature is 105 ~ 120 DEG C, time of drying 3 ~ 10h.
Dried nylon resin and alkali free glass fibre, oxidation inhibitor, coupling agent and nucleator mix and blend are obtained mixture.Wherein, mix and blend carries out in high-speed mixer, and the rotating speed of described mix and blend is 1000 ~ 2000r/min, and be preferably 1200 ~ 1800r/min, the time of described mix and blend is 3 ~ 10min.
After mixing terminates, described mixture is melt extruded.In the present invention, preferably adopt screw extrusion press to melt extrude, 6 sections of temperature of described screw extrusion press are for being respectively 160 ~ 240 DEG C, 180 ~ 250 DEG C, 190 ~ 270 DEG C, 200 ~ 275 DEG C, 220 ~ 280 DEG C, 230 ~ 280 DEG C.The engine speed of screw extrusion press is 50 ~ 100r/min.
The mixture melt extruded is carried out wire-drawing shape, and obtain the Reinforced Nylon matrix material printed for 3D, wherein, the string diameter of the matrix material of wire-drawing shape has 1.75mm and 3mm two kinds of specifications, and the precision of matrix material is ± 0.03mm, and circularity is ± 0.03mm.
In the present invention, also consumptive material can be prepared into particulate state or Powdered.Concrete, the preparation method of particulate state consumptive material is: the consumptive material after wire drawing is introduced dicing machine, carries out granulation, and granular size is determined, generally between 0.5mm ~ 5mm by the silk material diameter and granulate equipment extruding wire drawing.
The preparation method of powder material is: the consumptive material after particulate state consumptive material or wire drawing is carried out chilling fragmentation or dissolution with solvents precipitation, the diameter of powder material is at 10 ~ 100 microns.
Alkali free glass fibre is with the addition of in high-strength nylon based composites for 3D printing provided by the present invention, described glass fibre has very high modulus and intensity, far above nylon resin matrix, glass fibre and nylon resin interface good combination, power suffered by material can be transmitted on glass fibre, improves the mechanical strength of matrix material.Further, the interaction between raw material, also improves intensity and the modulus of matrix material.
The described high-strength nylon based composites for 3D printing has excellent physical strength, excellent dimensional stability, the alternative metallic substance for structure unit, be mainly used in machine structural parts, such as gear, bearing, fan blade, pump leaf, bicycle part, automotive industry spare and accessory parts, fishing gear and some precision engineering goods.
Result shows, the tensile strength >=84.5MPa of high-strength nylon based composites provided by the present invention, Young's modulus >=1862.2MPa, flexural strength >=117.6MPa, modulus in flexure >=3265.5MPa, shock strength is 47.1 ~ 79.8J/m, and fracture rate elongation is 5.3 ~ 30.9%.
In order to understand the present invention further, be described high-strength nylon based composites for 3D printing provided by the invention and preparation method thereof below in conjunction with embodiment, protection scope of the present invention is not limited by the following examples.
Embodiment 1
Take Nylon 6 2000g, short glass fiber 400g, four [β-(3 respectively, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and three [2.4-di-tert-butyl-phenyl] phosphorous acid ester 7.2g, coupling agent (KH-550) 9.6g, nano silicon 12g, put into high-speed mixer mixing 5min.Then extrude with screw extrusion press, shaping via wire-drawing shape equipment.The 6 sections of temperature melt extruded are respectively 200 DEG C, 220 DEG C, 225 DEG C, 232 DEG C, 237 DEG C, 240 DEG C, and screw speed is 80 revs/min.Be coiled into the consumptive material of volume through vacuum-drying, sealing is preserved.
Measure the mechanical strength of the high-strength nylon based composites for 3D printing obtained, the results are shown in Table 1, the performance of the high-strength nylon based composites for 3D printing that table 1 provides for embodiment 1 ~ 3 and comparative example 1.
Embodiment 2
Take Nylon 6 2000g respectively, length cuts glass fibre 600g, 3,5-di-t-butyl-4-hydroxybenzene propionyl-hexanediamine 7.8g, coupling agent (KH-560) 12g, nano aluminium oxide 13g, put into high-speed mixer mixing 5min.Then extrude with screw extrusion press, shaping via wire-drawing shape equipment.The 6 sections of temperature melt extruded are respectively 200 DEG C, 220 DEG C, 225 DEG C, 232 DEG C, 237 DEG C, 240 DEG C, and screw speed is 80 revs/min.Be coiled into the consumptive material of volume through vacuum-drying, sealing is preserved.
Measure the high-strength nylon based mechanical strength of the matrix material for 3D printing obtained, the results are shown in Table 1, the performance of the high-strength nylon based composites for 3D printing that table 1 provides for embodiment 1 ~ 3 and comparative example 1.
Embodiment 3
Take Nylon 66 2000g respectively, length cuts glass fibre 800g, 3,5-di-t-butyl-4-hydroxybenzene propionyl-hexanediamine and three [2.4-di-tert-butyl-phenyl] phosphorous acid ester 8.4g, coupling agent (KH-570) 11.2g, nano silicon 7g and nano calcium oxide 7g, put into high-speed mixer mixing 5min.Then extrude with screw extrusion press, shaping via wire-drawing shape equipment.The 6 sections of temperature melt extruded are respectively 210 DEG C, 250 DEG C, 265 DEG C, 270 DEG C, 275 DEG C, 270 DEG C, and screw speed is 100 revs/min.Be coiled into the consumptive material of volume through vacuum-drying, sealing is preserved.
Measure the high-strength nylon based mechanical strength of the matrix material for 3D printing obtained, the results are shown in Table 1, the performance of the high-strength nylon based composites for 3D printing that table 1 provides for embodiment 1 ~ 3 and comparative example 1.
Comparative example 1
Measure the mechanical strength of the Nylon-12 of Stratasys company, the results are shown in Table 1, the performance of the high-strength nylon based composites for 3D printing that table 1 provides for embodiment 1 ~ 3 and comparative example 1.
The performance of the high-strength nylon based composites for 3D printing that table 1 embodiment 1 ~ 3 and comparative example 1 provide
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1., for the high-strength nylon based composites that 3D prints, it is characterized in that, comprise the raw material of following weight part:
The nylon resin of 60 ~ 95 weight parts;
The alkali free glass fibre of 5 ~ 40 weight parts;
The oxidation inhibitor of 0.2 ~ 1 weight part;
The coupling agent of 0.3 ~ 2 weight part;
The nucleator of 0.2 ~ 1 weight part.
2. matrix material according to claim 1, is characterized in that, described nylon resin to be selected from PA6, PA66, PA11, PA12 and PA1010 one or more.
3. matrix material according to claim 1, is characterized in that, described alkali free glass fibre is that alkali-free short glass fiber and/or alkali-free length cut glass fibre.
4. matrix material according to claim 1, it is characterized in that, described oxidation inhibitor is selected from 3, 5-di-t-butyl-4-hydroxybenzene propionyl-hexanediamine (oxidation inhibitor 1098), tricresyl phosphite (2, 4-di-tert-butyl phenolic ester) (irgasfos 168), four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), copper halide, potassiumiodide, 1, 3, 5-trimethylammonium-2, 4, 6-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl) benzene, one or more in 2 '-bis-(4-methyl-6-tert butyl-phenol) methane.
5. matrix material according to claim 1, is characterized in that, described coupling agent is silane coupling agent.
6. matrix material according to claim 1, is characterized in that, described nucleator is selected from one or more in talcum powder, nano silicon, nano aluminium oxide, adipamide dimer, organic hypophosphite, nano calcium oxide.
7., for a preparation method for the high-strength nylon based composites of 3D printing, it is characterized in that, comprise the following steps:
Nylon resin, alkali free glass fibre, oxidation inhibitor, coupling agent and nucleator mix and blend are obtained mixture; By described mixture successively through melt extruding the flame-proof composite material obtaining with wire-drawing shape printing for 3D.
8. preparation method according to claim 7, is characterized in that, before described mix and blend, also comprises nylon resin dry.
9. preparation method according to claim 7, is characterized in that, the rotating speed of described mix and blend is 1000 ~ 2000r/min, and the mix and blend time is 3 ~ 10min.
10. preparation method according to claim 7, is characterized in that, described in 6 sections of temperature melt extruding be respectively 160 ~ 240 DEG C, 180 ~ 250 DEG C, 190 ~ 270 DEG C, 200 ~ 275 DEG C, 220 ~ 280 DEG C, 230 ~ 280 DEG C.
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