CN115449180A - Fiber-reinforced ABS material for additive manufacturing and preparation method thereof - Google Patents
Fiber-reinforced ABS material for additive manufacturing and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 68
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 51
- 239000000654 additive Substances 0.000 title claims abstract description 50
- 230000000996 additive effect Effects 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000003365 glass fiber Substances 0.000 claims abstract description 56
- 239000000835 fiber Substances 0.000 claims abstract description 53
- 229920005989 resin Polymers 0.000 claims abstract description 45
- 239000011347 resin Substances 0.000 claims abstract description 45
- 239000007822 coupling agent Substances 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 30
- 239000003822 epoxy resin Substances 0.000 claims abstract description 22
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 22
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 21
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- 238000001125 extrusion Methods 0.000 claims description 15
- 239000011521 glass Substances 0.000 claims description 14
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000011145 styrene acrylonitrile resin Substances 0.000 claims description 4
- 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 claims description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 abstract description 79
- 238000005452 bending Methods 0.000 abstract description 7
- 238000009776 industrial production Methods 0.000 abstract 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 abstract 1
- 229920000638 styrene acrylonitrile Polymers 0.000 abstract 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 78
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2355/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2323/00 - C08J2353/00
- C08J2355/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
- C08J2425/04—Homopolymers or copolymers of styrene
- C08J2425/08—Copolymers of styrene
- C08J2425/12—Copolymers of styrene with unsaturated nitriles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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Abstract
The invention discloses a fiber-reinforced ABS material for additive manufacturing and a preparation method thereof, and belongs to the technical field of additive manufacturing. The fiber-reinforced ABS material for additive manufacturing comprises the following components in parts by mass: 50-90 parts of ABS particles, 1-30 parts of glass fibers, 5-30 parts of SAN resin (styrene acrylonitrile copolymer), 1-10 parts of epoxy resin, less than or equal to 1 part of coupling agent, 0.1-3 parts of antioxidant and 0.5-5 parts of compatilizer; the bending resistance of the obtained fiber reinforced ABS material for additive manufacturing is obviously improved, when the fiber reinforced ABS material prepared by the invention is used for additive manufacturing, the anisotropy of an obtained printed product is obviously reduced, the cost of raw materials adopted by the preparation method is low, the operation is simple, the industrial production can be realized, and the application prospect is wide.
Description
Technical Field
The invention belongs to the technical field of additive manufacturing, and particularly relates to a fiber-reinforced ABS material for additive manufacturing and a preparation method thereof.
Background
When an acrylonitrile-butadiene-styrene (ABS) material is applied to an FDM process, due to the fact that the ABS material is poor in toughness and flowability, uneven shrinkage in the forming process and poor in bending resistance after the material is cooled and formed, warping, cracking and the like exist, the existing FDM modified material technology is mainly focused on wires for FDM equipment of a desktop machine, the desktop machine is small in space and convenient to control the environmental process, requirements for the material are low, and the bending resistance of the modified material is poor.
And the mechanical properties of the whole printed product are anisotropic due to the process characteristic limitation of FDM, especially the bending property (the mechanical properties are influenced by the printing direction, the mechanical properties are the best along the printing direction, the mechanical properties are the worst along the printing direction, and the bending property difference is generally more than 15%), thereby limiting the application of the FDM in the industrial field.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a fiber-reinforced ABS material for additive manufacturing and a preparation method thereof, which are used for solving the technical problems of poor flowability, easy material breakage, large warping deformation of a printed product, cracking and serious anisotropy of mechanical properties of the ABS material adopted in the conventional FDM printing process.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a fiber reinforced ABS material for additive manufacturing, which comprises the following raw materials in parts by mass: 50-90 parts of ABS particles, 1-30 parts of glass fibers, 5-30 parts of SAN resin, 1-10 parts of epoxy resin, no more than 1 part of coupling agent, 0.1-3 parts of antioxidant and 0.5-5 parts of compatilizer;
wherein the epoxy resin is one or more of E51, E44, E20 and E12.
Further, the coupling agent is a silane coupling agent or a titanate coupling agent; the antioxidant is one or more of antioxidant 1010, antioxidant 168 and antioxidant 264; the glass fiber is glass fiber T439, continuous glass ECT10L-4800 and glass fiber T442.
Further, the compatilizer is one or more of ABS-g-MAH, MBS, SMA and compatilizer 58816.
The invention also discloses a preparation method of the fiber reinforced ABS material for additive manufacturing, and when the glass fiber is continuous glass ECT10L-4800, the preparation method comprises the following steps:
s1: extruding ABS particles and glass fibers by using an extruder, cooling, and granulating to obtain a fiber master batch;
s2: uniformly mixing ABS particles, fiber master batch, SAN resin, epoxy resin, a coupling agent, an antioxidant and a compatilizer to obtain ABS mixed resin;
s3: extruding the ABS mixed resin by using an extruder, cooling, and granulating to obtain a fiber reinforced ABS material for additive manufacturing;
when the glass fiber is the glass fiber T439 or the glass fiber T442, the method comprises the following steps:
s11: uniformly mixing ABS particles, glass fibers, SAN resin, epoxy resin, a coupling agent, an antioxidant and a compatilizer to obtain ABS mixed resin;
s22: and extruding the ABS mixed resin by using an extruder, cooling, and granulating to obtain the fiber reinforced ABS material for additive manufacturing.
Further, the extruder is a double-screw double extruder, and the cooling treatment mode is water cooling and air cooling.
Further, the extruder is provided with a 10-section conveying section, and when the glass fiber is continuous glass ECT10L-4800, in S1, the glass fiber is added in a 5 th conveying section.
Further, when the glass fiber is continuous glass ECT10L-4800, the temperature during extrusion is 160-230 ℃ in S1, and the rotating speed is 50-150 r/min.
Further, when the glass fiber is continuous glass ECT10L-4800, in S2, the ABS particles, the fiber master batch, the SAN resin, the epoxy resin, the coupling agent, the antioxidant and the compatilizer are uniformly mixed by a high-speed mixer; when the glass fiber is the glass fiber T439 or the glass fiber T442, in S11, ABS particles, glass fiber, SAN resin, epoxy resin, coupling agent, antioxidant and compatilizer are uniformly mixed by a high-speed mixer.
Further, the temperature of the high-speed mixer is 50-150 ℃, the rotating speed is 500-1000 r/min, and the mixing time is 5-10 min.
Further, when the glass fiber is continuous glass ECT10L-4800, in S3, the temperature during extrusion is 160-230 ℃, and the rotating speed is 100-300 r/min; when the glass fiber is glass fiber T439 or glass fiber T442, in S22, the temperature during extrusion is 160-230 ℃, and the rotating speed is 100-300 r/min.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a fiber reinforced ABS material for additive manufacturing, which comprises ABS particles, glass fibers, 5-30 parts of SAN resin, epoxy resin, a coupling agent, an antioxidant and a compatilizer, wherein the epoxy resin is one or more of E51, E44, E20 and E12, the warping amount can be obviously reduced due to the addition of the glass fibers, the bending resistance is obviously improved due to the addition of the SAN resin, the anisotropy of an obtained printing piece is obviously reduced when the fiber reinforced ABS material prepared by the invention is used for additive manufacturing, the reinforcing effect of GF can be fully displayed only when the interfacial bonding force of the resin and the GF is enough, otherwise, the composite material is easily damaged from the interface of a resin matrix and the GF along with the increase of an external force, and the reinforcing effect is not obvious. After the compatilizer and the coupling agent are added into the material system, the tensile strength of a printed product is improved, the anisotropy degree of the tensile strength is weakened, GF is dispersed in an ABS matrix more uniformly, and the compatibility of GF and ABS is improved. The good interface bonding force of the fiber and the resin ensures that the external force required by the composite material to be damaged from the interface of the ABS and the GF is improved, so the mechanical property of a printed product is improved. By observing the surface appearance of the fracture of the printed part under SEM, the porosity of the printed part is obviously reduced after the coupling agent is added, which is the reason for improving the mechanical property of the printed part.
The invention also discloses a preparation method of the fiber reinforced ABS material for additive manufacturing, and the method has the advantages of low cost of adopted raw materials, simple operation, industrialized production and wide application prospect.
Drawings
FIG. 1 shows fracture morphology of a printed part of GF modified ABS material without adding a coupling agent;
FIG. 2 shows fracture morphology of a printed part of GF modified ABS material with coupling agent added;
wherein: a-parallel printing direction; b-perpendicular to the printing direction
Detailed Description
To make the features and effects of the present invention comprehensible to those skilled in the art, general description and definitions are made below with reference to terms and expressions mentioned in the specification and claims. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
All features defined herein as numerical ranges or percentage ranges, such as values, amounts, levels and concentrations, are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to cover and specifically disclose all possible subranges and individual numerical values (including integers and fractions) within the range.
In this document, unless otherwise specified, "comprising," including, "" containing, "" having, "or the like, means" consisting of … … "and" consisting essentially of … …, "e.g.," a comprises a "means" a comprises a and the other "and" a comprises a only.
In this context, for the sake of brevity, not all possible combinations of features in the various embodiments or examples are described. Therefore, the respective features in the respective embodiments or examples may be arbitrarily combined as long as there is no contradiction between the combinations of the features, and all the possible combinations should be considered as the scope of the present specification.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The following examples use instrumentation conventional in the art. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. The various starting materials used in the examples which follow, unless otherwise indicated, are conventional commercial products having specifications which are conventional in the art. In the description of the present invention and the following examples, "%" represents weight percent, "parts" represents parts by weight, and proportions represent weight ratios, unless otherwise specified.
Example 1
A fiber reinforced ABS material for additive manufacturing comprising the steps of:
s1: extruding fully dried ABS particles and continuous glass (ECT 10L-4800) by using a double-screw double-extruder in parts by mass, wherein the double-screw double-extruder is provided with a 10-section conveying section, the glass fiber is added into a 5 th section conveying section, and the temperature of each section of the conveying section is T 1 ＝180℃、T 2 ＝220℃、T 3 ＝230℃、T 4 ＝230℃、T 5 ＝230℃、T 6 ＝225℃、T 7 ＝225℃、T 8 ＝225℃、T 9 ＝225℃、T 10 =225 ℃, the rotation speed of the screw is 130r/min, water cooling and air cooling are carried out after extrusion, and the mixture is cut into particles by a granulator to obtain a fiber master batch, wherein the glass fiber content is 12%;
s2: adding 61 parts of fully dried ABS particles, 9 parts of fiber master batch (added in a master batch conversion mode), 25 parts of SAN resin, 1 part of epoxy resin, 0.5 part of coupling agent (KH 550), 0.5 part of antioxidant (1010) and 2 parts of compatilizer (58816) into a high-speed mixer, and uniformly mixing to obtain ABS mixed resin, wherein the temperature of the high-speed mixer is 70 ℃, the rotating speed is 700r/min, and the mixing time is 5min;
s3: extruding ABS mixed resin by adopting a double-screw double-extruder, wherein the temperature of each section is T 1 ＝180℃、T 2 ＝220℃、T 3 ＝230℃、T 4 ＝230℃、T 5 ＝230℃、T 6 ＝220℃、T 7 ＝225℃、T 8 ＝225℃、T 9 And the screw rotation speed is 300r/min at the temperature of 222 ℃ and T10=215 ℃, water cooling and air cooling are carried out after extrusion, and the materials are cut into particles by a granulator, so that the fiber reinforced ABS material for additive manufacturing is obtained.
Example 2
A fiber reinforced ABS material for additive manufacturing comprising the steps of:
s1: extruding the fully dried ABS particles and continuous glass (ECT 10L-4800) fibers by using a double-screw double-extruder in parts by massThe double extruder has 10 conveying sections, the glass fiber is added into the 5 th conveying section, and the temperature of each section of the conveying section is T 1 ＝180℃、T 2 ＝220℃、T 3 ＝230℃、T 4 ＝230℃、T 5 ＝230℃、T 6 ＝225℃、T 7 ＝225℃、T 8 ＝225℃、T 9 ＝225℃、T 10 =225 ℃, the rotation speed of the screw is 130r/min, water cooling and air cooling are carried out after extrusion, and the mixture is cut into particles by a granulator to obtain a fiber master batch, wherein the glass fiber content is 19%;
s2: adding 70 parts of fully dried ABS particles, 5 parts of fiber master batch (added by master batch conversion), 20 parts of SAN resin, 1 part of epoxy resin, 0.5 part of coupling agent KH560, 0.5 part of antioxidant (168) and 3 parts of compatilizer (ABS-g-MAH) into a high-speed mixer, and uniformly mixing to obtain ABS mixed resin, wherein the temperature of the high-speed mixer is 70 ℃, the rotating speed is 600r/min, and the mixing time is 5min;
s3: extruding ABS mixed resin by adopting a double-screw double-extruder, wherein the temperature of each section is T 1 ＝180℃、T 2 ＝220℃、T 3 ＝230℃、T 4 ＝230℃、T 5 ＝230℃、T 6 ＝220℃、T 7 ＝225℃、T 8 ＝225℃、T 9 And (4) keeping the screw rotation speed at 300r/min at 222 ℃, T10=215 ℃, performing water cooling and air cooling after extrusion, and dicing by using a dicing cutter to obtain the fiber reinforced ABS material for additive manufacturing.
Example 3
A fiber reinforced ABS material for additive manufacturing comprising the steps of:
adding 75 parts of fully dried ABS particles, 1 part of glass fiber (T439), 20 parts of SAN resin, 1 part of epoxy resin, 0.5 part of coupling agent (KH 560), 0.5 part of antioxidant (168) and 2 parts of compatilizer (ABS-g-MAH) into a high-speed mixer, and uniformly mixing to obtain ABS mixed resin, wherein the temperature of the high-speed mixer is 50 ℃, the rotating speed is 1000r/min, and the mixing time is 5min;
extruding ABS mixed resin by adopting a double-screw double-extruder, wherein the temperature of each section is T 1 ＝185℃、T 2 ＝220℃、T 3 ＝230℃、T 4 ＝230℃、T 5 ＝230℃、T 6 ＝220℃、T 7 ＝225℃、T 8 ＝225℃、T 9 And the screw rotation speed is 300r/min at the temperature of 225 ℃, T10=215 ℃, water cooling and air cooling are carried out after extrusion, and the materials are cut into particles by a granulator, so that the fiber reinforced ABS material for additive manufacturing is obtained.
Example 4
A fiber reinforced ABS material for additive manufacturing comprising the steps of:
adding 70 parts of fully dried ABS particles, 3 parts of glass fiber (T442), 20 parts of SAN resin, 1.5 parts of epoxy resin, 1 part of coupling agent (KH 550), 0.5 part of antioxidant (168) and 4 parts of compatilizer (SMA) into a high-speed mixer, and uniformly mixing to obtain ABS mixed resin, wherein the temperature of the high-speed mixer is 150 ℃, the rotating speed is 600r/min, and the mixing time is 10min;
extruding ABS mixed resin by adopting a double-screw double-extruder, wherein the temperature of each section is T 1 ＝180℃、T 2 ＝220℃、T 3 ＝230℃、T 4 ＝230℃、T 5 ＝230℃、T 6 ＝220℃、T 7 ＝225℃、T 8 ＝225℃、T 9 And the screw rotation speed is 100r/min at the temperature of 222 ℃ and T10=215 ℃, water cooling and air cooling are carried out after extrusion, and the materials are cut into particles by a granulator, so that the fiber reinforced ABS material for additive manufacturing is obtained.
Example 5
A fiber reinforced ABS material for additive manufacturing, comprising the steps of:
adding 70 parts of fully dried ABS particles, 2 parts of glass fiber (T439), 25 parts of SAN resin, 1 part of epoxy resin, 0.5 part of coupling agent (KH 550), 0.5 part of antioxidant (168) and 1 part of compatilizer (58816) into a high-speed mixer, and uniformly mixing to obtain ABS mixed resin, wherein the rotating speed is 700r/min, and the mixing time is 10min;
extruding ABS mixed resin by adopting a double-screw double-extruder, wherein the temperature of each section is T 1 ＝190℃、T 2 ＝220℃、T 3 ＝230℃、T 4 ＝230℃、T 5 ＝230℃、T 6 ＝220℃、T 7 ＝225℃、T 8 ＝225℃、T 9 =225 ℃, T10=220 ℃, spiroThe rotating speed of the rod is 250r/min, water cooling and air cooling are carried out after extrusion, and the material is cut into particles by a granulator, so that the fiber reinforced ABS material for additive manufacturing is obtained.
Example 6
A fiber reinforced ABS material for additive manufacturing comprising the steps of:
adding 50 parts of fully dried ABS particles, 30 parts of glass fiber (T439), 5 parts of SAN resin, 10 parts of epoxy resin, 0.5 part of coupling agent (KH 550), 0.5 part of antioxidant (168) and 4 parts of compatilizer (58816) into a high-speed mixer, and uniformly mixing to obtain ABS mixed resin, wherein the rotating speed is 700r/min, and the mixing time is 10min;
extruding ABS mixed resin by adopting a double-screw double-extruder, wherein the temperature of each section is T 1 ＝190℃、T 2 ＝220℃、T 3 ＝230℃、T 4 ＝230℃、T 5 ＝230℃、T 6 ＝220℃、T 7 ＝225℃、T 8 ＝225℃、T 9 And the screw rotation speed is 250r/min at the temperature of 225 ℃, T10=220 ℃, water cooling and air cooling are carried out after extrusion, and the materials are cut into particles by a granulator, so that the fiber reinforced ABS material for additive manufacturing is obtained.
Example 7
A fiber reinforced ABS material for additive manufacturing comprising the steps of:
adding 60 parts of fully dried ABS particles, 1 part of glass fiber (T439), 30 parts of SAN resin, 1 part of epoxy resin, 1 part of coupling agent (KH 550), 2 parts of antioxidant (264) and 5 parts of compatilizer (MBS) into a high-speed mixer, and uniformly mixing to obtain ABS mixed resin, wherein the rotating speed is 700r/min, and the mixing time is 10min;
extruding ABS mixed resin by adopting a double-screw double-extruder, wherein the temperature of each section is T 1 ＝190℃、T 2 ＝220℃、T 3 ＝230℃、T 4 ＝230℃、T 5 ＝230℃、T 6 ＝220℃、T 7 ＝225℃、T 8 ＝225℃、T 9 And (3) keeping the screw rotation speed at 300r/min at 225 ℃, T10=220 ℃, performing water cooling and air cooling after extrusion, and pelletizing by using a pelletizer to obtain the fiber reinforced ABS material for additive manufacturing.
Fig. 1 and fig. 2 show the fracture morphology of the printing piece of GF-modified ABS material without coupling agent added and the fracture morphology of the printing piece of GF-modified ABS material with coupling agent added, respectively, from which it can be seen that after the compatibilizer and the coupling agent are added to the material system, the tensile strength of the printing piece is improved, and the anisotropy degree of the tensile strength is weakened, GF is dispersed more uniformly in the ABS matrix, the compatibility between GF and ABS is improved, and after the coupling agent is added, the porosity of the printing piece is significantly reduced, which is the reason for the improvement of the mechanical properties of the printing piece.
The fiber reinforced ABS materials for additive manufacturing obtained in example 1 and example 2 were printed with a printing apparatus to obtain test samples, which were divided into two types:
1) And (3) testing the warpage rate, printing a single wall with the length, the width and the height =300mm, 50mm and 150mm, printing the single wall in a single-wall spiral mode with the printing parameters of 4mm of line width, 1.5mm of layer thickness, the printing temperature of 210 ℃ and the printing speed of 30mm/s, vertically pressing one end after printing, and measuring the warpage amount of the other end by using a feeler gauge.
2) The mechanical performance test is divided into 2 types, namely the mechanical performance along the printing direction and the mechanical performance vertical to the printing direction, the specific model is length, width, height =220mm, the printing parameters are line width 10mm, layer thickness 3mm, printing temperature 205 ℃, printing speed 30mm/s, printing is carried out in a single-wall spiral mode, the printed sample piece is mechanically processed along the printing direction and the vertical printing direction according to the size standard of tensile property-GB/T1040 and bending property-GB/T9341 respectively to remove steps and burrs, the processed sample piece is tested according to the standard requirements, and the obtained experimental data are shown in tables 1 and 2:
the fiber reinforced ABS materials for additive manufacturing obtained in different embodiments are used for printing test samples by adopting printing equipment, and the obtained experimental data are shown in tables 1 to 5. The ABS modified material prepared by the embodiment of the invention has balanced performances in all aspects for FDM printing process, is more suitable for FDM printing process than ABS raw material, and plays a beneficial role.
Table 1: experimental data of fiber reinforced ABS material for additive manufacturing obtained in example 1
Table 2: experimental data on fiber reinforced ABS material for additive manufacturing obtained in example 2
Table 3: experimental data on fiber reinforced ABS material for additive manufacturing obtained in example 3
Table 4: experimental data on fiber reinforced ABS material for additive manufacturing obtained in example 4
Table 5: experimental data on fiber reinforced ABS material for additive manufacturing obtained in example 5
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. The fiber-reinforced ABS material for additive manufacturing is characterized by comprising the following raw materials in parts by mass: 50-90 parts of ABS particles, 1-30 parts of glass fibers, 5-30 parts of SAN resin, 1-10 parts of epoxy resin, no more than 1 part of coupling agent, 0.1-3 parts of antioxidant and 0.5-5 parts of compatilizer;
wherein the epoxy resin is one or more of E51, E44, E20 and E12.
2. The fiber reinforced ABS material for additive manufacturing of claim 1 wherein the coupling agent is a silane coupling agent or a titanate coupling agent; the antioxidant is one or more of antioxidant 1010, antioxidant 168 and antioxidant 264; the glass fiber is glass fiber T439, continuous glass ECT10L-4800 and glass fiber T442.
3. The fiber reinforced ABS material for additive manufacturing according to claim 2, wherein the compatibilizer is one or more of ABS-g-MAH, MBS, SMA, compatibilizer 58816.
4. The method for preparing the fiber reinforced ABS material for the additive manufacturing, according to claim 3, wherein when the glass fiber is continuous glass ECT10L-4800, the method comprises the following steps:
s1: extruding ABS particles and glass fibers by using an extruder, cooling, and granulating to obtain a fiber master batch;
s2: uniformly mixing ABS particles, fiber master batch, SAN resin, epoxy resin, a coupling agent, an antioxidant and a compatilizer to obtain ABS mixed resin;
s3: extruding the ABS mixed resin by using an extruder, cooling, and granulating to obtain a fiber reinforced ABS material for additive manufacturing;
when the glass fiber is the glass fiber T439 or the glass fiber T442, the method comprises the following steps:
s11: uniformly mixing ABS particles, glass fibers, SAN resin, epoxy resin, a coupling agent, an antioxidant and a compatilizer to obtain ABS mixed resin;
s22: and extruding the ABS mixed resin by using an extruder, cooling, and granulating to obtain the fiber reinforced ABS material for additive manufacturing.
5. The preparation method of the fiber reinforced ABS material for the additive manufacturing according to claim 4, wherein the extruder is a twin-screw twin-extruder, and the cooling treatment is water cooling and air cooling.
6. The method for preparing the fiber reinforced ABS material for the additive manufacturing according to claim 4, wherein the extruder is provided with a 10-stage conveying section, and when the glass fiber is continuous glass ECT10L-4800, in S1, the glass fiber is added in a 5 th stage conveying section.
7. The method for preparing the fiber reinforced ABS material for additive manufacturing according to claim 4, wherein when the glass fiber is continuous glass ECT10L-4800, the temperature during extrusion is 160-230 ℃ and the rotation speed is 50-150 r/min in S1.
8. The method for preparing the fiber reinforced ABS material for additive manufacturing according to claim 4, wherein when the glass fiber is continuous glass ECT10L-4800, in S2, the ABS particles, the fiber master batch, the SAN resin, the epoxy resin, the coupling agent, the antioxidant and the compatilizer are mixed uniformly by a high speed mixer; when the glass fiber is glass fiber T439 or glass fiber T442, in S11, ABS particles, glass fiber, SAN resin, epoxy resin, coupling agent, antioxidant and compatilizer are uniformly mixed by a high-speed mixer.
9. The method for preparing the fiber reinforced ABS material for the additive manufacturing according to claim 8, wherein the temperature of the high-speed mixer is 50-150 ℃, the rotating speed is 500-1000 r/min, and the mixing time is 5-10 min.
10. The method for preparing the fiber reinforced ABS material for the additive manufacturing according to claim 4, wherein when the glass fiber is continuous glass ECT10L-4800, the temperature during the extrusion is 160-230 ℃ in S3, and the rotating speed is 100-300 r/min; when the glass fiber is glass fiber T439 or glass fiber T442, in S22, the temperature during extrusion is 160-230 ℃, and the rotating speed is 100-300 r/min.
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