CN114736499A - PC composite material, preparation method and application - Google Patents
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Abstract
The invention discloses a PC composite material and a preparation method and application thereof. The PC composite material comprises the following components in parts by weight: 70-85 parts of siloxane copolymerized polycarbonate resin, 15-25 parts of carbon fiber, 0-6 parts of an interface modifier, 1-5 parts of a toughening agent and 0.1-2 parts of a silane coupling agent; the silane coupling agent is a mixture of a silane coupling agent containing an amino group and a silane coupling agent containing an epoxy group. According to the invention, the siloxane copolymerized polycarbonate resin, the carbon fiber, the interface modifier, the toughening agent and the silane coupling agent are cooperated, so that the tone quality and tone color of musical instruments can be improved, and the good impact resistance of the PC composite material can be maintained.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a PC composite material, and a preparation method and application thereof.
Background
Currently, commercially available stringed instruments such as guitars and the like are generally manufactured by manually processing various structural and functional parts including back plates, front plates, side plates, neck, pillow and the like with specific wood materials, and then bonding and combining the parts with glue. The guitar processing and manufacturing method has the advantages of multiple working procedures, complex material variety, low production efficiency, high price and poor quality consistency. Moreover, from the perspective of long-term use, the wooden structure is greatly affected by the humidity of the environment, and is prone to generate deformation affecting the sound quality in a humid and dry environment. Because of the advantages of plastic materials in aspects of large freedom of product shape design, high processing efficiency, low cost, stable size and the like, the scheme of replacing wood with plastic becomes a great development direction of the musical instrument industry.
Patent CN 107958660A discloses a guitar and guitar shaped body and its preparation method, which realizes the integrated molding of back plate, side plate and neck of guitar, the integrated molding method is injection molding, the preferred material is carbon fiber reinforced ABS, the preferred carbon fiber material has the advantages of low density, high specific strength, smooth surface of the molded product, and high tone quality and tone color. Although the carbon fiber reinforced ABS can achieve a good tone quality effect, the uniqueness of tone color has limitations, such as unclear bass and stuffy voice. Patent CN 112812530A discloses a PC/ABS alloy and a preparation method and application thereof, and the technical characteristic is that a PC material is additionally added on the basis of the original carbon fiber reinforced ABS composition, so that the toughness of the composition is improved, the sound volume of a guitar finished product can be improved, and the bass effect is improved to some extent, but the improvement degree is limited.
Disclosure of Invention
The invention aims to provide a PC composite material, a preparation method and application thereof aiming at the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: the PC composite material comprises the following components in parts by weight: 70-85 parts of siloxane copolymerized polycarbonate resin, 15-25 parts of carbon fiber, 0-6 parts of an interface modifier, 1-5 parts of a toughening agent and 0.1-2 parts of a silane coupling agent; the silane coupling agent is a mixture of a silane coupling agent containing an amino group and a silane coupling agent containing an epoxy group; the toughening agent is a toughening agent containing silicon rubber.
The siloxane copolymerized polycarbonate resin is used as a base material, and the processability and dimensional stability of the PC composite material are improved by utilizing the properties of good fluidity and good toughness of the siloxane copolymerized polycarbonate resin. Therefore, the siloxane copolymerized polycarbonate resin and the toughening agent are compounded, so that the PC composite material not only has higher impact strength, but also has better processability; the invention selects the mixture of the silane coupling agent containing amino groups and the silane coupling agent containing epoxy groups as the silane coupling agent, and a small amount of the silane coupling agent not only can ensure that the PC composite material has the advantage of lower dynamic mechanical internal loss level, but also can ensure that the material still maintains better shock resistance at room temperature and low temperature. Meanwhile, the toughening agent containing silicon rubber is selected, so that the compatibility of the resin, the carbon fiber, the interface modifier, the toughening agent and the silane coupling agent in a PC composite material system can be improved, and further the notch impact strength, the bass tone quality and the tone color level of the PC composite material are improved.
Therefore, the siloxane copolymerized polycarbonate resin, the carbon fiber, the interface modifier, the toughening agent and the silane coupling agent are cooperated, so that the tone quality and the tone color of musical instruments can be improved, such as clear bass and no stuffiness, and the advantages of sound retention, large volume, good responsiveness in a wider frequency range and the like are facilitated; and can maintain the good impact resistance of the PC composite material.
As a preferred embodiment of the present invention, the interfacial modifier is present in an amount of 3 to 5 parts by weight. As a preferred embodiment of the invention, the glass transition temperature of the interface modifier is between 80 and 200 ℃ as tested according to test standard GBT 11998-.
The interface modifier is used for treating the surface of an object to improve or change the physical and chemical properties of the surface of the material, so that the influence of a plurality of interfaces in the material on sound vibration, sound velocity and dissipation can be weakened by using the interface modifier. In addition, the applicant of the invention discovers through a large number of experiments that when the glass transition temperature of the interface modifier is higher, the internal consumption of the material in the vibration process of lower frequency is low at normal temperature, and the bass tone quality are better. Therefore, when the glass transition temperature of the interface modifier is 80-200 ℃, the PC composite material has obvious internal friction absorption effect, can reduce the internal friction level to a low level of 0.0066, and keeps higher notch impact strength.
As a preferred embodiment of the present invention, the mass ratio of the silane coupling agent containing an amino group to the silane coupling agent containing an epoxy group is 0.66 to 1.5: 1.
as a preferred embodiment of the invention, the interface modifier is at least one of maleic anhydride grafted styrene-acrylonitrile and styrene-maleic anhydride-N-phenyl maleimide.
As a preferred embodiment of the invention, the toughening agent is a toughening agent with a core-shell structure consisting of methyl methacrylate, acrylate and organosilicon.
In a preferred embodiment of the present invention, the carbon fiber has an average diameter of 5 to 10 μm.
Experiments show that the average diameter of the carbon fibers influences the bass effect and the shock resistance of the PC composite material, and the bass effect and the shock resistance of the PC composite material are obviously reduced due to the excessively small average diameter of the carbon fibers; when the average diameter of the carbon fiber is too large, the mechanical properties of the PC composite material are degraded.
As a preferred embodiment of the present invention, the weight average molecular weight of the siloxane copolymerized polycarbonate resin is 10000-200000 g/mol. In order to improve the processing performance of the PC composite material, the siloxane copolymerized polycarbonate resin with the weight-average molecular weight of 10000-50000g/mol is selected.
As a preferable embodiment of the invention, the PC composite material also comprises 0-3 parts by weight of processing aid, and the processing aid is at least one of antioxidant and lubricant.
As a preferred embodiment of the present invention, the antioxidant is at least one of phosphite antioxidants, hindered phenol antioxidants and thioether antioxidants; the lubricant is at least one of a silicone lubricant, an ester lubricant, an amide lubricant and a polyethylene lubricant.
In addition, the invention provides a preparation method of the PC composite material, which comprises the following steps:
(1) uniformly mixing siloxane copolymerized polycarbonate resin, an interface modifier, a toughening agent and a processing aid to obtain a premix;
(2) and adding carbon fibers and a silane coupling agent into the premix through a side feeding port, carrying out melt blending, extruding and granulating to obtain the PC composite material.
As a preferred embodiment of the invention, the device for melt blending and extrusion granulation is a double-screw extruder; the temperature of the double-screw extruder from the feeding section to the head is as follows in sequence: the temperature of the T1 zone is 120-140 ℃, the temperature of the T2 zone is 210-230 ℃, the temperature of the T3 zone is 210-230 ℃, the temperature of the T4 zone is 220-240 ℃, the temperature of the T5 zone is 220-240 ℃, the temperature of the T6 zone is 220-240 ℃, the temperature of the T7 zone is 210-230 ℃, the temperature of the T8 zone is 210-230 ℃, the temperature of the T9 zone is 220-250 ℃, the temperature of the T10 zone is 220-250 ℃, the temperature of the T11 zone is 220-250 ℃, the temperature of the T12 zone is 220-250 ℃, the temperature of the head zone is 220-250 ℃, and the length-diameter ratio of the screw is (46-50): 1.
the PC composite material is applied to musical instruments; the instrument is a stringed instrument.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention selects the mixture of the silane coupling agent containing amino groups and the silane coupling agent containing epoxy groups as the silane coupling agent, and a small amount of the silane coupling agent not only can ensure that the PC composite material has the advantage of low dynamic mechanical internal loss level, but also can ensure that the material still has good impact resistance at room temperature and low temperature, thereby being beneficial to the molding processing of the material and the prevention of the impact damage of a workpiece. In addition, the toughening agent containing silicon rubber is selected, so that the compatibility of the resin, the carbon fiber, the interface modifier, the toughening agent and the silane coupling agent in a PC composite material system can be improved, and further the notch impact strength, the bass tone quality and the tone color level of the PC composite material are improved.
(2) According to the invention, the siloxane copolymerized polycarbonate resin, the carbon fiber, the interface modifier, the toughening agent and the silane coupling agent are cooperated, so that the tone quality and tone color of musical instruments can be improved, such as clear bass and no stuffiness, and the advantages of sound retention, large volume, good responsiveness in a wider frequency range and the like are facilitated; and can keep good impact resistance of the PC composite material.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
The following examples and comparative examples are illustrated by taking the following raw materials as examples, and other raw materials can be used in actual production, and the raw materials are as follows:
siloxane copolymerized polycarbonate resin a: bisphenol-A polycarbonate, copolymerized from bisphenol-A, phosgene and polysiloxane, having a weight average molecular weight of 53000, type LEXAN EXL1330, manufacturer GE;
siloxane copolymerized polycarbonate resin B: bisphenol-A polycarbonate, copolymerized from bisphenol-A, phosgene and a polysiloxane, having a weight-average molecular weight of 46000, type LEXAN EXL1112T, manufacturer GE;
carbon fiber A: the average diameter is 5 μm; model IM P303, provided by emperor Dongbangbang;
carbon fiber B: the average diameter was 7 μm; type 493, supplied by emperor dongpo;
an interface modifier A: maleic anhydride grafted styrene-acrylonitrile with a glass transition temperature of 100 ℃; model SAM-010, readily available from Okara;
an interface modifier B: styrene-maleic anhydride-N-phenylmaleimide, glass transition temperature 193 ℃; model number MS-NB, supplied by japan electrical chemistry;
interface modifier C: ethylene-acrylate-glycidyl acrylate, with a glass transition temperature of-50 ℃; model PTW, supplied by dupont;
interface modifier D: PiPA (isopropyl acrylate) -Co-MAH with a glass transition temperature of 5 ℃; model number PiPA-Co-MAH, available from kayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayikayi;
a toughening agent A: the graft copolymer with acrylate and organosilicon copolymer rubber as core and methyl methacrylate as shell has rubber content over 50%; the specific trade mark is as follows: s2001, by mitsubishi yang, japan;
a toughening agent B: the rubber content of the graft copolymer is more than 65 percent, wherein the acrylate and organic silicon copolymer is used as a core, and the methyl methacrylate is used as a shell; the specific trade mark is as follows: s2030, provided by mitsubishi yang, japan;
a toughening agent C: MBS, terpolymer of methyl methacrylate, butadiene and styrene, and the specific mark is as follows: m711, provided by the japanese brillouin company;
silane coupling agent a: a mixture formed by mixing a silane coupling agent containing amino groups and a silane coupling agent containing epoxy groups according to the mass ratio of 1: 1; a silane coupling agent containing an amino group, KH550, provided by Jeccard chemical industry, Hangzhou; KH560, a silane coupling agent containing epoxy groups, provided by the Hangzhou Jeccard chemical industry;
silane coupling agent B: the silane coupling agent containing amino groups, gamma-aminopropyl triethoxysilane, the specific trade name: KH550, provided by the Hangzhou Jeccard chemical industry;
silane coupling agent C: the silane coupling agent containing epoxy group, gamma-glycidol ether oxygen propyl trimethoxy silane, the concrete trade mark: KH560, available from the Hangzhou Jeccard chemical industry;
silane coupling agent D: silane coupling agent without polar group, vinyl triethoxy silane, specific trade mark: a151, provided by Jessica chemical;
silane coupling agent E: a mixture formed by mixing a silane coupling agent containing an amino group and a silane coupling agent containing an epoxy group according to the mass ratio of 0.67: 1; a silane coupling agent containing amino groups, KH550, provided by the Hangzhou Jessica chemical industry; KH560, a silane coupling agent containing epoxy groups, provided by the Hangzhou Jeccard chemical industry;
silane coupling agent F: a mixture formed by mixing a silane coupling agent containing amino groups and a silane coupling agent containing epoxy groups according to the mass ratio of 1.5: 1; a silane coupling agent containing amino groups, KH550, provided by the Hangzhou Jessica chemical industry; KH560, a silane coupling agent containing epoxy groups, provided by Jeccard chemical engineering, Hangzhou;
silane coupling agent G: a mixture formed by mixing a silane coupling agent containing amino groups and a silane coupling agent containing epoxy groups according to the mass ratio of 0.5: 1; a silane coupling agent containing amino groups, KH550, provided by the Hangzhou Jessica chemical industry; KH560, a silane coupling agent containing epoxy groups, provided by the Hangzhou Jeccard chemical industry;
silane coupling agent H: a mixture formed by mixing a silane coupling agent containing amino groups and a silane coupling agent containing epoxy groups according to the mass ratio of 3: 1; a silane coupling agent containing amino groups, KH550, provided by the Hangzhou Jessica chemical industry; KH560, a silane coupling agent containing epoxy groups, provided by the Hangzhou Jeccard chemical industry;
processing aid A: antioxidant: mixing the antioxidant 168 and the antioxidant 1076 according to the mass ratio of 1: 1; the same commercial product is used in the parallel experiment of the invention;
and (3) processing aid B: lubricant, zinc stearate, commercially available, the same commercial product was used in parallel experiments of the invention.
Comparative examples 9 and 10 according to the invention are typical in the art for improving bass, wherein the raw materials used are illustrated as follows:
PC resin: brand PC1300-22, manufacturer LG chemical;
ABS resin A: acrylonitrile-butadiene-styrene copolymer, rubber content 37%, designation ABS 8434, manufacturer brocade chemical;
ABS resin B: acrylonitrile-butadiene-styrene copolymer, 35% rubber content, brand PA-757, manufacturer qimei;
AS resin: styrene-acrylonitrile copolymer, EMI100, easy and easy to manufacture;
examples
The components of the PC composite material of embodiments 1-18 of the invention are shown in Table 1.
The preparation method of the PC composite material disclosed by the embodiment 1-18 comprises the following steps:
(1) uniformly mixing siloxane copolymerized polycarbonate resin, an interface modifier, a toughening agent and a processing aid to obtain a premix;
(2) adding carbon fibers and a silane coupling agent into the premix melt through a side feeding port of a double-screw extruder and a liquid feeding port respectively, melting, blending, extruding and granulating to obtain the PC composite material; the temperature of the double-screw extruder from the feeding section to the head is as follows in sequence: the temperature of the T1 zone is 120-140 ℃, the temperature of the T2 zone is 210-230 ℃, the temperature of the T3 zone is 210-230 ℃, the temperature of the T4 zone is 220-240 ℃, the temperature of the T5 zone is 220-240 ℃, the temperature of the T6 zone is 220-240 ℃, the temperature of the T7 zone is 210-230 ℃, the temperature of the T8 zone is 210-230 ℃, the temperature of the T9 zone is 220-250 ℃, the temperature of the T10 zone is 220-250 ℃, the temperature of the T11 zone is 220-250 ℃, the temperature of the T12 zone is 220-250 ℃, the temperature of the head zone is 220-250 ℃, and the length-diameter ratio of the screw is (46-50): 1.
TABLE 1
Comparative example
The compositions of the PC composite materials of comparative examples 1 to 11 of the present invention are shown in tables 2 and 3.
The preparation method of the PC composite material disclosed in the comparative examples 1-9 of the invention is the same as that of the embodiment of the invention.
The preparation method of the PC composite material of comparative examples 10-11 comprises the following steps:
(1) uniformly mixing ABS resin, PC resin, AS resin and a processing aid to obtain a premix;
(2) adding carbon fibers into the premix through a side feeding port of a double-screw extruder, carrying out melt blending, and carrying out extrusion granulation to obtain the PC composite material; the temperature of the double-screw extruder is 120-250 ℃, wherein the temperature of a T1 zone is 120-140 ℃.
TABLE 2
TABLE 3
Examples of effects
And (3) performance testing:
the products of the examples and comparative examples were tested according to the following criteria, and the relevant test methods and criteria are as follows:
(1) storage modulus: testing according to dynamic thermal mechanical analysis of high molecular polymer;
(2) energy consumption modulus: testing according to dynamic thermal mechanical analysis of high molecular polymer;
(3) tan delta is the ratio of the energy consumption modulus to the storage modulus;
(4) notched impact strength: the test was performed using the ISO180-20016 standard.
The PC composite materials of examples 1-13 and comparative examples 1-11 of the present invention have the performance test results shown in Table 4.
TABLE 4
As can be seen from the data in Table 4, the PC composites prepared in examples 1-13 have tan delta of 0.0084 or less and room temperature notched impact strength of 10.0kJ/m or more2The impact strength of the notch at 0 ℃ is more than or equal to 9.0kJ/m2Has good bass effect and keeps higher shock resistance at room temperature and low temperature.
According to the data of example 1 and comparative examples 1 to 3, the type of the silane coupling agent has a large influence on tan delta and impact resistance of the PC composite material; the mixture of the silane coupling agent containing an amino group and the silane coupling agent containing an epoxy group, the silane coupling agent, the material prepared therefrom, had tan δ lower than that of comparative examples 1-3 and also had room temperature and low temperature impact resistance superior to that of comparative examples 1-3.
From the data of examples 1-5, it can be seen that as the amount of the interfacial modifier added increases, the material's tan δ decreases and then increases, and the room temperature and low temperature impact properties gradually increase; however, it is understood from the data of comparative example 4 that when the addition amount of the interfacial modifier is too high, the prepared PC composite material has a large tan δ, the bass performance is not improved much, and the room temperature and low temperature impact resistance is remarkably decreased.
As can be seen from the data of examples 1 and 6 to 8, as the addition amount of the silane coupling agent increases, the tan delta of the material decreases and then increases, and the room-temperature and low-temperature impact resistance of the material is stronger; however, according to the data of comparative examples 7 to 8, when the amount of the silane coupling agent added was too low or too high, the prepared PC composite material had a large tan δ, the bass performance was not improved much, and the room temperature and low temperature impact resistance was significantly reduced.
From the data of examples 1, 12 to 15, it can be seen that as the mass ratio of the amino group-containing silane coupling agent to the epoxy group-containing silane coupling agent in the silane coupling agent increases, the tan δ of the material decreases and then increases, while the room-temperature and low-temperature impact resistance of the material increases and then decreases.
From the data of examples 1 and 9 to 11, it is clear that the glass transition temperature of the interface modifier is 80 to 200 ℃, the material has a small tan δ, good bass performance, and strong room temperature and low temperature impact resistance.
As can be seen from the data of examples 1 and 16 and comparative example 9, the kind of toughening agent has a large influence on tan delta and impact resistance of the PC composite material; the tougheners of examples 1, 16 containing silicone rubber produced materials with tan δ lower than that of comparative example 9, and also had room temperature and low temperature impact properties better than that of comparative example 9.
The comparative examples 7 to 8 are the common scheme of replacing wood by plastic at present, the tan delta of the composite material is 0.019, the improvement of the bass effect has obvious difference from the application, and the PC composite material also has good room temperature and low temperature impact resistance.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The PC composite material is characterized by comprising the following components in parts by weight: 70-85 parts of siloxane copolymerized polycarbonate resin, 15-25 parts of carbon fiber, 0-6 parts of an interface modifier, 1-5 parts of a toughening agent and 0.1-2 parts of a silane coupling agent; the silane coupling agent is a mixture of a silane coupling agent containing an amino group and a silane coupling agent containing an epoxy group; the toughening agent is a toughening agent containing silicon rubber.
2. The PC composite of claim 1, wherein the interfacial modifier is present in an amount of 3 to 5 parts by weight.
3. The PC composite of claim 1, wherein the interfacial modifier has a glass transition temperature of 80-200 ℃.
4. The PC composite material according to claim 1, wherein the mass ratio of the silane coupling agent having an amino group to the silane coupling agent having an epoxy group is 0.66 to 1.5: 1.
5. the PC composite material according to claim 1, wherein the toughening agent is a core-shell structure toughening agent composed of methyl methacrylate, acrylate and organosilicon.
6. The PC composite of claim 1, wherein the carbon fibers have an average diameter of 5 to 10 μ ι η; the weight average molecular weight of the siloxane copolymerized polycarbonate resin is 10000-200000 g/mol.
7. The PC composite of claim 1, further comprising 0-3 parts by weight of a processing aid; the processing aid is at least one of an antioxidant and a lubricant.
8. The method for preparing a PC composite according to claim 7, comprising the steps of:
(1) uniformly mixing siloxane copolymerized polycarbonate resin, an interface modifier, a toughening agent and a processing aid to obtain a premix;
(2) and adding carbon fibers and a silane coupling agent into the premix through a side feeding port, carrying out melt blending, extruding and granulating to obtain the PC composite material.
9. The method for preparing the PC composite material according to claim 8, wherein the device for melt blending and extrusion granulation is a twin-screw extruder; the temperature of the double-screw extruder from the feeding section to the head is as follows in sequence: the temperature of the T1 zone is 120-140 ℃, the temperature of the T2 zone is 210-230 ℃, the temperature of the T3 zone is 210-230 ℃, the temperature of the T4 zone is 220-240 ℃, the temperature of the T5 zone is 220-240 ℃, the temperature of the T6 zone is 220-240 ℃, the temperature of the T7 zone is 210-230 ℃, the temperature of the T8 zone is 210-230 ℃, the temperature of the T9 zone is 220-250 ℃, the temperature of the T10 zone is 220-250 ℃, the temperature of the T11 zone is 220-250 ℃, the temperature of the T12 zone is 220-250 ℃, the temperature of the head zone is 220-250 ℃, and the length-diameter ratio of the screw is (46-50): 1.
10. use of the PC composite material of any one of claims 1-7 in a musical instrument.
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| CN115612264A (en) * | 2022-12-20 | 2023-01-17 | 广州市威柏乐器制造有限公司 | PC/PCTG alloy and preparation method and application thereof |
| CN115746533A (en) * | 2022-11-30 | 2023-03-07 | 厦门元米新材料科技有限公司 | Spraying-free polycarbonate alloy and preparation method and application thereof |
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| CN115612264B (en) * | 2022-12-20 | 2023-03-14 | 广州市威柏乐器制造有限公司 | PC/PCTG alloy and preparation method and application thereof |
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