CN113881219B - Light-absorbing plastic for laser welding and preparation method thereof - Google Patents
Light-absorbing plastic for laser welding and preparation method thereof Download PDFInfo
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- CN113881219B CN113881219B CN202111138201.4A CN202111138201A CN113881219B CN 113881219 B CN113881219 B CN 113881219B CN 202111138201 A CN202111138201 A CN 202111138201A CN 113881219 B CN113881219 B CN 113881219B
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- 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
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- C08K3/02—Elements
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- C—CHEMISTRY; METALLURGY
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- C08K7/00—Use of ingredients characterised by shape
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- C08K7/14—Glass
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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
- C08K9/00—Use of pretreated ingredients
Abstract
The invention discloses a light-absorbing plastic for laser welding, which comprises the following components in parts by weight: 50-97 parts by weight of thermoplastic resin; 0-50 parts by weight of surface modified glass fiber; 0.01 to 2 parts by weight of carbon quantum dots; 0.1 to 0.5 weight portion of antioxidant; 0.3 to 1 weight portion of lubricant. The invention also discloses a preparation method of the light-absorbing plastic for laser welding. The invention has the advantages that: by adding the functionalized carbon quantum dots into the material, the material is used as a light absorption component in a welding material to absorb infrared laser, so that high heat is rapidly excited, a welding interface is melted, and a good welding effect is realized.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to light-absorbing plastic for laser welding and a preparation method thereof.
Background
Thermoplastic plastics are widely used in the fields of automobiles, furniture, biology and medical treatment with excellent properties such as low density, good toughness, low cost and the like. With the rapid development of industry, the connection requirements between plastic parts are becoming wider and wider to meet the requirements of product design diversification.
The connection between the plastic parts may be achieved by means of mechanical fastening, chemical bonding or welding. The mechanical fastening needs to be designed through a buckle or a thread, so that stress concentration is easy to generate, and the tightness is difficult to ensure completely. Chemical bonding has high requirement on the surface of the material and long processing period. The laser welding technology is applied to the connection of plastic parts, can greatly reduce the vibration stress and the thermal stress of products, has precise and firm welding, good sealing performance, less resin degradation in the welding process, more stable components in the parts or devices, and is also suitable for welding a plurality of different types of materials.
Patent CN 109929241a uses carbon black as the light absorbing component to prepare the light absorbing PA6 material, but we have found that the laser weld strength is not high and the welding window is narrow. The patent CN 112812549A adds metal doped carbon quantum dots to prepare PA6 material, and the doping of metal ions reduces the crystallinity of nylon, so that the light transmittance of the material is improved to a certain extent, and the material is beneficial to being used as a light transmitting material in the laser welding technology.
The carbon quantum dot is a novel carbon-based zero-dimensional material. The carbon quantum dot has the advantages of excellent optical property, environmental friendliness, wide raw material sources, low cost and the like, and the existing synthesis methods comprise an arc discharge method, a laser etching method, an electrochemical synthesis method, a chemical oxidation method, a combustion method, a hydrothermal synthesis method, a microwave synthesis method, a template method and the like. Carbon quantum dots are of little use in plastics additives, particularly as laser absorbing materials.
Disclosure of Invention
The invention provides a light-absorbing plastic for laser welding, which is prepared by adding amino-functionalized or carboxyl-modified carbon quantum dots into a material to serve as a light-absorbing component in a welding material, absorbing near infrared laser, exciting high heat and melting an interface, so that a good welding effect is realized.
The invention further aims at providing a preparation method of the light-absorbing plastic for laser welding.
The aim of the invention is achieved by the following technical scheme: the light-absorbing plastic for laser welding comprises the following components in parts by weight:
the thermoplastic resin is not limited to a variety including, but not limited to, polyamide, polyester, polyolefin, etc.; optionally PA, PBT, PC, POM, PPE, PPS, ABS, ASA, PP, PE, TPE.
The surface modified glass fiber is glass fiber subjected to surface treatment by adopting a coupling agent.
The carbon quantum dots are amino-functionalized carbon quantum dots or carboxyl-modified carbon quantum dots.
The antioxidant is one or two of hindered phenols and phosphite antioxidants, and the weight ratio of the hindered phenols to the phosphite antioxidants is 1:2.
The lubricant is one or more of stearate, stearate and silicone powder.
The preparation method of the light-absorbing plastic for laser welding comprises the following steps:
(1) Weighing raw materials: the weight portions are as follows:
(2) Adding the thermoplastic resin, the carbon quantum dots, the antioxidant and the lubricant in the step (1) into a high-speed mixer, and mixing for more than 20 seconds;
(3) Adding the mixed raw materials into a double-screw extruder, adding surface modified glass fibers in the step (1) through side feeding, melting and extruding at a proper extrusion temperature of resin, cooling and granulating to obtain the composite material.
The rotating speed of the high-speed mixer in the step (2) is 400-600 rpm; the thermoplastic resin is not limited to a variety including, but not limited to, polyamide, polyester, polyolefin, etc.; optionally PA, PBT, PC, POM, PPE, PPS, ABS, ASA, PP, PE, TPE; the surface modified glass fiber is glass fiber subjected to surface treatment by adopting a coupling agent; the carbon quantum dots are amino-functionalized carbon quantum dots or carboxyl-modified carbon quantum dots; the antioxidant is one or two of hindered phenols and phosphite antioxidants, and the weight ratio of the hindered phenols to the phosphite antioxidants is 1:2; the lubricant is one or more of stearate, calcium stearate, magnesium stearate and silicone powder.
The principle of the invention is as follows:
the mechanical property of the material can be improved by adding glass fiber for reinforcement modification. The glass fiber is subjected to surface treatment modification by using a coupling agent, and an effective chemical bond or interaction is formed between a functional group on the coupling agent and the resin, so that the compatibility between the glass fiber and the matrix resin is enhanced, and the mechanical property of the material is ensured.
By adding amino-functionalized or carboxyl-modified carbon quantum dots into the material, the material is used as a light absorption component in a welding material, absorbs near infrared laser, excites high heat and melts an interface, so that a good welding effect is realized.
Compared with the prior art, the invention has the advantages and effects that: the carbon quantum dots with the surface modified by the functionalization are added as the light absorber of the material, the near infrared light is absorbed to excite high heat, the material interface is melted, and the welding requirements of high quality, high precision, high speed, high efficiency and low deformation are realized.
Drawings
Fig. 1 is a transmission electron microscope image of the carbon quantum dots used in examples 1 to 5, in which (a) is a carboxyl group-modified carbon quantum dot used in examples 4 to 5, and (b) is an amino group-functionalized carbon quantum dot used in examples 1 to 3.
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto.
Example 1
78 parts of thermoplastic resin, 2 parts of carbon quantum dots, 0.5 part of antioxidant and 0.5 part of lubricant are weighed, added into a high-speed mixer according to a certain sequence and uniformly mixed, specifically, the thermoplastic resin, the carbon quantum dots, the antioxidant and the lubricant are added into the high-speed mixer and mixed for more than 20 seconds; adding 20 parts by weight of surface modified glass fibers into a double-screw extruder through a main feeding hopper, and simultaneously adding the surface modified glass fibers through side feeding, and melting, mixing, extruding and granulating the surface modified glass fibers through the double-screw extruder to obtain the light-absorbing plastic for laser welding, wherein the temperatures of all the sections are respectively as follows: the temperature of the first area is 200 ℃, the temperature of the second area is 240 ℃, the temperature of the third area is 240 ℃, the temperature of the fourth area is 240 ℃, the temperature of the fifth area is 240 ℃, the temperature of the sixth area is 240 ℃, the temperature of the seventh area is 230 ℃, the temperature of the eighth area is 230 ℃, and the temperature of the machine head is 235 ℃; the host rotation speed was 300rpm.
The thermoplastic resin in this example is polyamide 6 (PA 6).
The surface-modified glass fiber in this example is a glass fiber surface-treated with a coupling agent.
The carbon quantum dots in this embodiment are amino-functionalized near-infrared carbon quantum dots. The preparation process of the amino-functionalized near-infrared carbon quantum dot comprises the following steps: dissolving a small amount of citric acid serving as a carbon source in a proper amount of deionized water, magnetically stirring until the solution is clear, transferring the solution into a 100ml reaction kettle, preserving heat for 5 hours at 180 ℃, adding 1ml of ammonia water into the cooled reaction solution, carrying out ultrasonic treatment to uniformly mix the solution, heating the solution to 200 ℃ and preserving heat for 6 hours, cooling the solution, centrifuging the reaction solution, and filtering the solution to obtain the amino-functionalized near-infrared carbon quantum dot.
The antioxidant in the embodiment is one or two of hindered phenols and phosphite antioxidants, and the weight ratio of the hindered phenols to the phosphite antioxidants is 1:2.
The lubricant in this embodiment is one or more of stearate, silicone powder.
Example 2
Weighing 80 parts by weight of thermoplastic resin, 0.01 part by weight of carbon quantum dots, 0.1 part by weight of antioxidant and 0.5 part by weight of lubricant, adding the thermoplastic resin, the carbon quantum dots, the antioxidant and the lubricant into a high-speed mixer according to a certain sequence, and mixing uniformly, specifically, adding the thermoplastic resin, the carbon quantum dots, the antioxidant and the lubricant into the high-speed mixer, and mixing for more than 20 seconds; adding 20 parts by weight of surface modified glass fibers into a double-screw extruder through a main feeding hopper, and simultaneously adding the surface modified glass fibers through side feeding, and melting, mixing, extruding and granulating the surface modified glass fibers through the double-screw extruder to obtain the light-absorbing plastic for laser welding, wherein the temperatures of all the sections are respectively as follows: the temperature of the first area is 200 ℃, the temperature of the second area is 240 ℃, the temperature of the third area is 240 ℃, the temperature of the fourth area is 240 ℃, the temperature of the fifth area is 240 ℃, the temperature of the sixth area is 240 ℃, the temperature of the seventh area is 230 ℃, the temperature of the eighth area is 230 ℃, and the temperature of the machine head is 235 ℃; the host rotation speed was 300rpm.
The thermoplastic resin in this example was polyamide 6 (PA 6)
The surface-modified glass fiber in this example is a glass fiber surface-treated with a coupling agent.
The carbon quantum dots in this embodiment are amino-functionalized near-infrared carbon quantum dots. The preparation process of the amino-functionalized near-infrared carbon quantum dot comprises the following steps: dissolving a small amount of citric acid serving as a carbon source in a proper amount of deionized water, magnetically stirring until the solution is clear, transferring the solution into a 100ml reaction kettle, preserving heat for 5 hours at 180 ℃, adding 1ml of ammonia water into the cooled reaction solution, carrying out ultrasonic treatment to uniformly mix the solution, heating the solution to 200 ℃ and preserving heat for 6 hours, cooling the solution, centrifuging the reaction solution, and filtering the solution to obtain the amino-functionalized near-infrared carbon quantum dot.
The antioxidant in the embodiment is one or two of hindered phenols and phosphite antioxidants, and the weight ratio of the hindered phenols to the phosphite antioxidants is 1:2.
The lubricant in this embodiment is one or more of stearate, silicone powder.
Example 3
Weighing 80 parts by weight of thermoplastic resin, 0.2 part by weight of carbon quantum dots, 0.3 part by weight of antioxidant and 0.5 part by weight of lubricant, adding the thermoplastic resin, the carbon quantum dots, the antioxidant and the lubricant into a high-speed mixer according to a certain sequence, and mixing uniformly, specifically, adding the thermoplastic resin, the carbon quantum dots, the antioxidant and the lubricant into the high-speed mixer, and mixing for more than 20 seconds; adding 20 parts by weight of surface modified glass fibers into a double-screw extruder through a main feeding hopper, and simultaneously adding the surface modified glass fibers through side feeding, and melting, mixing, extruding and granulating the surface modified glass fibers through the double-screw extruder to obtain the light-absorbing plastic for laser welding, wherein the temperatures of all the sections are respectively as follows: the temperature of the first area is 200 ℃, the temperature of the second area is 240 ℃, the temperature of the third area is 240 ℃, the temperature of the fourth area is 240 ℃, the temperature of the fifth area is 240 ℃, the temperature of the sixth area is 240 ℃, the temperature of the seventh area is 230 ℃, the temperature of the eighth area is 230 ℃, and the temperature of the machine head is 235 ℃; the host rotation speed was 300rpm.
The thermoplastic resin in this example was polyamide 6 (PA 6)
The surface-modified glass fiber in this example is a glass fiber surface-treated with a coupling agent.
The carbon quantum dots in this embodiment are amino-functionalized near-infrared carbon quantum dots. The preparation process of the amino-functionalized near-infrared carbon quantum dot comprises the following steps: dissolving a small amount of citric acid serving as a carbon source in a proper amount of deionized water, magnetically stirring until the solution is clear, transferring the solution into a 100ml reaction kettle, preserving heat for 5 hours at 180 ℃, adding 1ml of ammonia water into the cooled reaction solution, carrying out ultrasonic treatment to uniformly mix the solution, heating the solution to 200 ℃ and preserving heat for 6 hours, cooling the solution, centrifuging the reaction solution, and filtering the solution to obtain the amino-functionalized near-infrared carbon quantum dot.
The antioxidant in the embodiment is one or two of hindered phenols and phosphite antioxidants, and the weight ratio of the hindered phenols to the phosphite antioxidants is 1:2.
The lubricant in this embodiment is one or more of stearate, silicone powder.
Example 4
Weighing 80 parts by weight of thermoplastic resin, 0.2 part by weight of carbon quantum dots, 0.3 part by weight of antioxidant and 0.5 part by weight of lubricant, adding the thermoplastic resin, the carbon quantum dots, the antioxidant and the lubricant into a high-speed mixer according to a certain sequence, and mixing uniformly, specifically, adding the thermoplastic resin, the carbon quantum dots, the antioxidant and the lubricant into the high-speed mixer, and mixing for more than 20 seconds; adding 20 parts by weight of surface modified glass fibers into a double-screw extruder through a main feeding hopper, and simultaneously adding the surface modified glass fibers through side feeding, and melting, mixing, extruding and granulating the surface modified glass fibers through the double-screw extruder to obtain the light-absorbing plastic for laser welding, wherein the temperatures of all the sections are respectively as follows: the temperature of the first area is 200 ℃, the temperature of the second area is 240 ℃, the temperature of the third area is 240 ℃, the temperature of the fourth area is 240 ℃, the temperature of the fifth area is 240 ℃, the temperature of the sixth area is 240 ℃, the temperature of the seventh area is 230 ℃, the temperature of the eighth area is 230 ℃, and the temperature of the machine head is 235 ℃; the host rotation speed was 300rpm.
The thermoplastic resin in this example is polybutylene terephthalate (PBT).
The surface-modified glass fiber in this example is a glass fiber surface-treated with a coupling agent.
The carbon quantum dots in this embodiment are carboxyl-modified carbon quantum dots. The preparation process of the carboxyl modified carbon quantum dot comprises the following steps: dissolving a small amount of citric acid serving as a carbon source in a proper amount of deionized water, magnetically stirring until the solution is clear, transferring the solution into a 100ml reaction kettle, preserving heat for 5 hours at 180 ℃, and adding sodium hydroxide solution into the cooled reaction solution while stirring until the solution is neutral by using PH test paper. And finally, filtering, freezing and drying to obtain the carboxyl modified carbon quantum dot.
The antioxidant in the embodiment is one or two of hindered phenols and phosphite antioxidants, and the weight ratio of the hindered phenols to the phosphite antioxidants is 1:2.
The lubricant in this embodiment is one or more of stearate, silicone powder.
Example 5
90 parts of thermoplastic resin, 0.2 part of carbon quantum dots, 0.3 part of antioxidant and 0.5 part of lubricant are weighed and added into a high-speed mixer according to a certain sequence to be uniformly mixed, specifically, the thermoplastic resin, the carbon quantum dots, the antioxidant and the lubricant are added into the high-speed mixer to be mixed for more than 20 seconds; adding 10 parts by weight of surface modified glass fibers into a double-screw extruder through a main feeding hopper, and simultaneously adding the surface modified glass fibers through side feeding, and melting, mixing, extruding and granulating the surface modified glass fibers through the double-screw extruder to obtain the light-absorbing plastic for laser welding, wherein the temperatures of all the sections are respectively as follows: the temperature of the first area is 220 ℃, the temperature of the second area is 260 ℃, the temperature of the third area is 260 ℃, the temperature of the fourth area is 255 ℃, the temperature of the fifth area is 250 ℃, the temperature of the sixth area is 250 ℃, the temperature of the seventh area is 250 ℃, the temperature of the eighth area is 250 ℃, and the temperature of the machine head is 265 ℃; the host rotation speed was 300rpm.
The thermoplastic resin in this embodiment is Polycarbonate (PC).
The surface-modified glass fiber in this example is a glass fiber surface-treated with a coupling agent.
The carbon quantum dots in this embodiment are carboxyl-modified carbon quantum dots. The preparation process of the carboxyl modified carbon quantum dot comprises the following steps: dissolving a small amount of citric acid as a carbon source in a proper amount of deionized water, magnetically stirring until the solution is clear, transferring the solution into a 100ml reaction kettle, preserving the heat for 5 hours at 180 ℃, and adding sodium hydroxide solution into the cooled reaction solution while stirring until the solution is neutral by using PH test paper. And finally, filtering, freezing and drying to obtain the carboxyl modified carbon quantum dot.
The antioxidant in the embodiment is one or two of hindered phenols and phosphite antioxidants, and the weight ratio of the hindered phenols to the phosphite antioxidants is 1:2.
The lubricant in this embodiment is one or more of stearate, silicone powder.
Comparative example 1
Weighing 80 parts by weight of PA6 resin, 0.2 part by weight of carbon black, 0.3 part by weight of antioxidant and 0.5 part by weight of lubricant, adding the components into a high-speed mixer according to a certain sequence, and uniformly mixing, specifically adding the PA6 resin, the carbon quantum dots, the antioxidant and the lubricant into the high-speed mixer, and mixing for more than 20 seconds; adding 20 parts by weight of surface modified glass fibers into a double-screw extruder through a main feeding hopper, and simultaneously adding the surface modified glass fibers through side feeding, and melting, mixing, extruding and granulating the surface modified glass fibers through the double-screw extruder to obtain the light-absorbing plastic for laser welding, wherein the temperatures of all the sections are respectively as follows: the temperature of the first area is 200 ℃, the temperature of the second area is 240 ℃, the temperature of the third area is 240 ℃, the temperature of the fourth area is 240 ℃, the temperature of the fifth area is 240 ℃, the temperature of the sixth area is 240 ℃, the temperature of the seventh area is 230 ℃, the temperature of the eighth area is 230 ℃, and the temperature of the machine head is 235 ℃; the host rotation speed was 300rpm.
Comparative example 2
Weighing 75 parts by weight of PA6 resin, 0.2 part by weight of carbon black, 0.1 part by weight of carbon quantum dots, 0.3 part by weight of antioxidant and 0.5 part by weight of lubricant, adding the materials into a high-speed mixer according to a certain sequence, and uniformly mixing, specifically adding the PA6 resin, the carbon quantum dots, the antioxidant and the lubricant into the high-speed mixer, and mixing for more than 20 seconds; adding 20 parts by weight of surface modified glass fibers into a double-screw extruder through a main feeding hopper, and simultaneously adding the surface modified glass fibers through side feeding, and melting, mixing, extruding and granulating the surface modified glass fibers through the double-screw extruder to obtain the light-absorbing plastic for laser welding, wherein the temperatures of all the sections are respectively as follows: the temperature of the first area is 200 ℃, the temperature of the second area is 240 ℃, the temperature of the third area is 240 ℃, the temperature of the fourth area is 240 ℃, the temperature of the fifth area is 240 ℃, the temperature of the sixth area is 240 ℃, the temperature of the seventh area is 230 ℃, the temperature of the eighth area is 230 ℃, and the temperature of the machine head is 235 ℃; the host rotation speed was 300rpm.
Examples and comparative examples were tested for performance according to the following criteria:
tensile strength, flexural strength and impact strength were tested according to the ISO 527, ISO 178 and ISO 179 standards, respectively; the reinforced thermoplastic with the same glass fiber content as that of the embodiment or the comparative example is selected as a light transmission material, a welding experiment is carried out on a light absorption material sample and a light transmission material sample (1.6X12.8X103 mm), a quasi-synchronous welding mode is adopted, a tensile test (the tensile rate is 5 mm/min) is carried out on a welded sample after welding, and a tensile value (N) at the time of fracture is used as a welding effect evaluation standard. The results of the performance tests and the results of the comparative examples of examples 1 to 4 of the present invention are shown in Table 1.
Table 1 test results of composite materials obtained in examples 1 to 4 and comparative examples 1 to 2
| Comparative example 1 | Comparative example 2 | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Welding strength (N) | 630 | 830 | 860 | 680 | 780 | 680 | 710 |
The coupling agent surface modified glass fiber reinforced plastic has excellent mechanical properties.
From the test data of the examples and comparative examples, the following conclusions were drawn: carbon quantum dots are added into the material to serve as light absorption components, and the material has higher welding strength when matched with the corresponding light transmission components; in comparative example 1, carbon black was added as a light absorber, and the welding strength corresponding to the material was low.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (8)
1. The light-absorbing plastic for laser welding is characterized by comprising the following components in parts by weight:
2. the light-absorbing plastic for laser welding according to claim 1, wherein: the thermoplastic resin is selected from polyamide, polyester and polyolefin; further selected from one or more complexes of PA, PBT, PC, POM, PPE, PPS, ABS, ASA, PP, PE, TPE.
3. The light-absorbing plastic for laser welding according to claim 1, wherein: the surface modified glass fiber is glass fiber subjected to surface treatment by adopting a coupling agent.
4. The light-absorbing plastic for laser welding according to claim 1, wherein the carbon quantum dots are amino-functionalized carbon quantum dots or carboxyl-modified carbon quantum dots.
5. The light-absorbing plastic for laser welding according to claim 1, wherein: the antioxidant is one or two of hindered phenols and phosphite antioxidants, and the weight ratio of the hindered phenols to the phosphite antioxidants is 1:2.
6. The light-absorbing plastic for laser welding according to claim 1, wherein: the lubricant is one or more of stearate, stearate and silicone powder.
7. The method for producing a light-absorbing plastic for laser welding according to any one of claims 1 to 6, comprising the steps of:
(1) Weighing raw materials: the weight portions are as follows:
(2) Adding the thermoplastic resin, the carbon quantum dots, the antioxidant and the lubricant in the step (1) into a high-speed mixer, and mixing for more than 20 seconds;
(3) Adding the mixed raw materials into a double-screw extruder, adding surface modified glass fibers in the step (1) through side feeding, melting and extruding at a proper extrusion temperature of resin, cooling and granulating to obtain the composite material.
8. The method for producing a light-absorbing plastic for laser welding according to claim 7, wherein: the rotating speed of the high-speed mixer in the step (2) is 200-600 rpm; the extrusion parameters are processed according to different resins by adopting generally known proper extrusion parameters; the thermoplastic resin is selected from polyamide, polyester and polyolefin; the surface modified glass fiber is glass fiber subjected to surface treatment by adopting a coupling agent; the carbon quantum dots are amino-functionalized carbon quantum dots or carboxyl-modified carbon quantum dots; the antioxidant is one or two of hindered phenols and phosphite antioxidants, and the weight ratio of the hindered phenols to the phosphite antioxidants is 1:2; the lubricant is one or more of stearate, stearate and silicone powder.
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| CN113881219A (en) | 2022-01-04 |
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