CN112342543B - Method for sintering and coating polymer material on metal surface by using laser - Google Patents

Method for sintering and coating polymer material on metal surface by using laser Download PDF

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CN112342543B
CN112342543B CN201910731529.3A CN201910731529A CN112342543B CN 112342543 B CN112342543 B CN 112342543B CN 201910731529 A CN201910731529 A CN 201910731529A CN 112342543 B CN112342543 B CN 112342543B
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powder
laser
polymer material
sintering
metal substrate
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CN112342543A (en
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陈天青
宋寰欣
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Jingra Optoelectronic Technology Co ltd
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Jingra Optoelectronic Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Laser Beam Processing (AREA)

Abstract

The invention discloses a method for sintering and coating a high polymer material on a metal surface by utilizing a laser, which comprises the following steps: a. grinding the particle size of the polymer material powder to 40-90 μm by a ball mill; b. focusing and scanning a metal substrate by a laser source to generate a plurality of microstructures on the surface of the metal substrate, wherein the pulse frequency of the laser is 0.5-0.75kHz; spreading the polymer material powder on the surface of the metal base material by a powder spreading system, and directly irradiating the metal base material with the polymer material powder by using a laser as a heat radiation light source for sintering.

Description

Method for sintering and coating polymer material on metal surface by using laser
Technical Field
The invention relates to a method for sintering and coating a polymer material on a metal surface by utilizing a laser and improving the adhesiveness of the polymer material on the metal surface. The invention belongs to the field of high polymer material sintering.
Background
Along with the continuous fermentation of green energy, environmental protection issues and the like in intelligent manufacturing, the industries of intelligent manufacturing, solar energy, green lighting, electric vehicles and the like begin to pay attention to the development of power module management, and the manufacturing process of the intelligent power module is gradually developed towards high power, small size and thin type. Therefore, in order to meet the requirements of light weight, small size, convenient transportation, high density, high power, high transmission speed, high efficiency, etc., the heat dissipation efficiency of the packaging technology and the corresponding packaging material is not negligible.
Moreover, the selective laser sintering has the advantage of rapid prototyping and manufacturing of high polymer materials, metals, ceramics and composite materials. Therefore, the common heat conducting materials such as metal materials, ceramic materials and polymer materials are subject to the following problems due to heat dissipation:
the metal material has poor chemical corrosion resistance and electrical insulation, and cannot meet the heat dissipation requirements of electric insulation occasions and chemical corrosion occasions.
Inorganic ceramic materials have good insulation properties, but have high processing and molding costs and poor impact resistance. On the other hand, graphite materials are excellent in heat conduction, but are poor in insulation and mechanical properties.
Therefore, the heat conducting materials are limited in industrial technical development in aspects of microelectronic packaging, electrical insulation, LED illumination and the like due to the performances of the heat conducting materials, and the high polymer materials have good mechanical properties and fatigue resistance, excellent electrical insulation, chemical corrosion resistance and light weight and are widely applied.
The most developed polymer material is thermoplastic plastic, wherein Polyamide commonly called Nylon (PA) is the thermoplastic resin generally called with the molecule main chain containing repeated amide group- (NHCO) and is widely applied to the automobile and electronic industries to replace metal, and the aim is to manufacture lighter and cheaper components. Meanwhile, nylon is a high-molecular material with high Tg glass transition temperature of 220 ℃ to 250 ℃ and low thermal expansion coefficient of 2.7 to 7.2X10-5/K, and has high temperature resistance, excellent chemical corrosion resistance and high insulation property. However, nylon has a thermal conductivity of about 0.29 k/W/(m.k) and does not have good heat dissipation properties, and thus, the industry has been mostly dealing with the production of mixed metal, ceramic or carbon powders.
However, in order to coat the polymer material on the metal substrate, the bonding between the two materials often has poor bonding strength due to a too large difference in melting point temperature, so that the adhesion between the polymer material and the metal material is extremely poor. On the other hand, since the polymer material itself has low absorptivity to the fiber laser, it is often sintered by the CO2 laser, but the CO2 laser transmission medium is air, and only can be transmitted straight, and the transmission direction must be changed depending on the mirror, and therefore, the polymer material is easily affected by the external environment, and the maintenance and the repair of the mirror are required frequently.
In view of the above, the present inventors have felt to be perfected and have exhausted their mind and have made many years of accumulated experience in the industry, and have further provided a method for sintering and coating a polymer material on a metal surface by using a laser, so as to improve the above-mentioned drawbacks of the prior art.
Disclosure of Invention
The present invention provides a method for sintering polymer material on metal surface by laser to improve adhesion of polymer material during sintering coating on metal surface.
Thus, the present invention discloses a method for sintering and coating a polymer material on a metal surface by using a laser, which comprises the following steps: a. grinding the particle size of the polymer material powder to 40-90 μm by a ball mill; b. focusing and scanning a metal substrate by using a laser source to generate a plurality of microstructures on the surface of the metal substrate, wherein the pulse frequency of the laser is 0.5-0.75kHz; spreading the polymer material powder on the surface of the metal base material by a powder spreading system, and directly irradiating the metal base material with the polymer material powder by using a laser as a heat radiation light source for sintering.
Preferably, the polymer powder is one of polylactic acid (PLA), resin (ABS), polyamide (Nylon) -6, polyamide (PA) 66 (Nylon-66), polyvinyl alcohol (PVA), polystyrene (PS) and acrylic (PMMA).
Preferably, the polymer powder is made of one of nylon-based mixed copper, aluminum, zinc, gold, silver, iron and nickel.
Preferably, the polymer powder is one of nylon-based mixed alumina, aluminum nitride, silicon carbide, magnesium oxide and silicon dioxide.
Preferably, the microstructures are arranged at intervals, and the distance between the microstructures is 1mm.
Preferably, the metal substrate is made of one of iron-based, nickel-based, cobalt-based, chromium-based, molybdenum-based, aluminum-based and copper-based metals or alloy materials thereof.
Preferably, the wavelength of the laser is in the range of 400nm to 11000nm.
Preferably, the thickness of the polymer material powder after sintering is 0.2-10mm.
Therefore, the method provided by the invention can utilize the laser to sinter and coat the polymer material layer by layer on the metal substrate and is not easy to fall off, thereby improving the adhesiveness of the polymer material and meeting the requirements of various industries for coating the polymer material on the surface of the metal material.
Drawings
FIG. 1 is a step diagram of a preferred embodiment of the present invention;
FIG. 2 is a schematic diagram of a laser sintering apparatus according to a preferred embodiment of the present invention;
FIG. 3 is a schematic diagram of a metal substrate and polymer powder sintered according to a preferred embodiment of the present invention;
FIG. 4 is an optical image of a microstructure produced by laser surface treatment in various embodiments of the present invention;
wherein (a) - (i) correspond to examples 1-8 and comparative example, respectively.
Symbol description:
1. laser source
2. Optical fiber
3. Polymer material powder
4. Metal substrate
41. Microstructure of microstructure
S01 to S03 steps
Distance d
Thickness t
Detailed Description
The invention will be further described with reference to specific embodiments, and advantages and features of the invention will become apparent from the description. These examples are merely exemplary and do not limit the scope of the invention in any way. Fig. 1 to 3 are schematic views of a laser sintering apparatus and a schematic view of a sintered metal substrate and polymer powder according to a preferred embodiment of the invention. As shown in the drawing, the present invention discloses a method for sintering and coating polymer material on metal surface, which comprises grinding the particle size of polymer material powder 3 to 40-90 μm by ball mill (step S01), wherein the polymer material powder 3 is made of polylactic acid (PLA), resin (ABS), polyamide (Nylon) -6, polyamide (PA) 66 (Nylon-66), polyvinyl alcohol (PVA), polystyrene (PS), acrylic (PMMA) or one of Nylon-based mixed copper, aluminum, zinc, gold, silver, iron, nickel, aluminum oxide, aluminum nitride, silicon carbide, magnesium oxide and silicon dioxide, nylon is taken as an example, but not limited thereto, and the laser used in the present embodiment is an optical fiber laser as experimental basis, but can also be a CO2 laser, but not limited thereto.
Then, a metal substrate 4 is scanned by the laser source 1 through the optical fiber 2 to generate a plurality of microstructures 41 on the surface of the metal substrate 4 (step S02), wherein in this embodiment, the microstructures 41 are arranged at intervals, the distance d between the microstructures 41 is 1mm, as shown in fig. 3, and the pulse frequency of the fiber laser used is 0.5-0.75kHz, the pulse width is 750 μs, the wavelength range is 400 nm-11000 nm, the power is 150W, the scanning speed is 20mm/S, and the scanning range is 100mm×100mm. The material of the metal substrate 4 may be one of iron-based, nickel-based, cobalt-based, chromium-based, molybdenum-based, aluminum-based, and copper-based metals or an alloy thereof, and stainless steel is used as an example in the present embodiment, but not limited thereto.
Finally, the polymer powder 3 is spread on the surface of the metal substrate 4 by a powder spreading system, and is directly irradiated on the metal substrate 4 spread with the polymer powder 3 by using an optical fiber laser as a heat radiation light source for sintering (step S03), wherein the thickness t of the polymer powder 3 after sintering is 0.2-10mm.
Various embodiments are provided below, with reference to FIG. 4 and Table 1 below, which are tables of microstructured optical images produced by laser surface treatment and attachment area data for various embodiments of the present invention.
Example 1
The detailed experimental procedure of this example is that the particle size of the polymer powder 3 of nylon is first ground to 40-90 μm by ball mill, then scanned at a scanning speed of 20mm/s, a scanning interval of 1mm, a pulse frequency of 0.04375kHz, a pulse width of 750 μm, and a scanning range of 100×100mm with a fiber laser power of 150W 2 The metal substrate 4 of stainless steel is surface-treated to produce the microstructures 41 on the surface as shown in part (a) of FIG. 4, then the polymer material powder 3 is spread on the surface-treated metal substrate 4 by a powder spreading system, and a fiber laser 20-100W is used as a heat radiation source, and the scanning speed is 70mm/s, the scanning interval is 0.025mm, the pulse frequency is 0.75kHz, the pulse width is 500 mu s, and the scanning range is 100X 100mm 2 Is directly irradiated onto the metal base material 4 on which the polymer material powder 3 is laidSintering, and the sintering thickness t is set to 1mm.
Example 2
The detailed experimental procedure of this example is that the particle size of the polymer powder 3 of nylon is first ground to 40-90 μm by ball mill, then the scanning speed is 20mm/s, the scanning interval is 1mm, the pulse frequency is 0.0875kHz, the pulse width is 750 μm, and the scanning range is 100×100mm by fiber laser power 150W 2 The metal substrate 4 of stainless steel is surface-treated to produce the microstructures 41 on the surface as shown in part (b) of FIG. 4, then the polymer material powder 3 is spread on the surface-treated metal substrate 4 by a powder spreading system, and a fiber laser 20-100W is used as a heat radiation source, and the scanning speed is 70mm/s, the scanning interval is 0.025mm, the pulse frequency is 0.75kHz, the pulse width is 500 mu s, and the scanning range is 100X 100mm 2 Directly irradiating the metal base material 4 on which the polymer material powder 3 is laid, and sintering the metal base material, wherein the sintering thickness t is set to be 1mm.
Example 3
The detailed experimental procedure of this example is that the particle size of the polymer powder 3 of nylon is first ground to 40-90 μm by ball mill, then scanned at a scanning speed of 20mm/s, a scanning interval of 1mm, a pulse frequency of 0.175kHz, a pulse width of 750 μm, and a scanning range of 100×100mm with a fiber laser power of 150W 2 The metal substrate 4 of stainless steel is surface-treated to produce the microstructures 41 on the surface as shown in part (c) of FIG. 4, then the polymer material powder 3 is spread on the surface-treated metal substrate 4 by a powder spreading system, and a fiber laser 20-100W is used as a heat radiation source, and the scanning speed is 70mm/s, the scanning interval is 0.025mm, the pulse frequency is 0.75kHz, the pulse width is 500 mu s, and the scanning range is 100X 100mm 2 Directly irradiating the metal base material 4 on which the polymer material powder 3 is laid, and sintering the metal base material, wherein the sintering thickness t is set to be 1mm.
Example 4
The detailed experimental procedure of this example is to grind the particle size of the polymer powder 3 of nylon by ball millTo 40-90 μm, and scanning with a fiber laser power of 150W, a scanning speed of 20mm/s, a scanning interval of 1mm, a pulse frequency of 0.25kHz, a pulse width of 750 μm, and a scanning range of 100×100mm 2 The metal substrate 4 of stainless steel is surface-treated to produce the microstructures 41 on the surface as shown in part (d) of FIG. 4, then the polymer material powder 3 is spread on the surface-treated metal substrate 4 by a powder spreading system, and a fiber laser 20-100W is used as a heat radiation source, and the scanning speed is 70mm/s, the scanning interval is 0.025mm, the pulse frequency is 0.75kHz, the pulse width is 500 mu s, and the scanning range is 100X 100mm 2 Directly irradiating the metal base material 4 on which the polymer material powder 3 is laid, and sintering the metal base material, wherein the sintering thickness t is set to be 1mm.
Example 5
The detailed experimental procedure of this example is that the particle size of the polymer powder 3 of nylon is first ground to 40-90 μm by ball mill, then scanned at a scanning speed of 20mm/s, a scanning interval of 1mm, a pulse frequency of 0.5kHz, a pulse width of 750 μm, and a scanning range of 100×100mm with a fiber laser power of 150W 2 The metal substrate 4 of stainless steel is surface-treated to produce the microstructures 41 on the surface as shown in part (e) of fig. 4, then the polymer material powder 3 is spread on the surface-treated metal substrate 4 by a powder spreading system, and the metal substrate 4 is directly irradiated with a fiber laser 20-100W as a heat radiation source at a scanning speed of 70mm/s and a scanning interval of 0.025mm, a pulse frequency of 0.75kHz and a pulse width of 500 mus in a scanning range of 100 x 100mm2 for sintering, and a sintering thickness t is set to 1mm.
Example 6
The detailed experimental procedure of this example is that the particle size of the polymer powder 3 of nylon is first ground to 40-90 μm by ball mill, then scanned at a scanning speed of 20mm/s, a scanning interval of 1mm, a pulse frequency of 0.75kHz, a pulse width of 750 μm, and a scanning range of 100×100mm with a fiber laser power of 150W 2 The metal base material 4 of stainless steel is subjected to surface treatment to produce the metal base material on the surfaceThe microstructure 41 is shown in FIG. 4 (f), and the polymer powder 3 is spread on the metal substrate 4 after the surface treatment by a powder spreading system, and then the metal substrate 4 is directly irradiated with a fiber laser 20-100W as a heat radiation source at a scanning speed of 70mm/s, a scanning interval of 0.025mm, a pulse frequency of 0.75kHz, a pulse width of 500 μs and a scanning range of 100×100mm2 for sintering, wherein the sintering thickness t is set to 1mm.
Example 7
The detailed experimental procedure of this example is that the particle size of the polymer powder 3 of nylon is first ground to 40-90 μm by ball mill, then scanned at a scanning speed of 20mm/s, a scanning interval of 1mm, a pulse frequency of 1kHz, a pulse width of 750 μm, and a scanning range of 100X 100mm by fiber laser power of 150W 2 The metal substrate 4 of stainless steel is surface-treated to produce the microstructures 41 on the surface as shown in part (g) of FIG. 4, then the polymer material powder 3 is spread on the surface-treated metal substrate 4 by a powder spreading system, and a fiber laser 20-100W is used as a heat radiation source, and the scanning speed is 70mm/s, the scanning interval is 0.025mm, the pulse frequency is 0.75kHz, the pulse width is 500 mu s, and the scanning range is 100X 100mm 2 Directly irradiating the metal base material 4 on which the polymer material powder 3 is laid, and sintering the metal base material, wherein the sintering thickness t is set to be 1mm.
Example 8
The detailed experimental procedure of this example is that the particle size of the polymer powder 3 of nylon is first ground to 40-90 μm by ball mill, then scanned at a scanning speed of 20mm/s, a scanning interval of 1mm, a pulse frequency of 2kHz, a pulse width of 750 μm, and a scanning range of 100×100mm with a fiber laser power of 150W 2 The metal substrate 4 of stainless steel is subjected to surface treatment to produce the microstructures 41 on the surface as shown in part (h) of FIG. 4, and then the polymer material powder 3 is spread on the metal substrate 4 after the surface treatment by a powder spreading system, and a fiber laser 20-100W is used as a heat radiation source at a scanning speed of 70mm/s between scansDistance from 0.025mm, pulse frequency 0.75kHz, pulse width 500 μs, scan range 100X 100mm 2 Directly irradiating the metal base material 4 on which the polymer material powder 3 is laid, and sintering the metal base material, wherein the sintering thickness t is set to be 1mm.
Comparative example
The detailed experimental procedure of this comparative example was that the particle size of the polymer material powders 3 of nylon was first ground to 40-90 μm by a ball mill without any treatment of the surface of the metal substrate 4 of stainless steel as shown in part (i) of FIG. 4, then the polymer material powders 3 were spread on the metal substrate 4 without any treatment by a powder spreading system, and then a fiber laser 20-100W was used as a heat radiation source with a scanning speed of 70mm/s, a scanning interval of 0.025mm, a pulse frequency of 0.75kHz, a pulse width of 500. Mu.s, and a scanning range of 100X 100mm 2 Directly irradiating the metal base material 4 on which the polymer material powder 3 is laid, and sintering the metal base material, wherein the sintering thickness is set to be 1mm.
TABLE 1
From the above data in table 1, it can be seen that the sintering coating process according to the experimental procedures of examples 5 and 6 significantly improves the adhesion of the polymer, i.e. the pulse frequency of the fiber laser must be between 0.5 and 0.75kHz during the process of producing the microstructures 41 on the metal substrate 4, the polymer powder 3 can be effectively adhered to the metal substrate 4, and thus the data table can also prove that the defect of the existing laser can be solved under the conditions provided by the present invention, the adhesion of the polymer to the metal can be improved, and the thickness can reach more than 1mm, so as to show that the method provided by the present invention has the advantages.
The foregoing description is only of the preferred embodiments of the present invention and is not intended to limit the scope of the invention; equivalent changes and modifications are intended to be included within the scope of the present invention without departing from the spirit and scope thereof.

Claims (7)

1. A method for sintering and coating a polymer material on a metal surface by using a laser, which is characterized by comprising the following steps:
a. grinding the particle size of the polymer material powder to 40-90 mu m by a ball mill;
b. focusing and scanning a metal substrate by using a laser source to generate a plurality of microstructures on the surface of the metal substrate, wherein the microstructures are arranged at intervals, the distance between the microstructures is 1mm, the pulse frequency of the laser is 0.5-0.75kHz, the pulse width is 750 mu s, the wavelength range is 400-11000 nm, the power is 150W, the scanning speed is 20mm/s, and the scanning range is 100mm multiplied by 100mm;
c. and spreading the polymer material powder on the surface of the metal substrate by a powder spreading system, and directly irradiating the metal substrate with the polymer material powder by using a laser as a heat radiation light source for sintering.
2. The method of claim 1, wherein the polymer powder is one of polylactic acid (PLA), resin (ABS), polyamide (Nylon) -6, polyamide (PA) 66 (Nylon-66), polyvinyl alcohol (PVA), polystyrene (PS), and acryl (PMMA).
3. The method of claim 1, wherein the polymer powder is a nylon-based mixed polymer powder formed from one of copper, aluminum, zinc, gold, silver, iron and nickel.
4. The method of claim 1, wherein the polymer powder is a nylon-based mixed polymer powder formed from one of diamond, graphite, carbon fiber and graphene.
5. The method of claim 1, wherein the polymer powder is a mixed polymer powder formed from one of nylon-based mixed alumina, aluminum nitride, silicon carbide, magnesium oxide and silicon dioxide.
6. The method of claim 1, wherein the metal substrate is one of an iron-based, nickel-based, cobalt-based, chromium-based, molybdenum-based, aluminum-based, and copper-based alloy material.
7. The method of claim 1, wherein the polymeric powder has a thickness of 0.2 to 10 a mm a after sintering.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3437983C1 (en) * 1984-10-17 1986-03-20 Eisen- und Stahlwerk Pleissner GmbH, 3420 Herzberg Method for applying a metallic protective film onto a metallic substrate
CN1196401A (en) * 1997-04-17 1998-10-21 哈尔滨工业大学 Low-temp. method and device for preparation of large area eka-diamond carbon film
CN102380711A (en) * 2010-09-01 2012-03-21 中国科学院光电研究院 Selective sintering laser processing system
CN103665831A (en) * 2012-08-28 2014-03-26 Ems专利股份公司 Polyamide moulding material and its application
CN104742310A (en) * 2013-12-31 2015-07-01 比亚迪股份有限公司 Plastic-metal composite and preparation method thereof
CN109877341A (en) * 2019-02-21 2019-06-14 武汉大学 A kind of smelting process and its patterned method of nano-metal particle

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3437983C1 (en) * 1984-10-17 1986-03-20 Eisen- und Stahlwerk Pleissner GmbH, 3420 Herzberg Method for applying a metallic protective film onto a metallic substrate
CN1196401A (en) * 1997-04-17 1998-10-21 哈尔滨工业大学 Low-temp. method and device for preparation of large area eka-diamond carbon film
CN102380711A (en) * 2010-09-01 2012-03-21 中国科学院光电研究院 Selective sintering laser processing system
CN103665831A (en) * 2012-08-28 2014-03-26 Ems专利股份公司 Polyamide moulding material and its application
CN104742310A (en) * 2013-12-31 2015-07-01 比亚迪股份有限公司 Plastic-metal composite and preparation method thereof
CN109877341A (en) * 2019-02-21 2019-06-14 武汉大学 A kind of smelting process and its patterned method of nano-metal particle

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