CN111250871B - Amorphous alloy coloring method, amorphous alloy and application thereof - Google Patents
Amorphous alloy coloring method, amorphous alloy and application thereof Download PDFInfo
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- CN111250871B CN111250871B CN202010160275.7A CN202010160275A CN111250871B CN 111250871 B CN111250871 B CN 111250871B CN 202010160275 A CN202010160275 A CN 202010160275A CN 111250871 B CN111250871 B CN 111250871B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/36—Removing material
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/14—Working by laser beam, e.g. welding, cutting or boring using a fluid stream, e.g. a jet of gas, in conjunction with the laser beam; Nozzles therefor
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C45/00—Amorphous alloys
- C22C45/001—Amorphous alloys with Cu as the major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/08—Amorphous alloys with aluminium as the major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C45/00—Amorphous alloys
- C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
Abstract
The invention provides an amorphous alloy coloring method, which comprises the step of processing the surface of an amorphous alloy by nanosecond or picosecond laser in the air or in a protective gas environment, wherein the processed surface of the amorphous alloy has a color in a visible light range. Also provides amorphous alloy and application thereof. The method has the advantages of high laser coloring speed, low price and capability of realizing high-flux coloring treatment; the method is simple and easy to implement; the color is controllable, and the surface color of the amorphous alloy can be controlled by adjusting laser parameters; the product has no size limitation and can process large-area amorphous alloy materials; amorphous alloy products having two-dimensional or three-dimensional complex shapes can be processed.
Description
Technical Field
The invention belongs to the field of amorphous alloy, and particularly relates to an amorphous alloy coloring method, an amorphous alloy and application thereof.
Background
Amorphous alloys, i.e., amorphous metal materials, have been receiving wide attention because of their excellent properties such as high strength, high hardness, high elasticity, and high wear resistance, and are being popular and receiving much attention in the market as they can be used as small-sized structural material members such as sports equipment, electronic products, acoustic materials, wear-resistant coatings, and the like. Since colored metal surfaces are becoming a new aesthetic requirement for consumers, the development of surface coloring technology of amorphous alloys is becoming a heat generation point of the present invention. The existing metal surface coloring technology can be divided into the following types: doping, coating, oxidation, and photolithography of nanostructures. However, the existing method has many problems, including that the doping reduces the material performance, the coating is easy to crack, the oxidation process is complex and has poor universality, and the nano-structure photoetching consumes time and is difficult to meet the requirement of large-scale industrial production.
Surface plasmons are a novel color generation mechanism. Under the action of light waves (electromagnetic waves), surface plasmons are generated on the metal surface with the nano structure, and when the frequency of incident light is the same as the oscillation frequency of the metal surface plasmons, free electrons on the metal surface resonate with the incident light waves, so that color is generated. The color produced by the surface plasmon polariton method is stable and fadeless, the color resolution is high, and the problems in other coloring mechanisms can not be caused.
Disclosure of Invention
Therefore, the present invention aims to overcome the defects in the prior art and provide an amorphous alloy coloring method, an amorphous alloy and applications thereof.
In order to achieve the above object, a first aspect of the present invention provides an amorphous alloy coloring method, the method comprising treating an amorphous alloy with a nanosecond or picosecond laser in air or under a protective atmosphere, the treated surface of the amorphous alloy having a color in a visible light range;
preferably, the protective atmosphere is selected from one or more of: nitrogen, helium.
The method according to the first aspect of the present invention, wherein the method generates a nanoporous structure on the surface of the amorphous alloy using nanosecond or picosecond laser processing;
preferably, the laser power is 100W or less, preferably 50W or less, most preferably 20W.
The method according to the first aspect of the present invention, wherein the amorphous alloy is selected from one or more of: amorphous thin film, amorphous strip, amorphous block.
The method according to the first aspect of the present invention, wherein the composition of the amorphous alloy is selected from one or more of: zr, Cu, Al, Ni, Y, Co, La, Ti, Mg, Ag.
The method according to the first aspect of the present invention, wherein the method comprises one or more laser treatments of the surface of the amorphous alloy.
The method according to the first aspect of the present invention, wherein the surface treatment is a scribe face treatment and/or a fill scribe face treatment.
The method according to the first aspect of the present invention, wherein the nanosecond laser processing parameters are:
the scanning speed is 10-5000 mm/s;
power factor: 50-100%;
defocusing or over-focusing amount is 1-10 mm;
the laser pulse width is 1-250 ns;
the repetition frequency is 10-400 kHz; and/or
Line spacing: 0.001 to 0.01 mm.
The method according to the first aspect of the invention, wherein the picosecond laser treatment parameters are:
the scanning speed is 10-8000 mm/s;
the power factor is 50% -100%;
defocusing or over-focusing amount is 1-10 mm;
the repetition frequency is 200-2000 kHz;
the laser pulse width is 7 ps; and/or
Line spacing: 0.001 to 0.01 mm.
A second aspect of the present invention provides an amorphous alloy that is colored according to the coloring method of the first aspect.
The present invention belongs to the coloring technology of amorphous alloy material. In particular to a method for coloring the surface of the amorphous alloy by treating the surface of the amorphous alloy with nanosecond or picosecond laser.
The invention aims to provide a method which has low cost and high efficiency and can color the surface of amorphous alloy.
Compared with the prior art, the invention has the following characteristics:
the invention can process film samples of several microns, has the processing thickness of less than 1 micron, extremely high thickness resolution ratio and wide application range, can process films, strips and blocks comprising amorphous alloys and has no amorphous alloy size limitation. In the existing laser high-power thermal effect quenching coloring technology, the processed thickness of a sample reaches dozens of micrometers, so that a film sample cannot be processed.
The nanosecond laser selected by the invention has the spot diameter range of 0.05-0.1 mm, and because the spot diameter is small, although the laser output power is only 20W (compared with the prior art, the laser output power can be reduced by nearly 100 times), the nanosecond laser can generate extremely high power density (5.1 multiplied by 10)9～1×1010) The sample is rapidly melted into liquid state, and the laser induces the amorphous alloy and air to generate high-temperature dissolution and cooling desolventization.
The amorphous alloy of the invention has a plurality of color types after being colored, and can show most of colors (black, red, brown, pink, gray, golden, green, blue, yellow and purple) in the visible light range. The existing high-power laser coloring technology can only generate two colors of blue and golden.
The invention also utilizes picosecond laser treatment, which can lead the amorphous alloy area after treatment to keep amorphous state and still keep the excellent characteristics of high strength, corrosion resistance, wear resistance and the like of the amorphous alloy.
The invention realizes a plurality of colors of the amorphous alloy, has simple processing environment, can generate a plurality of unexpected colors only in the air, but has limited color generation in the prior high-power laser and complex required environment.
The invention has the advantages of high processing precision, high processing speed and high-flux processing effect.
The invention utilizes nanosecond laser with short pulse width to process amorphous alloy, thereby generating a nano structure with multiple sizes, and light waves excite plasmons to generate colors. Compared with the color generated by the quenching heat effect of a large-power laser spot (1.8-15 mm) in the prior art and the surface grating nano-structure which can be generated by photoetching on the metal surface by using femtosecond laser, the principles are completely different, and the color generated by the invention has extremely high resolution.
Based on the characteristics, the invention is different from the existing high-power laser coloring technology, and is a novel, effective and practical amorphous alloy coloring technology.
The purpose of the invention is realized by the following technical scheme:
1. firstly, preparing amorphous alloy films, strips and blocks with different component systems, and then scanning the surface of an amorphous alloy sample by using nanosecond laser. By adjusting the process parameters of nanosecond laser, a uniform nano porous structure with stable size and spacing is spontaneously formed on the surface of an amorphous alloy sample, so that the surface plasmons are excited by light to generate different colors. The essential difference between the method and the traditional method lies in the spontaneous preparation of the nano porous structure, namely, the air dissolved in the metal melting liquid under high-energy laser is utilized to spontaneously precipitate in the cooling of a sample to generate holes, so that the method is different from the traditional porous photoetching method designed according to a program and the processing method of high-power laser quenching in the prior art. The laser process parameters involved in the new method include matching adjustment of scanning speed, laser power, defocus or defocus amount, laser pulse width, repetition frequency, line spacing, and the like. By utilizing a structural characterization means, the size and the distance of the surface porous structures of samples with different colors can be detected, the relationship between the nano porous structures and the colors is determined, and the color regulation and control of laser are realized through the corresponding relationship. The surface of the amorphous alloy is treated by optimizing process parameters, and the color can be regulated and controlled on the surfaces of amorphous alloy films, strips and blocks with different components.
2. Preparing amorphous alloy films, strips and blocks with different component systems, then carrying out scribing scanning treatment on the surface of an amorphous alloy sample by utilizing picosecond laser, wherein the surface of the amorphous alloy can generate different colors by adjusting laser process parameters, and the amorphous alloy can keep the amorphous state.
The invention provides a coloring method of the amorphous alloy, which comprises the following steps:
1. preparing amorphous alloy film, strip or block samples.
2. The amorphous alloy film, strip or block is fixed by a certain mechanical device or adhesive tape, so that the sample is ensured to be firm and the surface is polished to be flat during laser processing.
3. Nanosecond or picosecond laser is used, and linear scanning, linear filling, concentric circle or square-shaped filling and wiring modes are adopted.
4. And measuring the area of the colored sample by using an optical microscope and a scanning electron microscope.
The method of the invention uses nanosecond or picosecond laser and adopts scribing or filling treatment to treat the amorphous alloy film, the strip and the block, and the treated surface can realize most colors in the visible light range.
The method can be used for coloring samples with different amorphous alloy components by nanosecond or picosecond laser.
The invention provides a method for processing amorphous alloy coloring by laser, which can process amorphous alloy samples with different sizes, including but not limited to amorphous films, strips and blocks, by nanosecond or picosecond laser.
The method of the present invention may utilize nanosecond or picosecond laser processing of amorphous thin films deposited on silicon substrates, including but not limited to the use of silicon as the substrate.
The processing mode adopted by the method is linear processing and filling processing with line spacing. Including but not limited to the above-described path patterns.
The method can change the times of laser treatment to adjust the surface color. The laser treatment can be performed once or multiple times.
The method of the present invention may have, but is not limited to, the following beneficial effects:
1. the laser coloring speed is high, the price is low, and high-flux coloring treatment can be realized;
2. the method is simple and easy to implement;
3. the color is controllable, and the surface color of the amorphous alloy can be controlled by adjusting laser parameters;
4. the product has no size limitation and can process large-area amorphous alloy materials;
5. amorphous alloy products having two-dimensional or three-dimensional complex shapes can be processed.
Drawings
Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
fig. 1 shows a nanosecond laser coloring matter diagram of the zirconium-based amorphous alloy thin film in example 1.
Fig. 2 shows an optical microscope image of the zirconium-based amorphous alloy thin film after nanosecond laser coloring in example 1.
Fig. 3 shows a scanning electron microscope image of the zirconium-based amorphous alloy thin film after nanosecond laser coloring in example 1.
Fig. 4 shows a chinese fu paper-cut pattern of the zirconium-based amorphous alloy bulk after nanosecond laser coloring in example 4.
Fig. 5 shows an optical microscope image of the bulk of the zirconium based amorphous alloy after nanosecond laser coloring in example 4.
Detailed Description
The invention is further illustrated by the following specific examples, which, however, are to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.
This section generally describes the materials used in the testing of the present invention, as well as the testing methods. Although many materials and methods of operation are known in the art for the purpose of carrying out the invention, the invention is nevertheless described herein in as detail as possible. It will be apparent to those skilled in the art that the materials and methods of operation used in the present invention are well within the skill of the art, provided that they are not specifically illustrated.
The reagents and instrumentation used in the following examples are as follows:
reagent:
silicon substrate, available from syn-living electronics technologies, ltd;
Al86Ni7Y5Co1La1amorphous alloy ribbon, Zr65Cu15Ni10Al10Bulk amorphous alloy sample, Ti34Zr11Cu47Ni8Amorphous alloy block, Mg54Cu28Ag7Y11Amorphous alloy block, Zr65Cu15Ni10Al10The amorphous alloy sheet is prepared by the first inventor by the method recognized in the field, and the element simple substance is purchased from Jiaming platinum industry GmbH.
The instrument comprises the following steps:
a nanosecond laser, which is purchased from Jerpt photoelectricity corporation of Shenzhen, model JPT YDFLP-20-M6 +;
a dual-ion beam sputter coating machine, which is purchased from ADVANCED ion beam technology research institute, model LDJ-2A-F100-100;
optical microscope, available from Leica, germany, model DM 7200M;
a desktop scanning electron microscope, available from Phenom world, model number Phenom XL scanning, the Netherlands;
picosecond laser, available from Phootonics Industries, USA, model RX-355-20.
Example 1
This example is for illustrating the coloring method of the amorphous alloy according to the present invention.
Selecting ion beam sputtering on a silicon substrate under vacuum degree of 2.4 × 10-4In the Pa argon gas environment, the main cathode current is 6.5A, the screen grid voltage is 50V, the ion beam current is 80mA, the ion energy is 750eV, the working time is 2350s, and four times of plating are carried out at the same time. Zr with the thickness of 1.5 microns is prepared according to the parameters46Cu46Al8Amorphous alloy film (in atomic percentage). The surface of the film has a mirror surface with smooth flatness at an atomic level. The film sample is placed on a laser processing platform, the mirror surface faces upwards, a nanosecond laser is utilized, the output power of the nanosecond laser is 20W, the wavelength is 1064nm, the diameter of a focusing light spot is 0.05mm, and the pulse width range is as follows: 2-250 ns, and performing scanning scribing surface treatment or filling scribing treatment (the routing path is not limited to a straight line) in the air. Selecting the adjusted laser process parameters as a fixed defocusing amount of 4mm, selecting a power factor of 50-100%, a scanning speed of 10-5000 mm/s, a repetition frequency of 10-400 kHz, and a line spacing: 0.001 to 0.01 mm. After nanosecond laser treatment, the surface of the amorphous alloy film shows different colors, as shown in table 1.
TABLE 1 relationship between color of amorphous alloy thin film surface and treatment method in example 1
Fig. 1 is a color picture of a zirconium-based amorphous alloy thin film after laser treatment. FIG. 2 is a surface view of a colored sample obtained and characterized by an optical microscope. Fig. 3 shows that the colored surface is observed by a scanning electron microscope, and samples with different colors have different nano-porous microstructures. The result shows that the nanosecond laser can color the surface of the zirconium-based amorphous alloy film sample. The coloring mechanism includes: firstly, surface plasmon resonance excited by a nano porous microstructure; secondly, the surface generates an oxide film to generate thin film interference.
Example 2
This example is for illustrating the coloring method of the amorphous alloy according to the present invention.
Selecting ion beam sputtering on a silicon substrate under vacuum degree of 2.4 × 10-4Under the environment of Pa argon, the main cathode current is 6.5A, the screen grid voltage is 50V, the ion beam current is 80mA, the ion energy is 750eV, the working time is 2350s, the same time is adopted for 6 times of plating, and the Zr with the thickness of 2 microns is prepared46Cu46Al8Amorphous alloy film (in atomic percentage). The surface of the film has a mirror surface with smooth flatness at an atomic level. The film sample was placed on a laser processing platform with the mirror facing up, using a picosecond laser with an output power of 20W, a wavelength of 355nm, a focused spot diameter of 0.02mm, and a pulse width of 7 ps. The defocusing amount is 1mm through fixation, a power factor is selected to be 50-100%, the scanning speed is 10-8000 mm/s, the repetition frequency is 200-2000 kHz, and the line spacing is as follows: 0.001 to 0.01 mm. The assay was the same as in example 1. After picosecond laser treatment, the surface of the amorphous alloy film presents different colors and keeps amorphous state. The resulting color is related to the process parameters as shown in table 2.
TABLE 2 relationship between color of amorphous alloy thin film surface and treatment method in example 2
Example 3
This example is for illustrating the coloring method of the amorphous alloy according to the present invention.
Selecting Al with the thickness of 40 microns86Ni7Y5Co1La1And (3) carrying out ultrasonic cleaning on the amorphous alloy strip by using alcohol, and then processing the surface of the amorphous alloy strip by using nanosecond laser. The treatment and detection were carried out as described in example 1. The resulting color is related to the process parameters as shown in table 3.
TABLE 3 relationship between color of amorphous alloy strip surface and treatment method in example 3
Example 4
This example is for illustrating the coloring method of the amorphous alloy according to the present invention.
Selecting Zr with the thickness of 2mm65Cu15Ni10Al10An amorphous alloy bulk sample was polished on its surface using sandpaper nos. 600, 800, 1,000, and 1,200 in this order, then polished with a 1 micron diamond particle polishing paste to a mirror surface smooth, ultrasonically cleaned with alcohol, and then treated with a nanosecond laser. The processing and effect detection method was as in example 1. The resulting color is related to the process parameters as shown in table 4.
TABLE 4 relationship between color of amorphous alloy bulk surface and treatment method in example 4
Fig. 4 shows a chinese fu paper-cut pattern of the zirconium-based amorphous alloy bulk after nanosecond laser coloring in example 4. Fig. 5 shows an optical microscope image of the bulk of the zirconium based amorphous alloy after nanosecond laser coloring in example 4.
Example 5
This example is for illustrating the coloring method of the amorphous alloy according to the present invention.
Ti with the thickness of 2mm is selected34Zr11Cu47Ni8Amorphous alloy block. Firstly, grinding the prepared amorphous alloy sample by using No. 600, No. 800, No. 1,000 and No. 1,200 sand paper in sequence, polishing the sample by using 1 micron diamond particle polishing paste until the mirror surface is smooth, carrying out ultrasonic cleaning by using alcohol, and then carrying out nanosecond laser treatment. The treatment and detection were carried out as described in example 1. The resulting color is related to the process parameters as shown in table 5.
TABLE 5 relationship between color of amorphous alloy bulk surface and treatment method in example 5
Example 6
This example is for illustrating the coloring method of the amorphous alloy according to the present invention.
Selecting Mg with the thickness of 2mm54Cu28Ag7Y11Amorphous alloy block. Firstly, grinding the prepared amorphous alloy sample by using No. 600, No. 800, No. 1,000 and No. 1,200 sand paper in sequence, polishing the sample by using 1 micron diamond particle polishing paste until the mirror surface is smooth, carrying out ultrasonic cleaning by using alcohol, and then carrying out nanosecond laser treatment. The treatment and detection were carried out as described in example 1. The resulting color is related to the process parameters as shown in table 6.
TABLE 6 relationship between color of amorphous alloy bulk surface and treatment method in example 6
Example 7
This example is for illustrating the coloring method of the amorphous alloy according to the present invention.
Selecting Zr with the thickness of 2mm65Cu15Ni10Al10On the surface of the amorphous alloy plate (by atom percentage), firstly, the prepared amorphous alloy sample is sequentially ground by No. 600, No. 800, No. 1,000 and No. 1,200 sand papers, polished by 1 micron diamond particle polishing paste to be smooth in mirror surface, and then subjected to scribing or filling scribing surface treatment (the path of the line is not limited to a straight line) on the amorphous film sample in the air by picosecond laser after being subjected to ultrasonic cleaning by alcohol. The processing and detection method is as in example 2. As shown in table 7.
TABLE 7 relationship between color and treatment method of surface of amorphous alloy sheet in example 7
The above examples show the effectiveness and feasibility of nano/picosecond lasers for coloring amorphous alloy surfaces. The amorphous alloy and air are induced by laser to generate high-temperature dissolution and cooling desolventization, so that uniform nano porous structures with different sizes and intervals are generated on the surface of a sample, and surface plasmons are excited to generate colors. The method is suitable for coloring the surfaces of amorphous alloy samples with different sizes and shapes, including films, strips and blocks. Therefore, the laser processing method can be suitable for the surface coloring of all amorphous alloy components so as to meet the appearance application requirements of more amorphous alloy products.
Although the present invention has been described to a certain extent, it is apparent that appropriate changes in the respective conditions may be made without departing from the spirit and scope of the present invention. It is to be understood that the invention is not limited to the described embodiments, but is to be accorded the scope consistent with the claims, including equivalents of each element described.
Claims (11)
1. The amorphous alloy coloring method is characterized by comprising the steps of processing an amorphous alloy by nanosecond or picosecond laser in air or in a protective atmosphere, wherein the surface of the processed amorphous alloy has a color in a visible light range; wherein the content of the first and second substances,
the method utilizes nanosecond or picosecond laser processing to generate a nano porous structure on the surface of the amorphous alloy; the surface treatment mode is scribing surface treatment and/or filling scribing surface treatment; air dissolved in the metal melting liquid under laser is spontaneously separated out in the sample cooling to generate holes;
under the action of light waves, enabling the metal surface with the nano structure to generate surface plasmons, and when the frequency of incident light is the same as the oscillation frequency of the metal surface plasmons, free electrons on the metal surface resonate with the incident light waves, so that color is generated;
the laser power is 100W or less.
2. The amorphous alloy coloring method according to claim 1, wherein said protective atmosphere is selected from one or more of: nitrogen, helium.
3. The method of claim 1, wherein the laser power is 50W or less.
4. The method of claim 1, wherein the laser power is 20W.
5. The amorphous alloy coloring method according to claim 1, wherein said amorphous alloy is selected from one or more of: amorphous thin film, amorphous strip, amorphous block.
6. The method of coloring an amorphous alloy according to claim 1, wherein the composition of the amorphous alloy is selected from one or more of: zr, Cu, Al, Ni, Y, Co, La, Ti, Mg, Ag.
7. The method of claim 1, wherein the method comprises one or more laser treatments of the surface of the amorphous alloy.
8. The amorphous alloy coloring method according to claim 1, wherein said nanosecond laser processing parameters are:
the scanning speed is 10-5000 mm/s;
power factor: 50-100%;
defocusing or over-focusing amount is 1-10 mm;
the laser pulse width is 1-250 ns;
the repetition frequency is 10-400 kHz; and/or
The line spacing is 0.001-0.01 mm.
9. The method of coloring an amorphous alloy according to claim 1, wherein the picosecond laser processing parameters are:
the scanning speed is 10-8000 mm/s;
the power factor is 1% -100%;
defocusing or over-focusing amount is 1-10 mm;
the repetition frequency is 200-2000 kHz;
the laser pulse width is 7 ps; and/or
The line spacing is 0.001-0.01 mm.
10. An amorphous alloy, characterized in that it is colored according to the amorphous alloy coloring method as recited in any one of claims 1 to 9.
11. A method for producing an amorphous alloy, characterized in that the method comprises the method for coloring an amorphous alloy according to any one of claims 1 to 9.
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| CN101569962A (en) * | 2009-04-30 | 2009-11-04 | 苏州德龙激光有限公司 | Double light path green light micropore processing device |
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