Patent Application
20180185958
The present invention relates to methods of, and apparatus for, laser blackening surfaces.
Laser blackening of a surface may refer to the application of laser radiation to a surface to modify the surface so as to reduce the reflectivity of the surface, for example to reduce the reflectivity of the surface for visible light.
There is a growing interest in marking of metals, for example in the creative industries or for security/identification applications. Laser marking is used widely in the manufacture of automotive steels, medical glasses, smartphone materials etc to create either a black or white mark.
It is desired to provide improved or at least alternative methods for laser blackening of surfaces.
In a first aspect of the invention there is provided a method of blackening a surface, comprising:
The use of such power densities may change the reflectivity or emissivity of the surface at visible or infrared wavelengths. The blackening may be at visible or infrared wavelengths, or at other suitable wavelengths of electro-magnetic radiation. Optionally at least some of the pulses may be interleaved with lower power laser pulses.
Optionally the power density may be in a range 1 GW/cm2 to 45 GW/cm2 or 0.1 TW/cm2 to 2 TW/cm2, optionally in a range 2 GW/cm2 to 30 GW/cm2 or 0.3 TW/cm2 to 2 TW/cm2, optionally in a range 4 GW/cm2 to 10 GW/cm2 or 0.4 TW/cm2 to 1.5 TW/cm2, further optionally in a range 0.38 TW/cm2 to 0.6 TW/cm2, 0.16 TW/cm2 to 0.54 TW/cm2.
By using laser pulses having such power densities, a periodic arrangement of structures that provides a surface with desired properties may be obtained. For example a surface having a desired value or range of values of emissivity or reflectivity, or a desired blackening, at a wavelength or range of wavelengths of interest may be obtained.
The laser pulses may have a duration less than a thermal relaxation time of the material of the surface. Alternatively the laser pulses may have a duration larger than the thermal relaxation time. The laser pulses may have a duration such that the electrons and the atomic lattice of the material of the surface have a substantially different temperature substantially throughout application of the laser pulses. The laser pulses may have a duration such that material of the surface is at least one of evaporated or vaporised or removed without substantial melting and/or flowing of the surface. The laser pulses may have a duration such that some material of the surface is at least one of evaporated or vaporised or removed without substantial melting and/or flowing of the remaining material of the surface.
A pulse duration of the laser pulses may be in a range 200 femtoseconds (fs) to 1000 picoseconds (ps) or may be in a range 1000 ps to 200 nanoseconds (ns).
The periodic arrangement of structures on the surface may comprise a periodic series of peaks and troughs substantially parallel to each other, and the peaks may be substantially flat on top and/or may be rounded on top and/or may have substantially no pointed and/or or sharp regions on top. The peaks may substantially have a top hat shape and/or a truncated pyramidal shape, for example a top hat shape and/or a truncated pyramidal shape in cross-sectional profile. Thus, for example, a desired value of electron work function and/or desired electron or photon trapping properties may be obtained. The peaks may extend in a longitudinal direction and may be referred to as ridges.
The peak to trough distance for at least some of the peaks, and/or an average or median peak to trough distance, may be in a range 500 nm to 500 μm, optionally in a range 500 nm to 100 μm, optionally in a range 100 μm to 500 μm, optionally in a range 5 μm to 100 μm, optionally in a range 20 μm to 80 μm, optionally in a range 1 μm to 60 μm, optionally in a range 30 μm to 60 μm.
The periodic arrangement of structures may comprise a cross-hatched arrangement or an arrangement of substantially parallel lines of peaks and troughs (for example, ridges and valleys) substantially without cross-hatching. The periodic arrangement of structures may, for example, be produced by a single pass of a laser source that provided the laser radiation.
The surface may be on an at least one underlying layer (for example, at least one of steel, stainless steel) and the laser radiation may be such as to substantially not remove or move material of the surface in such a way as to expose the underlying layer.
In a further aspect of the invention, which may be provided independently, there is provided a laser treated surface comprising a laser-formed periodic arrangement of structures on the surface, wherein at least one of:
In a further aspect of the invention, which may be provided independently, there is provided an apparatus for blackening a surface, comprising:
In a further aspect of the invention, there is provided a method of laser blackening a surface, comprising:
The surface may be the surface of a target.
The pulse duration may be in a range 1 ps to 100 ps or 1 ns to 100 ns. The pulse duration may be in a range 1 ps to 50 ps or 1 ns to 100 ns. The pulse duration may be in a range 5 ps to 500 ps or 5 ns to 200 ns
The laser radiation may comprise a pulsed laser beam that has a focal spot diameter on the surface in a range 1 μm to 50 μm or in a range 1 μm to 100 μm.
The pulsed radiation may have a pulse repetition rate in a range 10 kHz to 1 MHz.
An average power of the laser radiation may be in a range 0.3 W to 100 W, or in a range 0.3 W to 50 W, or in a range 0.3 W to 2 W, or in a range 1 W to 30 W, or in a range 1 W to 20 W, or in a range 1 W to 5 W, or in a range 0.1 W to 1 W, or in a range 0.1 W to 2 W, or in a range 0.3 W to 5 W.
The applying of the laser radiation to the surface may comprise scanning (for example, undirectionally or bidirectionally) a pulsed laser beam over the surface, and a scan speed for the scanning may be in a range 1 mm/s to 200 mm/s, optionally in a range 1 mm/s to 100 mm/s.
The scanning of the pulsed laser beam over the surface may be repeated between 2 and 20 times, or between 2 and 10 times, or may be performed once.
An angle of incidence of the laser radiation to the surface may be in a range from 0 to 30 degrees. The angle of incidence of the laser radiation to the surface may be in a range from 90 degree to 60 degrees.
A wavelength of the radiation may be in a range 100 nm to 2,000 nm, optionally 532 nm or 528 nm or 1030 nm or 1064 nm or 1070 nm.
The structures may comprise peaks and troughs. The periodic arrangement of structures may comprise a periodic series of peaks and troughs. The peaks and troughs may be substantially parallel to each other.
The periodic arrangement of structures may comprise a first series of peaks and troughs arranged in a first direction, and a second series of peaks and troughs arranged in a second, different direction. The first and second directions may be substantially orthogonal. The first series of peaks and troughs and the second series of peaks and troughs may intersect such that the periodic arrangement of structures comprises a cross-hatched arrangement.
A period of the periodic arrangement may be in a range 0.5 μm to 100 μm. The separation of adjacent peaks (or troughs) of the periodic structure may be in a range 0.5 μm to 100 μm. A hatch distance of the cross-hatched arrangement may be in a range 0.5 μm to 100 μm.
The surface may comprise or form part of a surface of, or a surface of a component of, for example, one or more of a computing device, an energy storage device, a communications device, a security device, a medical device, an identification device, a financial transaction device, an optical device, a storage device.
The method may comprise applying the laser radiation to the surface to produce a periodic arrangement of structures on the surface over a selected area. The selected area may comprise or represent one or more of an image, an identifier, a marker. The marker may comprise a security marker.
The method may comprise applying the laser radiation such as to produce the periodic arrangement of structures on the surface to form at least one of an image, an identifier, a marker, a security marker.
The laser radiation may be such that the applying of the laser radiation to the surface comprises producing further structures. The further structures may be smaller than the structures of the periodic arrangement of structures.
That feature may be particularly important, so in another aspect of the invention, which may be provided independently, there is provided a method of laser blackening a surface, comprising:
The further structures may comprise further periodic structures. The further structures may comprise ripples. The further structures may comprise nano-ripples. The further structures may be further periodic structures. The further structures may comprise laser induced periodic surface structures (LIPPS). The further structures may have a periodicity in a range 10 nm to 1 μm, optionally in a range 100 nm to 1 μm.
The further structures may cover at least part of the periodic array of structures. The further structures may be formed in the troughs and/or on the peaks of the periodic arrangement of structures.
The surface may be a metal surface. The surface and/or target may comprise copper, aluminium, stainless steel or titanium. The metal of the metal surface may be a metal selected from copper, aluminium, stainless steel, or titanium. The surface may form part of a laminated structure, for example a laminated target, for instance comprising one of copper, aluminium, stainless steel, titanium and at least one other material, and/or a laminated structure comprising at least two of copper, aluminium, stainless steel, titanium.
The surface may be the surface of a foil. The target may be a foil.
An average or peak fluence or other property of the laser radiation may be above an ablation threshold of the surface and within 100% to 300%, optionally 105%, optionally 102%, optionally 101% of the ablation threshold.
The radiation may be such as to at least partially melt the surface and/or to provide flow of material at the surface.
The pulses may be such that, for each pulse, a plasma is formed at the surface. The plasma may, for example, have substantially the same density as underlying material of the surface. The method may comprise applying the radiation using a solid-state laser, optionally the solid state laser comprises a Nd:YVO4 or Nd:YAG or Yb:YAG or Nd:KGW or Nd:KYW or Yb:KGW or Yb:KYW laser, or a pulsed fibre laser, optionally a Yb, Tm or Nd pulsed fibre laser. The applied radiation may comprise the fundamental wavelengths of operation such lasers or their second or third harmonics.
In a further aspect of the invention, which may be provided independently, there is provided an apparatus for laser blackening a surface, comprising:
In another aspect of the invention, which may be provided independently there is provided a laser treated surface comprising a periodic arrangement of structures on the surface formed using a method according to any other aspect.
In a further aspect of the invention, which may be provided independently, there is provided a laser treated surface comprising a laser-formed periodic arrangement of structures on the surface and further laser-formed structures on the surface.
The further structures may comprise further periodic structures. The further structures may comprise ripples. The further structures may comprise nano-ripples. The further structures may be further periodic structures. The further structures may comprise laser induced periodic surface structures (LIPPS). The further structures may have a periodicity in a range 10 nm to 1 μm, optionally in a range 100 nm to 1 μm.
The structures may comprise peaks and troughs. The periodic arrangement of structures may comprise a periodic series of peaks and troughs. The peaks and troughs may be substantially parallel to each other.
The periodic arrangement of structures may comprise a first series of peaks and troughs arranged in a first direction, and a second series of peaks and troughs arranged in a second, different direction. The first and second directions may be substantially orthogonal. The first series of peaks and troughs and the second series of peaks and troughs may intersect such that the periodic arrangement of structures comprises a cross-hatched arrangement.
A period of the periodic arrangement may be in a range 0.5 μm to 100 μm or may be in a range 100 μm to 500 μm. The separation of adjacent peaks (or troughs) of the periodic structure may be in a range 0.5 μm to 100 μm. A hatch distance of the cross-hatched arrangement may be in a range 0.5 μm to 100 μm.
The further structures may comprise further periodic structures. The further structures may comprise ripples. The further structures may comprise nano-ripples. The further structures may be further periodic structures. The further structures may comprise laser induced periodic surface structures (LIPPS). The further structures may have a periodicity in a range 10 nm to 1 μm, optionally in a range 100 nm to 1 μm.
The further structures may cover at least part of the periodic array of structures. The further structures may be formed in the troughs of the periodic arrangement of structures.
The surface may comprise or form part of a surface of, or a surface of a component of, for example, one or more of a computing device, a communications device, a security device, a medical device, an identification device, a financial transaction device, an optical device, a storage device.
The periodic arrangement of structures may be arranged on the surface over a selected area. The selected area may comprise or represent one or more of an image, an identifier, a marker. The marker may comprise a security marker.
The surface may be a metal surface. The surface may comprise copper, aluminium, stainless steel or titanium. The metal of the metal surface may be selected from copper, aluminium, stainless steel, titanium. The surface may form part of a laminated structure, for example a laminated target, for instance comprising one of copper, aluminium, stainless steel, titanium and at least one other material, and/or a laminated structure comprising at least two of copper, aluminium, stainless steel, titanium.
In another aspect of the invention, which may be provided independently, there is provided a computing device, an energy storage device, a communications device, a security device, a medical device, an identification device, a financial transaction device, an optical device, a storage device that includes a surface according to any other suitable aspect of the invention.
There is also provided a computing device, a communications device, a security device, a medical device, an identification device, a financial transaction device, an optical device, or a storage device comprising a surface including an image, an identifier, a marker, a security marker formed using a method as claimed or described herein.
In further aspects of the invention there are provided a method, a surface, a structure comprising a surface, an apparatus, a component, a computing device, a communications device, a security device, a medical device, an identification device, a financial transaction device, an optical device, or a storage device as described and/or illustrated herein.
Any feature in any one aspect of the invention may be applied to any other one or more of the aspects of the invention in any appropriate combination.
Embodiments of the invention are further described hereinafter with reference to the accompanying drawings, in which:
The system 2 of
In embodiments, the laser may be one of a Nd:YVO4 or Nd:YAG or Yb:YAG or Nd:KGW or Nd:KYW or Yb:KGW or Yb:KYW laser and the main operating wavelength or one of the second or third harmonics may be used. Alternatively the laser may be a pulsed fibre laser, for example a Yb, Tm or Nd pulsed fibre laser, and the main operating wavelength or one of the second or third harmonics may be used. Any other suitable laser may be used in alternative embodiments. In the embodiment of
The controller may comprise a dedicated controller, or a suitably programmed computer. The controller may be implemented in software, hardware or any suitable combination of hardware and software. In some embodiments, the controller may comprise more ASICs (application specific integrated circuits) or FPGAs (field programmable gate arrays) or other suitable circuitry.
In the embodiment of
In the embodiment of
In operation pulsed laser radiation of desired characteristics is scanned across the surface of the target 10 by the laser 6 under control of the laser controller 4 to produce a periodic arrangement of structures on the surface. For example, in order to form peaks and troughs arranged in parallel rows, the laser beam may be scanned along parallel, spaced-apart paths across the surface to form parallel troughs separated by peaks. Any other suitable arrangements of structures can be formed by suitable scanning of the laser beam over the surface. The laser can be controlled to form the structures over a desired area. The desired area may comprise or represent, for example, one or more of an image, an identifier, a marker. The marker may, for instance, comprise a security marker.
Operating parameters of the laser, and certain equations linking such parameters, can be represented as follows,
Wavelength (λ) [m]
Repetition rate of the laser (γ) [Hz]
Pulse length of the laser (τ) [s]
Average power of the laser (Pavg) [W]—represents the energy flow over one period t
Energy per pulse (Ep) [J]
Fluence of the laser (F) [J/cm2]
Beam spot radius on the target (r) [m]
Beam spot area on the target (A=πr2) [m2]
Number of times surface of the target was scanned by the laser beam (N) dimensionless
Speed at which surface of the target was scanned by the laser beam (V) [m/s]
Number of pulses fired per each spot on the surface of the target (n) [dimensionless]
Time interval between the pulses—one period (t) [s]
Peak Power (Ppeak) [W]—defines the energy flow within a single pulse
Power density or Intensity (I) [W/cm2]
Suitable operating parameters can be selected, for example based on the equations and representations above, to obtain pulsed laser radiation of desired properties, for example a desired power density of the pulses.
Table 1 provides operating parameters of the laser to produce a desired periodic arrangement of structures on the surface, for an embodiment where the surface is copper. Three sets of operating parameters according to an embodiment are provided in table 1. The laser processing of the surface is performed in air in this case.
In some other embodiments where the target is copper, operating parameters are selected as follows:
Table 2 provides operating parameters of the laser to produce a desired periodic arrangement of structures on the surface, for an embodiment where the surface is aluminium.
In some other embodiments where the target is aluminium, operating parameters are selected as follows:
Table 3 provides operating parameters of the laser to produce a desired periodic arrangement of structures on the surface, for an embodiment where the surface is stainless steel.
In some other embodiments where the target is stainless steel, operating parameters are selected as follows:
The power density (intensity) used for stainless steel may be selected to be in a range from 0.01 TW/cm2 to 1 TW/cm2, for example by suitable choice of wavelength and of other operating parameters such as those recited in paragraphs a) or b) above.
In a further embodiment, stainless steel samples were laser processed by the apparatus of
The samples were referred to by the references PS10HDS (picosecond pulsed laser treatment), PS15HDS (picosecond pulsed laser treatment), PS15HD+ (picosecond pulsed laser treatment), NSHS (nanosecond pulsed laser treatment providing fluence of 4.8 GW/cm2), and NSPS (nanosecond pulsed laser treatment providing fluence of 5.5 GW/cm2). The samples were samples of 316LN steel that were laser-processed using the parameters as set out in the table.
A further stainless steel sample referred to as NSHSD was also processed. The same processing parameters were used for the NSHSD sample as for the NSHS sample, as provided in Tables 7 and 8, except that the laser writing was unidirectional rather than bidirectional. In an example of bidirectional writing the laser writes a line from (say) left to right and then the next line is from right to left. In an example of unidirectional writing the laser writes a line from, say, left to right and then the next line is also from left to right. Further parameters for the NSPS, NSHS and NSHSD samples are provided in Table 8 below.
Each of the PS10HDS, PS15HDS, PS15HD+, NSHS, NSPS, and NSHD samples were of diameter 20 mm, and emissivity measurements were performed on the samples. The samples were stored in silk paper in a plastic box prior to the measurements being performed. Emissivity measurements were also performed on two stainless steel samples (of stainless steel type 304LN and 316LN) referred to as the 304LN and 316LN samples, that were not subject to laser processing and were used as reference samples.
The emissivity of the samples was measured using infra-red light with wavelength from 2.5 μm to 25 μm. Each sample was measured several times turning it randomly to measure at different incidence angles (incident light in respect to the laser structure).
The bottom two lines plotted on the graph of
As can be seen from
Results of emissivity measurements for the PS10HDS and PSA5HD+ samples are shown in
As can be seen from
Samples a) of
Sample b) of
SEM images of regions of the surface of sample b) are also shown in
Appendix 1 provides further operating parameters of the laser to produce a desired periodic arrangement of structures on the surface according to further embodiments.
Without wishing to be bound by theory, and without limitation to the scope of protection, the following comments are provided which relate to processes which may occur in relation to at least some embodiments.
Laser engineering provides an overarching methodology that provides for the formation of periodic structures according to embodiments. Precision laser engineering is expected to excite free electrons within metals, vibrations within insulators, and indeed both types of excitations within semiconductors. The mechanisms by which lasers can engineer materials include the following:
(i) Photo-thermal interaction (PTI)—commonly achieved using laser beams providing short dwell time (e.g. lasers with nanosecond pulsewidth);
(ii) Photo-ablation interaction (PAI)—envisaged using laser beams providing ultra-short dwell time (e.g. lasers with picosecond or femtosecond pulsewidth).
In the PTI regime the focused laser beam acts as a spatially confined, intense heat source. Targeted material is heated up rapidly, eventually causing it to be vaporized. Without wishing to imply any limitation to the scope of protection, the targeted material could be referred to as being boiled away. An advantage of this approach is that it may enable rapid removal of relatively large amount of target material. However, the peripheral heat affected zone (HAZ) damage and the presence of some recast material after processing present limitations in terms of heat confinement for precision laser materials engineering.
In the PAI regime, the laser drives multi-photon absorption of light inside the material. This strips electrons from the material, which then explode away due to Coulomb repulsion. Because PAI involves directly breaking the molecular or atomic bonds that hold the material together, rather than simply heating it, it is intrinsically not a ‘hot’ process. Since the material is removed in a very short timeframe, the ablated material carries away most of the energy before heat can spread into the surrounding material. These effects may result in a significantly reduced HAZ. Furthermore, this is a clean process and may leave minimal recast material, thereby eliminating the need for elaborate post-processing. The PAI mechanism is compatible with a very broad range of materials, including high band-gap materials that have low linear optical absorption and therefore are difficult to engineer with existing techniques. The PAI mechanism can be considered ‘wavelength neutral’; that is, nonlinear absorption can be reduced even if the material is normally transmissive at the laser wavelength.
The PAI mechanism should allow for custom design of electron work function of surfaces.
The PTI and PAI mechanism are illustrated schematically in
It is a further feature of embodiments that the characteristics of the pulsed radiation that is applied to the surface, for example the use of pulse durations in the picosecond range or less, are such that the periodic structures that are formed are of shallower depth and/or more gently sloped than features formed using pulsed radiation of higher energy and/or longer duration for example pulse durations in the nano-second range.
Again, without wishing to be bound by theory, and without limitation to the scope of protection, the following comments are provided which relate to processes which may occur in relation to at least some embodiments.
In irradiation at very high intensities (or high irradiance) one is confronted with the issue of a dense, strongly absorbing material, in the first few tens of nm of which energy at a rate of some 1020 W/cm3 is liberated. Part of this energy, once randomised, is conducted into the bulk of the material, while part is converted into directed kinetic energy by thermal expansion of the heated layer. Two regimes are distinguished in this respect.
1. Nanosecond pulsed laser interaction which is dominated by the expansion and ablation of material. Here the thermal pressure of the heated layer is sufficient to cause significant compression of the underlying target material.
2. Picosecond pulsed laser interaction (for example in accordance with some embodiments described herein) which is heat conduction dominated since hydrodynamic motion during the pulse duration is negligible (laser pulses here may be 1000 times or more shorter than nanosecond ones). An important point here is that in the picosecond regime the strong heating of the dense material occurs before hydrodynamic expansion of the processed layer has even started. The plasmas produced in this regime have essentially the same density as the solid target itself. This—upon cooling—leads to the formation of fine structures—in the range from 1 micrometres to 50 micrometres depending on the irradiation parameters—covered with nano-structures.
Using picosecond duration pulsed radiation according to some embodiments can in some cases also cause formation of nano-ripples or other small scale structures on the surface in addition to the larger scale peaks and troughs obtained by scanning the laser beam in an appropriate pattern over the surface. It is possible that such nano-ripples or other small scale structures may in some cases decrease the reflectivity of the surface further, in addition to the reduction obtained by larger periodic peak and trough structures. Furthermore, in some cases the nano-ripples or other small scale structures and/or the shallower peaks and troughs associate with picosecond rather than nanosecond pulses may also provide other improved or alternative properties of the surface, for example reduced induction, and/or can provide the surface with an increased area at the nano- or micro-scale.
It will be understood that the present invention has been described above purely by way of example, and modifications of detail can be made within the scope of the invention. Each feature in the description, and (where appropriate) the drawings may be provided independently or in any appropriate combination with any other such feature.
| Number | Date | Country | Kind |
|---|---|---|---|
| 1511153.7 | Jun 2015 | GB | national |
| 1511154.5 | Jun 2015 | GB | national |
| 1517232.3 | Sep 2015 | GB | national |
| 1517235.6 | Sep 2015 | GB | national |
| 1603991.9 | Mar 2016 | GB | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/GB2016/051908 | 6/24/2016 | WO | 00 |
