LiDAR reflective materials and marking systems

Abstract

A method of marking dark surfaces with a dark LiDAR-reflective material, and a marking composition comprising a dark LiDAR-reflective material and a marking support. In particular, the dark LiDAR-reflective material comprises a reflectance in the visible spectrum of electromagnetic radiation of < 10%, and a reflectance in the near-infrared and LiDAR spectrum of electromagnetic radiation of > 10%.

Description

Technical Field

[0001] Cross-references to related applications

[0002] This application claims priority to U.S. Patent Application No. 18 / 118,853, filed March 8, 2023, pursuant to 35 U.SC §119, the contents of which are incorporated herein by reference.

[0003] This specification generally relates to methods for marking surfaces with LiDAR (Light Detection and Ranging) reflective materials, compositions of LiDAR reflective materials, and delivery systems comprising a marking carrier and LiDAR reflective materials. Background Technology

[0004] LiDAR electromagnetic radiation (near-infrared (IR), typically 905 nm or 1050 nm) is invisible to the human eye, but can be used by LiDAR detection devices to detect objects that reflect this radiation. However, this electromagnetic radiation is typically absorbed by dark-colored materials. Therefore, there is a need for methods to mark surfaces with dark-colored LiDAR reflective materials to achieve or enhance LiDAR detection, and for compositions of LiDAR reflective materials that can be applied to surfaces, especially dark-colored surfaces. Summary of the Invention

[0005] The first aspect includes a method for marking a surface with a LiDAR reflective material, comprising: selecting a surface to be marked; applying the LiDAR reflective material to the surface, wherein the LiDAR reflective material comprises: ≤10% reflectivity in the visible spectrum of electromagnetic radiation; and ≥10% reflectivity in the near-infrared and LiDAR spectra of electromagnetic radiation.

[0006] The second aspect includes the method of the first aspect, wherein applying LiDAR reflective material to the surface includes applying a delivery system comprising LiDAR reflective material and a marker carrier to the surface.

[0007] The third aspect includes the method of the first or second aspect, wherein applying LiDAR reflective material to the surface includes spraying the surface with LiDAR reflective material.

[0008] The fourth aspect includes the method of the first or second aspect, wherein applying the LiDAR reflective material to the surface includes applying the LiDAR reflective material to the surface using an applicator.

[0009] The fifth aspect includes the method of the fourth aspect, wherein the applicator is selected from at least one of the group consisting of a stamp, a brush, a marker, a pen, a stylus, a roller, and a needle.

[0010] The sixth aspect includes the method of the first or second aspect, wherein applying the LiDAR reflective material to the surface comprises contacting a membrane encapsulating the LiDAR reflective material with the surface, wherein the membrane is selected from the group consisting of: gelatin, polyethylene terephthalate (PET), polystyrene, gelatin, nylon, polycarbonate, epoxy resin, phenolic resin, urethane, polyester, vinyl ester, polyethylene, polypropylene, polyvinyl chloride, polymethyl methacrylate, acrylonitrile-butadiene-styrene (ABS), polydimethylsiloxane, polysulfide, or a combination of two or more thereof; and rupturing the membrane upon contact with the surface.

[0011] The seventh aspect includes the methods of the first to sixth aspects, wherein the LiDAR reflective material is applied to the surface as a unique marking design.

[0012] The eighth aspect includes the method of the seventh aspect, wherein the unique marking design is a glyph, barcode, or QR code.

[0013] The ninth aspect includes a labeling composition comprising: a LiDAR reflective material; and a labeling carrier, wherein the LiDAR reflective material comprises: ≤10% reflectivity in the visible spectrum of electromagnetic radiation; and ≥10% reflectivity in the near-infrared and LiDAR spectra of electromagnetic radiation.

[0014] The tenth aspect includes the labeling composition of the ninth aspect, wherein the labeling composition is encapsulated in a film selected from the group consisting of: gelatin, polyethylene terephthalate (PET), polystyrene, gelatin, nylon, polycarbonate, epoxy resin, phenolic resin, urethane, polyester, vinyl ester, polyethylene, polypropylene, polyvinyl chloride, polymethyl methacrylate, acrylonitrile-butadiene-styrene (ABS), polydimethylsiloxane, polysulfides, and combinations thereof.

[0015] The eleventh aspect includes the marking composition of the ninth aspect, wherein the composition further comprises a propellant selected from the group consisting of: difluorochloromethane, dimethyl ether, methyl ethyl ether, tetrafluoroethane, heptafluoropropane, hydrofluoroolefins, low molecular weight hydrocarbons, butane, isobutylene, propane, nitrous oxide, carbon dioxide, nitrogen, and combinations thereof.

[0016] The twelfth aspect includes the labeling composition of the ninth to eleventh aspects, wherein the labeling carrier is a gas selected from the group consisting of argon, nitrogen, oxygen, difluorochloromethane, dimethyl ether, methyl ethyl ether, tetrafluoroethane, heptafluoropropane, hydrofluoroolefins, chlorofluorocarbons, low molecular weight hydrocarbons, butane, isobutylene, propane, nitrous oxide, carbon dioxide, and combinations thereof.

[0017] The thirteenth aspect includes the labeling composition of aspects nine through eleven, wherein the labeling carrier is a fluid selected from the group consisting of: water, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl pentyl ketone, isophorene, diacetone alcohol, diisobutyl ketone, ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, glycol ether ester, propylene glycol monomethyl ether acetate, ethanol, butanol, propanol, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, and combinations thereof.

[0018] The fourteenth aspect includes the labeling composition of the ninth to eleventh aspects, wherein the labeling carrier is a polymer selected from the group consisting of gelatin, polyethylene terephthalate (PET), polystyrene, nylon, polycarbonate, epoxy resin, phenolic resin, urethane, polyester, vinyl ester, polyethylene, polypropylene, polyvinyl chloride, polymethyl methacrylate, acrylonitrile-butadiene-styrene (ABS), polydimethylsiloxane, polysulfides, and combinations thereof.

[0019] The fifteenth aspect comprises the labeling composition of aspects nine through eleven, wherein the labeling carrier is a combination of a gas and a fluid, wherein the gas is selected from: argon, nitrogen, oxygen, difluorochloromethane, dimethyl ether, methyl ethyl ether, tetrafluoroethane, heptafluoropropane, hydrofluoroolefins, chlorofluorocarbons, low molecular weight hydrocarbons, butane, isobutylene, propane, nitrous oxide, carbon dioxide, and combinations thereof; and the fluid is selected from: water, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl pentyl ketone, isophorone, diacetone alcohol, diisobutyl ketone, ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, glycol ether ester, propylene glycol monomethyl ether acetate, ethanol, butanol, propanol, ethylene glycol monobutyl ether, ethylene glycol mono-n-propyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, and combinations thereof.

[0020] The sixteenth aspect comprises the labeling composition of aspects nine through eleven, wherein the labeling carrier is a combination of a fluid and a polymer, wherein the fluid is selected from: water, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl pentyl ketone, isophorone, diacetone alcohol, diisobutyl ketone, ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, glycol ether ester, propylene glycol monomethyl ether acetate, ethanol, butanol, propanol, ethylene glycol monobutyl ether, ethylene glycol mono-n-propyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, and combinations thereof; and the polymer is selected from: gelatin, polyethylene terephthalate (PET), polystyrene, gelatin, nylon, polycarbonate, epoxy resin, phenolic resin, urethane, polyester, vinyl ester, polyethylene, polypropylene, polyvinyl chloride, polymethyl methacrylate, acrylonitrile-butadiene-styrene (ABS), polydimethylsiloxane, polysulfide, and combinations thereof.

[0021] The seventeenth aspect comprises the marking composition of aspects nine through sixteen, wherein the LiDAR reflective material contains an average particle size of 5 nm to 15 nm; and a blackness M of 130 to 170. y .

[0022] The eighteenth aspect includes the marking compositions of aspects nine through seventeen, wherein the LiDAR reflective material comprises an average particle size of 8 nm to 12 nm.

[0023] The nineteenth aspect comprises the marking composition of aspects nine through eighteen, wherein the LiDAR reflective material contains a blackness M of 150 to 170. y .

[0024] The twentieth aspect includes the marking composition of aspects nine through nineteen, wherein the LiDAR reflective material contains ≤5% reflectivity in the visible spectrum of electromagnetic radiation.

[0025] The twenty-first aspect includes the marking composition of aspects nine to twenty, wherein the LiDAR reflective material contains ≥20% reflectivity in the near-infrared and LiDAR spectra of electromagnetic radiation.

[0026] The twenty-second aspect includes the marking composition of aspects nine through twenty-one, wherein the LiDAR reflective material comprises a dark pigment selected from the group consisting of: CuO microcrystals, carbon black, ferrochrome oxide and its derivatives, or a combination of two or more thereof.

[0027] The twenty-third aspect includes the marking composition of the twenty-second aspect, wherein the dark pigment comprises CuO microcrystals having an intensity ratio of (-111) / (111) of 0.5 to 1.5.

[0028] The twenty-fourth aspect includes the marking composition of the twenty-second aspect, wherein the dark pigment comprises CuO microcrystals having an intensity ratio of (-111) / (111) of 0.9 to 1.1.

[0029] These and additional features provided by the embodiments described herein will be more fully understood in light of the following detailed description taken in conjunction with the accompanying drawings. Attached Figure Description

[0030] The embodiments illustrated in the accompanying drawings are illustrative and exemplary in nature and are not intended to limit the subject matter defined by the claims. The following detailed description of the illustrative embodiments can be understood when read in conjunction with the following drawings, wherein the same structures are indicated by the same reference numerals, and wherein:

[0031] Figure 1A Displaying LiDAR detection of dark objects graphically;

[0032] Figure 1B The diagram illustrates how marking surface features of dark objects can enhance LiDAR detection of dark objects.

[0033] Figure 1C LiDAR detection of dark objects in a graphical manner can include identifying additional information (e.g., object orientation) by marking patterns that encode information.

[0034] Figure 2 The relationship between reflectance and wavelength is graphically depicted for carbon black, commercial "cool black", commercial N-CuO-C and N-CuO-A pigments;

[0035] Figure 3 The blackness My values ​​of paints containing carbon black, commercial "cold black", commercial N-CuO-C and N-CuO-A pigments were depicted, and photographs were inserted to reveal the blackness differences of these four samples.

[0036] Figure 4A This is a schematic diagram of a demonstration setup simulating an autonomous driving car using a robot car equipped with a 905 nm 2D laser scanner.

[0037] Figure 4B Depicting a robot car in 8 o Comparison of LiDAR intensity obtained from coated panels containing carbon black, N-CuO-A, N-CuO-B, commercial N-CuO-C, and cool black pigments, respectively;

[0038] Figure 4CThis is a schematic diagram illustrating a robotic car impacting a carbon black-coated panel, where the LiDAR intensity threshold is set to 100; and

[0039] Figure 4D This is a schematic diagram showing a robotic car stopping in front of a coated panel containing N-CuO-A pigment, with the LiDAR intensity threshold set to 100. Detailed Implementation

[0040] The methods disclosed and described herein mark surfaces with a LiDAR reflective material that reflects near-infrared electromagnetic radiation. This material comprises LiDAR having a wavelength greater than or equal to 800 nm and less than or equal to 2500 nm, but also being dark in color (such as dark brown or black). In embodiments, the methods disclosed and described herein include a delivery system comprising the LiDAR reflective material and a marking carrier that can apply the LiDAR reflective material to a surface (e.g., parts of a vehicle, parts of a structure, parts of a document, parts of a fabric, etc.) such that even when both the surface and the LiDAR reflective material are dark, near-infrared and LiDAR detection systems can detect surfaces coated with the LiDAR reflective material.

[0041] As used in this article, the term "near-infrared electromagnetic radiation" refers to electromagnetic radiation with wavelengths greater than or equal to 800 nm and less than or equal to 2500 nm.

[0042] As used in this article, the term “LiDAR” refers to electromagnetic radiation with wavelengths greater than or equal to 905 nm and less than or equal to 1550 nm.

[0043] As used in this article, the term "visible spectrum" refers to electromagnetic radiation with wavelengths greater than or equal to 350 nm and less than or equal to 750 nm.

[0044] Therefore, it is desirable to be able to mark articles and structures using dark LiDAR reflective materials. Dark LiDAR reflective materials can be used to mark dark articles or structures without intending the markings to be perceptible to the naked eye. For example, dark articles or structures intended to be marked with images intended for a selected group rather than the general public can be marked using a delivery system containing dark LiDAR reflective material, such that the markings are perceptible only to those viewing the markings through LiDAR detection devices. In this scenario, if conventional light-colored LiDAR reflective materials were used, the markings would be visible to anyone. An exemplary use could be, for example, dark structures that are intended to be detectable by autonomous vehicles or robots, but whose aesthetic appeal is not compromised by light-colored LiDAR reflective materials.

[0045] To date, delivery systems for marking articles and structures using dark LiDAR reflective materials have incorporated lighter-colored LiDAR reflective materials into dark carriers. Generally, these known systems do not achieve a good balance between LiDAR reflectivity and dark color. This disclosure addresses this problem by providing a marking system for applying dark LiDAR reflective materials to articles and structures. This disclosure further provides marking compositions comprising dark LiDAR reflective materials and marking carriers. The embodiments shown herein are exemplary and are not intended to be exhaustive or limit the scope of the claimed subject matter. Various components of this marking system and methods of using the marking system will now be discussed.

[0046] LiDAR reflective materials

[0047] Dark LiDAR reflective materials that can be used in the systems and methods disclosed herein contain ≤10% reflectance in the visible spectrum of electromagnetic radiation and ≥10% reflectance in the near-infrared and LiDAR spectra of electromagnetic radiation.

[0048] As mentioned above, the performance and accuracy of LiDAR detection depend on the intensity of LiDAR light reflected from an object and received by the LiDAR system. However, dark pigments and colorants (e.g., black pigments used in paints and other materials to provide a dark color) absorb not only visible electromagnetic radiation to provide a dark color, but also near-infrared electromagnetic radiation with wavelengths greater than about 750 nm, including LiDAR electromagnetic radiation.

[0049] Commonly used dark pigments include carbon black and ferrochrome oxide. Carbon black is the standard for "pure black," possessing a blackness (M) of approximately 165 as measured by an X-Rite spectrophotometer. y However, carbon black absorbs electromagnetic radiation across the entire visible, infrared, and near-infrared (LiDAR) spectrum. Therefore, the LiDAR reflectance of carbon black is close to zero. Consequently, carbon black is not an ideal candidate for applications requiring infrared or LiDAR reflection. On the other hand, ferrochrome oxide and its derivatives exhibit high absorption in visible light but reflect infrared and / or LiDAR light. Ferrochrome oxide has a blackness of approximately 142 or less. The reduced blackness of ferrochrome oxide compared to "pure black" is significant. Therefore, some commercial pigment products containing ferrochrome oxide and its derivatives are available as "cool black" and exhibit red or blue undertones, thus not being considered "pure black."

[0050] Therefore, a dark-colored LiDAR reflective material is needed, which has a blackness similar to carbon black and also reflects near-infrared and LiDAR electromagnetic radiation. To meet this requirement, a dark-colored LiDAR reflective material is needed so that it has a very sharp increase in reflectivity just outside the visible spectrum of electromagnetic radiation.

[0051] This abrupt shift in reflectivity or absorption is typically determined by the band gap of a material. As used herein, "band gap" generally refers to the energy difference (in electron volts or eV) between the top of the valence band (VB) and the bottom of the conduction band (CB). VB is the highest-energy electron-filled band, and CB is the lowest-energy electron-vacant band. The band gap is generally the threshold energy at which electrons in VB can be absorbed and thus move from VB to CB. In optics, the threshold energy refers to the photon energy (E, in eV) or wavelength (λ, in nm) that can be absorbed by a material. It should be noted that photon energy is inversely proportional to photon wavelength according to the following equation:

[0052]

[0053] Therefore, without being bound by any particular theory, the band gap determines which wavelengths or portions of the electromagnetic spectrum the material can absorb. Given this, promising dark, LiDAR-reflective materials require a band gap of 1.5 eV to 1.8 eV (approximately 688 nm to 826 nm) to absorb electromagnetic radiation in the visible spectrum and transmit or reflect LiDAR.

[0054] The band gap of a material can be manipulated in various ways, such as by adding dopants in the case of semiconductors, reducing particle size and shape in the case of nanoparticles, controlling crystal structure in the case of microcrystals, and many other methods. One dark-colored material of interest for band gap engineering in LiDAR applications is copper(II) oxide, or copper oxide (CuO). It has been found that the band gap of CuO can be tuned through various methods, such as dopants, synthesis solvents and stoichiometry, nanoparticle size, and the shape and morphology of nanostructures.

[0055] CuO is a monoclinic p-type semiconductor with an indirect band gap experimentally determined to be in the range of 1.2 eV to 2.2 eV. CuO is a black solid in its natural state. However, not all copper oxides possess this black color. Another stable copper oxide is cuprous oxide (Cu₂O), which is a red solid in its natural state. CuO is a product of copper mining and a precursor to many other copper-containing products and compounds. CuO is commonly used as a pigment, such as in ceramics and glazes, and can be used to provide high-quality black finishes.

[0056] However, without manipulation, bulk CuO has a reported band gap of 2.0 eV, which is beyond the 1.2 eV to 1.8 eV required for absorbing electromagnetic radiation in the visible spectrum and reflecting electromagnetic radiation in the near-infrared and LiDAR spectra. Bulk CuO also has a blackness M of 128. yThe value is significantly lower than the blackness of carbon black, which is approximately 165. When CuO is manipulated to have a band gap that is more suitable for reflecting electromagnetic radiation in the near-infrared or LiDAR spectra, the color of CuO deteriorates to a brownish-black, which is unsuitable for certain applications, such as automotive coatings and fabrics.

[0057] On the other hand, without being bound by any specific theory, it is believed that CuO crystallites can be designed to exhibit excellent blackness in the visible spectrum of electromagnetic radiation and high reflectivity in near-infrared and LiDAR electromagnetic radiation wavelengths. CuO nanoparticles can be fabricated by processing CuO using mechanical methods such as ball milling and jet milling. These CuO nanoparticles are transmissive in the infrared wavelength range and absorptive in the visible wavelength range. Furthermore, CuO nanoparticles can have a reflectivity of less than 10% in the visible light range, thus making them suitable for use as black pigments. By manipulating CuO, it has been found that CuO crystallites with a sharp transition in absorbance to wavelengths around 700 nm (approximately 1.77 eV) can be formed. These CuO crystallites can be made indistinguishable from carbon black, possessing the same level of measured blackness (M). y (Value 135.5), but the LiDAR detectability of these nanocrystalline CuOs is 1500% better than that of carbon black.

[0058] Without being bound by any particular theory, this abrupt transition in CuO crystallites is considered to be attributable to the near-1 ratio of the (−111) / (111) crystal planes and the approximately 100 Å crystal size of the (−111) planes. Specifically, the (111) planes are considered to have a valence band (VB) maximum edge of approximately 1.2 eV (or −1030 nm) and a band gap energy of 1.5 eV, while the (−111) planes have a slightly larger VB maximum edge of approximately 2.1 eV (or −620 nm) and a slightly larger band gap energy of 1.6 eV. Therefore, visual observation suggests that the (−111) planes are the primary cause of visible light reflection, as it begins at the larger VB maximum edge of approximately 620 nm. Thus, a smaller (−111) / (111) ratio or a smaller crystallite size in the (−111) planes may result in higher blackness levels, while a larger ratio and crystallite size would benefit near-infrared reflectivity. In other words, the ratio of (−111) / (111) planes in the microcrystalline phase and the average crystallite size are two key guiding indicators.

[0059] An embodiment of the LiDAR reflective material used to form the marking composition will now be described.

[0060] Typically, LiDAR reflective materials contain less than or equal to 10% reflectance in the visible spectrum of electromagnetic radiation; and greater than or equal to 10% reflectance in the near-infrared and LiDAR spectra of electromagnetic radiation.

[0061] In an embodiment, the LiDAR reflective material that can be used to form the marking composition comprises a reflectance in the visible spectrum of electromagnetic radiation of the following values: less than or equal to 10%, such as less than or equal to 9.0%, less than or equal to 8.0%, less than or equal to 7.0%, less than or equal to 6.0%, less than or equal to 5.0%, less than or equal to 4.0%, less than or equal to 3.0%, less than or equal to 2.0%, less than or equal to 1.0%, or less than or equal to 0.5%, less than or equal to 0.1%.

[0062] In the implementation, the LiDAR reflective material described herein has a reflectivity of 10% or greater in the near-infrared and LiDAR spectra of electromagnetic radiation, such as 15% or greater, 20% or greater, 25% or greater, 30% or greater, 35% or greater, 40% or greater, 45% or greater, 50% or greater, 55% or greater, or 60% or greater. In one or more embodiments, the LiDAR reflective material has a reflectivity in the near-infrared and LiDAR spectra of electromagnetic radiation that is greater than or equal to 10% and less than or equal to 80%, such as greater than or equal to 15% and less than or equal to 80%, greater than or equal to 20% and less than or equal to 80%, greater than or equal to 25% and less than or equal to 80%, greater than or equal to 30% and less than or equal to 80%, greater than or equal to 35% and less than or equal to 80%, greater than or equal to 40% and less than or equal to 80%, greater than or equal to 45% and less than or equal to 80%, greater than or equal to 50% and less than or equal to 80%, greater than or equal to 55% and less than or equal to 80%, greater than or equal to 60% and less than or equal to 80%, greater than or equal to 65% and less than or equal to 80%, greater than or equal to 70% and less than or equal to 80%, or greater than or equal to 75% and less than or equal to 80%.

[0063] In the implementation, the LiDAR reflective material has a blackness (My) greater than or equal to 130 and less than or equal to 170, such as greater than or equal to 135 and less than or equal to 170, greater than or equal to 140 and less than or equal to 170, greater than or equal to 145 and less than or equal to 170, greater than or equal to 150 and less than or equal to 170, greater than or equal to 155 and less than or equal to 170, greater than or equal to 160 and less than or equal to 170, greater than or equal to 165 and less than or equal to 170, greater than or equal to 130 and less than or equal to 165, greater than or equal to 135 and less than or equal to 165, greater than or equal to 140 and less than or equal to 165, greater than or equal to 145 and less than or equal to 165, greater than or equal to 150 and less than or equal to 165, greater than or equal to 155 and less than or equal to 165, or greater than or equal to 160 and less than or equal to 165.

[0064] In the implementation, the LiDAR reflective material can have an average particle size greater than or equal to 5 nm and less than or equal to 2000 nm, such as greater than or equal to 6 nm and less than or equal to 2000 nm, greater than or equal to 7 nm and less than or equal to 2000 nm, greater than or equal to 8 nm and less than or equal to 2000 nm, greater than or equal to 9 nm and less than or equal to 2000 nm, greater than or equal to 10 nm and less than or equal to 2000 nm, greater than or equal to 11 nm and less than or equal to 2000 nm, greater than or equal to 12 nm and less than or equal to 2000 nm, greater than or equal to 13 nm and less than or equal to 2000 nm, greater than or equal to 14 nm and less than or equal to 2000 nm, greater than or equal to 15 nm and less than or equal to 2000 nm, greater than or equal to 50 ... nm and less than or equal to 2000 nm, greater than or equal to 1000 nm and less than or equal to 2000 nm, greater than or equal to 1500 nm and less than or equal to 2000 nm, greater than or equal to 5 nm and less than or equal to 1500 nm, greater than or equal to 6 nm and less than or equal to 1500 nm, greater than or equal to 7 nm and less than or equal to 1500 nm, greater than or equal to 8 nm and less than or equal to 1500 nm, greater than or equal to 9 nm and less than or equal to 1500 nm, greater than or equal to 10 nm and less than or equal to 1500 nm, greater than or equal to 11 nm and less than or equal to 1500 nm, greater than or equal to 12 nm and less than or equal to 1500 nm, greater than or equal to 13 nm and less than or equal to 1500 nm, greater than or equal to 14 nm and less than or equal to 1500 nm, greater than or equal to 15 nm and less than or equal to 1500 nm, greater than or equal to 50 nm and less than or equal to 1500 nm, greater than or equal to 10 ... nm and less than or equal to 1500 nm, greater than or equal to 200 nm and less than or equal to 1500 nm, or greater than or equal to 500 nm and less than or equal to 1500 nm, or greater than or equal to 1000 nm and less than or equal to 1500 nm.

[0065] An implementation scheme for a LiDAR reflective material containing CuO microcrystals in a dark pigment will now be described.

[0066] In the implementation, the CuO microcrystals may have a (-111) / (111) ratio greater than or equal to 0.8 and less than or equal to 1.3, such as greater than or equal to 0.9 and less than or equal to 1.3, greater than or equal to 1.0 and less than or equal to 1.3, greater than or equal to 1.1 and less than or equal to 1.3, greater than or equal to 1.2 and less than or equal to 1.3, greater than or equal to 0.8 and less than or equal to 1.2, greater than or equal to 0.9 and less than or equal to 1.2, greater than or equal to 1.0 and less than or equal to 1.2, greater than or equal to 1.1 and less than or equal to 1.2, greater than or equal to 0.8 and less than or equal to 1.1, greater than or equal to 0.9 and less than or equal to 1.1, greater than or equal to 1.0 and less than or equal to 1.1, greater than or equal to 0.8 and less than or equal to 1.0, greater than or equal to 0.9 and less than or equal to 1.0, or greater than or equal to 0.8 and less than or equal to 0.9.

[0067] By reducing the size of CuO crystallites, such as reducing them to the average particle size disclosed below, the band gap of CuO is reduced. In the implementation scheme, the band gap measured by X-ray photoelectron spectroscopy (XPS) of CuO nanoparticles is greater than or equal to 1.2 eV and less than or equal to 1.8 eV, such as greater than or equal to 1.3 eV and less than or equal to 1.8 eV, greater than or equal to 1.4 eV and less than or equal to 1.8 eV, greater than or equal to 1.5 eV and less than or equal to 1.8 eV, greater than or equal to 1.6 eV and less than or equal to 1.8 eV, greater than or equal to 1.7 eV and less than or equal to 1.8 eV, greater than or equal to 1.2 eV and less than or equal to 1.7 eV, such as greater than or equal to 1.3 eV and less than or equal to 1.7 eV, greater than or equal to 1.4 eV and less than or equal to 1.7 eV, greater than or equal to 1.5 eV and less than or equal to 1.7 eV, greater than or equal to 1.6 eV and less than or equal to 1.7 eV, and greater than or equal to 1.2 eV and less than or equal to 1.6 eV. eV, such as greater than or equal to 1.3 eV and less than or equal to 1.6 eV, greater than or equal to 1.4 eV and less than or equal to 1.6 eV, greater than or equal to 1.5 eV and less than or equal to 1.6 eV, greater than or equal to 1.2 eV and less than or equal to 1.5 eV, such as greater than or equal to 1.3 eV and less than or equal to 1.5 eV, greater than or equal to 1.4 eV and less than or equal to 1.5 eV, greater than or equal to 1.2 eV and less than or equal to 1.4 eV, such as greater than or equal to 1.3 eV and less than or equal to 1.4 eV, or greater than or equal to 1.2 eV and less than or equal to 1.3 eV.

[0068] Without being bound by any particular theory, it is generally accepted that the smaller the average crystal size of CuO nanoparticles, the lower the band gap of the CuO nanoparticles will be. Therefore, according to the embodiments disclosed and described herein, by reducing bulk CuO particles to CuO nanoparticles, the band gap of the CuO nanoparticles is in the range of electromagnetic radiation that will reflect near-infrared and LiDAR spectra, such as having a band gap between 1.5 eV and 2.0 eV.

[0069] In the embodiment, CuO microcrystals may have an average particle size greater than or equal to 5 nm and less than or equal to 15 nm, such as greater than or equal to 6 nm and less than or equal to 15 nm, greater than or equal to 7 nm and less than or equal to 15 nm, greater than or equal to 8 nm and less than or equal to 15 nm, greater than or equal to 9 nm and less than or equal to 15 nm, greater than or equal to 10 nm and less than or equal to 15 nm, greater than or equal to 11 nm and less than or equal to 15 nm, greater than or equal to 12 nm and less than or equal to 15 nm, greater than or equal to 13 nm and less than or equal to 15 nm, greater than or equal to 14 nm and less than or equal to 15 nm, greater than or equal to 5 nm and less than or equal to 14 nm, greater than or equal to 6 nm and less than or equal to 14 nm, greater than or equal to 7 nm and less than or equal to 14 nm, greater than or equal to 8 nm and less than or equal to 14 nm, greater than or equal to 9 nm and less than or equal to 14 nm, greater than or equal to 10 nm and less than or equal to 14 nm, greater than or equal to 11 nm and less than or equal to 15 nm. nm and less than or equal to 14 nm, greater than or equal to 12 nm and less than or equal to 14 nm, greater than or equal to 13 nm and less than or equal to 14 nm, greater than or equal to 5 nm and less than or equal to 13 nm, greater than or equal to 6 nm and less than or equal to 13 nm, greater than or equal to 7 nm and less than or equal to 13 nm, greater than or equal to 8 nm and less than or equal to 13 nm, greater than or equal to 9 nm and less than or equal to 13 nm, greater than or equal to 10 nm and less than or equal to 13 nm, greater than or equal to 11 nm and less than or equal to 13 nm, greater than or equal to 12 nm and less than or equal to 13 nm, greater than or equal to 5 nm and less than or equal to 12 nm, greater than or equal to 6 nm and less than or equal to 12 nm, greater than or equal to 7 nm and less than or equal to 12 nm, greater than or equal to 8 nm and less than or equal to 12 nm, greater than or equal to 9 nm and less than or equal to 12 nm, greater than or equal to 10 nm and less than or equal to 12 nm, greater than or equal to 11 nm and less than or equal to 12 nm, greater than or equal to 5 nm and less than or equal to 14 nm, greater ...4 nm, greater than or equal to 14 nm, greater than or equal to 14 nm, less than or equal to 14 nm, greater than or equal to 14 nm, greater nm and less than or equal to 11 nm, greater than or equal to 6 nm and less than or equal to 11 nm, greater than or equal to 7 nm and less than or equal to 11 nm, greater than or equal to 8 nm and less than or equal to 11 nm, greater than or equal to 9 nm and less than or equal to 11 nm, greater than or equal to 10 nm and less than or equal to 11 nm, greater than or equal to 5 nm and less than or equal to 10 nm, greater than or equal to 6 nm and less than or equal to 10 nm, greater than or equal to 7 nm and less than or equal to 10 nm, greater than or equal to 8 nm and less than or equal to 10 nm, greater than or equal to 9 nm and less than or equal to 10 nm, greater than or equal to 5 nm and less than or equal to 9 nm.Greater than or equal to 6 nm and less than or equal to 9 nm, greater than or equal to 7 nm and less than or equal to 9 nm, greater than or equal to 8 nm and less than or equal to 9 nm, greater than or equal to 5 nm and less than or equal to 8 nm, greater than or equal to 6 nm and less than or equal to 8 nm, greater than or equal to 7 nm and less than or equal to 8 nm, greater than or equal to 5 nm and less than or equal to 7 nm, greater than or equal to 6 nm and less than or equal to 7 nm, or greater than or equal to 5 nm and less than or equal to 6 nm.

[0070] In the implementation, the blackness My (i.e., the measure of blackness) of the CuO microcrystals is greater than or equal to 130 and less than or equal to 170, such as greater than or equal to 135 and less than or equal to 170, greater than or equal to 140 and less than or equal to 170, greater than or equal to 145 and less than or equal to 170, greater than or equal to 150 and less than or equal to 170, greater than or equal to 160 and less than or equal to 170, greater than or equal to 165 and less than or equal to 170, greater than or equal to 130 and less than or equal to 165, greater than or equal to 135 and less than or equal to 165, greater than or equal to 140 and less than or equal to 165, greater than or equal to 145 and less than or equal to 165, greater than or equal to 150 and less than or equal to 165, greater than or equal to 155 and less than or equal to 165, or greater than or equal to 160 and less than or equal to 165.

[0071] The copper oxide microcrystals according to the embodiments disclosed and described herein have a reflectance in the visible spectrum of electromagnetic radiation of less than or equal to 10.0%, such as less than or equal to 9.0%, less than or equal to 8.0%, less than or equal to 7.0%, less than or equal to 6.0%, less than or equal to 5.0%, less than or equal to 4.0%, less than or equal to 3.0%, less than or equal to 2.0%, less than or equal to 1.0%, or less than or equal to 0.5%.

[0072] The copper oxide microcrystals according to the embodiments disclosed and described herein have a reflectance in the near-infrared and LiDAR spectra of electromagnetic radiation greater than or equal to 10%, such as greater than or equal to 15%, greater than or equal to 20%, greater than or equal to 25%, greater than or equal to 30%, greater than or equal to 35%, greater than or equal to 40%, greater than or equal to 45%, greater than or equal to 50%, greater than or equal to 55%, or greater than or equal to 60%. In one or more embodiments, the copper oxide microcrystals have a reflectance in the near-infrared and LiDAR spectra of electromagnetic radiation that is greater than or equal to 10% and less than or equal to 60%, such as greater than or equal to 15% and less than or equal to 60%, greater than or equal to 20% and less than or equal to 60%, greater than or equal to 25% and less than or equal to 60%, greater than or equal to 30% and less than or equal to 60%, greater than or equal to 35% and less than or equal to 60%, greater than or equal to 40% and less than or equal to 60%, greater than or equal to 45% and less than or equal to 60%, greater than or equal to 50% and less than or equal to 60%, or greater than or equal to 55% and less than or equal to 60%.

[0073] Combining CuO microcrystals with carbon black, ferrochrome oxide, and their derivatives or combinations thereof can further improve the blackness or near-infrared reflectivity of dark pigments. An embodiment of a LiDAR reflective material in which the dark pigment comprises CuO microcrystals and at least one selected from carbon black, ferrochrome oxide, and their derivatives or combinations thereof will now be described.

[0074] In this embodiment, the dark pigment is a core-shell system comprising an inner core and an outer shell. The core is composed of carbon black or ferrochrome oxide and its derivatives, and the shell is composed of CuO microcrystals. The CuO microcrystal shell reflects near-infrared and LiDAR radiation and absorbs visible light radiation. When the pigment has a core composed of carbon black, residual visible light radiation passing through the CuO microcrystal shell can be further absorbed by the carbon black core, resulting in increased blackness. When the pigment has a core composed of ferrochrome oxide and its derivatives, residual near-infrared and LiDAR radiation passing through the CuO microcrystal shell can be reflected by the ferrochrome oxide core, resulting in increased reflectivity in near-infrared and LiDAR wavelengths.

[0075] marker carrier

[0076] LiDAR reflective materials are typically solids. While fine powders of LiDAR reflective materials can be applied directly to surfaces via brushing, electrostatic spraying, etc., pigments are often used in conjunction with additional marking carriers to expand the available application methods, such as coating and wet spraying. Therefore, the marking methods discussed herein can also include applying a delivery system comprising LiDAR reflective material and a marking carrier to a surface. The marking carriers disclosed herein are reagents that facilitate and promote the application of LiDAR reflective materials to selected surfaces.

[0077] Surface marking typically involves subjecting an object's surface to a layer of marking material (e.g., LiDAR reflective material) and retaining the marking material layer on the object's surface for an intended application (e.g., LiDAR detection). Various surface marking methods exist, ranging from simple approaches (such as pen writing, brushing, and aerosol spraying) to more advanced techniques (such as thermal spraying, solution deposition, laser deposition, electrochemical deposition, electrostatic deposition, etc.). However, the reliability of a marking method varies depending on the type (e.g., metallic or non-metallic) and properties (e.g., porous, hydrophilic, or hydrophobic) of the surface chosen. Furthermore, different methods or techniques require different material states (liquid, solid (including molten), and gaseous) and different material properties (concentration, viscosity, density, melting point, boiling point, etc.). For example, simple spraying typically requires a liquid marking material, while thermal spraying requires a molten marking material.

[0078] After the labeling material is applied to a surface, many applications, including LiDAR detection, require the labeling layer to be permanently or temporarily retained on the surface for minutes, hours, or days to make the intended application operational. Retention of the labeling material on a surface can be achieved through physical interactions (e.g., electrostatic interactions) or through chemical bonding (e.g., surface modification). For example, ultrafine carbon black powder can adhere to a glass surface using electrostatic forces, and hydrophilic surface modifiers can form hydrogen bonds to link the pigment to hydroxyl groups on the glass surface. Therefore, depending on the intended application, several labeling carriers may be required.

[0079] According to the implementation scheme, the labeling carrier can be a fluid, polymer, gas, or a combination thereof. Each of these labeling carriers will be discussed in more detail below.

[0080] Implementation schemes of fluid labeling carriers will now be described. The LiDAR reflective material disclosed above can be incorporated into a fluid labeling carrier (such as a solvent) that allows the LiDAR reflective material to be sprayed or applied using stamps, brushes, markers, pens, styluses, rollers, needles, etc. In one embodiment, the solvent containing the LiDAR reflective material can be present in a pressurized container or a container further comprising a propellant, allowing the solvent containing the LiDAR reflective material to be applied as an aerosol (similar to spray paint). In other embodiments, the solvent containing the LiDAR reflective material can be absorbed into an absorbent material, allowing it to be applied using a physical applicator (such as a wooden or rubber stamp). In one embodiment, the stamp can have a unique design, such as, for example, fonts, QR codes, barcodes, etc. Other labeling carriers may include liquid solvents containing LiDAR reflective material, allowing the solvent containing the LiDAR reflective material to be applied using brushes, markers, pens, etc. The viscosity of the liquid solvent containing the LiDAR reflective material can vary depending on the desired end use. In the implementation scheme, the liquid solvent containing the LiDAR reflective material can have high viscosity and exhibit viscous or sticky properties. By incorporating the LiDAR reflective material into the solvent, the application of the LiDAR reflective material to the article or structure can be controlled, making it easier for users to apply the LiDAR reflective material in the design. In this way, the image or design may be almost invisible to the naked eye but easily detected by LiDAR detection devices.

[0081] Forming a solvent containing LiDAR reflective material involves combining the LiDAR reflective material with one or more solvent systems to form a solvent doped with LiDAR reflective material. In embodiments, the solvent doped with LiDAR reflective material can be one or more suspensions of LiDAR reflective material, or one or more suspensions of LiDAR reflective material gels. For example, in embodiments, the solvent can be a ketone (such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl pentyl ketone, isophorone, diacetone alcohol, diisobutyl ketone, etc.), an ester (such as ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, glycol ether esters, propylene glycol monomethyl ether acetate, etc.), an alcohol (such as ethanol, butanol, propanol, etc.), or a glycol ether (such as ethylene glycol monobutyl ether, ethylene glycol mono-n-propyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, etc.). Of course, combinations of solvents can be used as needed. Solvents may include various additives to enhance their performance, such as thickeners, stabilizers, emulsifiers, and dispersants.

[0082] Solvents containing LiDAR reflective materials can also be dispensed and encapsulated in diaphragms for remote application of the LiDAR reflective material. Optionally, the diaphragm can be designed to rupture upon impact with an article or structure under elevated force, allowing the solvent containing the LiDAR reflective material to be applied to the article or structure upon impact. These diaphragms can be made of plastics (such as PET, polystyrene, etc.) or can be gelatin-based diaphragms. The solvent-filled diaphragm can then be delivered via a pressurized delivery device that allows for marking of articles or structures from a distance using the solvent containing the LiDAR reflective material.

[0083] In an embodiment where the labeling carrier is a fluid, the labeling carrier is a fluid selected from the following: water, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl pentyl ketone, isophorone, diacetone alcohol, diisobutyl ketone, ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, glycol ether ester, propylene glycol monomethyl ether acetate, ethanol, butanol, propanol, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, and combinations thereof.

[0084] The boiling point of the fluid label carrier at 760 mmHg is greater than or equal to 0°C and less than or equal to 300°C, such as greater than or equal to 20°C and less than or equal to 280°C, greater than or equal to 40°C and less than or equal to 260°C, greater than or equal to 60°C and less than or equal to 240°C, greater than or equal to 80°C and less than or equal to 200°C, greater than or equal to 100°C and less than or equal to 180°C, or greater than or equal to 120°C and less than or equal to 160°C.

[0085] Polymer-labeled carriers can also be used to apply LiDAR reflective materials, wherein the polymer-labeled carriers physically or chemically form a network to maintain the LiDAR reflective material as a film. The polymer-labeled carriers can form a network by exposure to heat or light. Embodiments of polymer-labeled carriers will now be described.

[0086] In embodiments where the labeling carrier is a polymer, the labeling carrier may be a polymer selected from the following: gelatin, polyethylene terephthalate (PET), polystyrene, gelatin, nylon, polycarbonate, epoxy resin, phenolic resin, urethane, polyester, vinyl ester, polyethylene, polypropylene, polyvinyl chloride, polymethyl methacrylate, acrylonitrile-butadiene-styrene (ABS), polydimethylsiloxane, polysulfides, and combinations thereof.

[0087] The tensile strength of the polymer labeling carrier is greater than or equal to 10 MPa and less than or equal to 220 MPa, such as greater than or equal to 20 MPa and less than or equal to 200 MPa, greater than or equal to 30 MPa and less than or equal to 180 MPa, greater than or equal to 40 MPa and less than or equal to 160 MPa, greater than or equal to 50 MPa and less than or equal to 140 MPa, greater than or equal to 60 MPa and less than or equal to 120 MPa, or greater than or equal to 70 MPa and less than or equal to 100 MPa.

[0088] The polymer labeling carrier contains a transmittance of 90% or more in the near-infrared and LiDAR spectra of electromagnetic radiation, such as 91% or more, 92% or more, 93% or more, 94% or more, 95% or more, 96% or more, 97% or more, 98% or more, or 99% or more.

[0089] A gaseous labeling carrier can be used to apply dry LiDAR reflective material or powder in the same manner as described above. For example, LiDAR reflective material can be applied via dry aerosol to mark surfaces for LiDAR visibility. In embodiments, the films discussed above can encapsulate dry LiDAR reflective material (with or without a labeling carrier), enabling long-distance delivery of the LiDAR reflective material. Embodiments using gaseous labeling carriers will now be described.

[0090] In embodiments where the labeling carrier is a gas, the gas can be selected from the group consisting of: argon, nitrogen, oxygen, difluorochloromethane, dimethyl ether, methyl ethyl ether, tetrafluoroethane, heptafluoropropane, hydrofluoroolefins, chlorofluorocarbons, low molecular weight hydrocarbons, butane, isobutylene, propane, nitrous oxide, carbon dioxide, and combinations thereof. Non-limiting examples of uses for gaseous labeling carriers include thermal spraying processes, where a gas is used to carry dry LiDAR reflective material and / or provide an energy source, such as for flames, plasmas, etc.

[0091] In some embodiments, the labeling carrier can be a combination of fluid and polymer or fluid and gas. Combining fluid and polymer can form a polymer gel that imparts enhanced coverage and elasticity to the LiDAR reflective film. Certain solvents can also be used to weaken or enhance the fracture toughness of the polymer. The solvent can then be removed. Combining fluid and gas can refine the sprayed particle size and result in a smoother finish with a reduced grain size, thereby reducing the scattering loss of reflected LiDAR radiation. Embodiments of fluid-polymer labeling carriers will now be described.

[0092] In embodiments where the labeling carrier is a combination of a fluid and a polymer, the fluid may be selected from the group consisting of: water, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl pentyl ketone, isophorone, diacetone alcohol, diisobutyl ketone, ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, glycol ether ester, propylene glycol monomethyl ether acetate, ethanol, butanol, propanol, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, and combinations thereof; and the polymer may be selected from the group consisting of: gelatin, polyethylene terephthalate (PET), polystyrene, gelatin, nylon, polycarbonate, epoxy resin, phenolic resin, urethane, polyester, vinyl ester, polyethylene, polypropylene, polyvinyl chloride, polymethyl methacrylate, acrylonitrile-butadiene-styrene (ABS), polydimethylsiloxane, polysulfides, and combinations thereof. Non-limiting examples of fluid-polymer combinations include polyethylene glycol and water, polyurethane and dimethyl sulfoxide, polymethyl methacrylate, polystyrene and ethyl acetate, etc.

[0093] The fluid-polymer labeling carrier contains a transmittance of 90% or more in the near-infrared and LiDAR spectra of electromagnetic radiation, such as 91% or more, 92% or more, 93% or more, 94% or more, 95% or more, 96% or more, 97% or more, 98% or more, or 99% or more.

[0094] An implementation scheme for a fluid-gas labeling carrier will now be described.

[0095] In embodiments where the carrier is a combination of gas and fluid, the gas may be selected from the group consisting of: argon, nitrogen, oxygen, difluorochloromethane, dimethyl ether, methyl ethyl ether, tetrafluoroethane, heptafluoropropane, hydrofluoroolefins, chlorofluorocarbons, low molecular weight hydrocarbons, butane, isobutylene, propane, nitrous oxide, carbon dioxide, and combinations thereof; and the fluid may be selected from the group consisting of: water, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl pentyl ketone, isophorone, diacetone alcohol, diisobutyl ketone, ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, glycol ether esters, propylene glycol monomethyl ether acetate, ethanol, butanol, propanol, ethylene glycol monobutyl ether, ethylene glycol mono-n-propyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, and combinations thereof. Non-limiting examples of fluid-gas carrier applications include purging oxygen contained in a solvent to reduce the degradation of LiDAR reflective materials, etc.

[0096] Additionally, in some embodiments, portions of the label carrier can be physically mixed with the LiDAR reflective material, and portions of the label carrier can be chemically bonded to the LiDAR reflective material. Specifically, in cases where the label carrier comprises a polymer portion and a fluid portion, the polymer portion can be chemically bonded to the LiDAR reflective material to form a polymer shell surrounding the LiDAR reflective material. In some cases, the polymer shell can act as a surface modifier and allow the LiDAR reflective core-shell particles to adhere to the surface. In embodiments where such a polymer shell is formed around the LiDAR reflective material, the polymer is capable of transmitting LiDAR radiation.

[0097] Delivery system

[0098] The delivery system disclosed herein enables the customized application of LiDAR reflective materials to a variety of surfaces for different purposes. Non-limiting examples of surfaces include natural or synthetic fabrics, paper, plastics, concrete or rock, metals, elastomers, etc.

[0099] The delivery system for applying LiDAR reflective material to a selected surface includes the aforementioned LiDAR reflective material and a marker carrier. The total weight percentage of the marker carrier in the delivery system is greater than or equal to 0.01 wt% and less than or equal to 99 wt%, such as greater than or equal to 0.1 wt% and less than or equal to 99 wt%, greater than or equal to 1 wt% and less than or equal to 99 wt%, greater than or equal to 5 wt% and less than or equal to 99 wt%, greater than or equal to 10 wt% and less than or equal to 99 wt%, greater than or equal to 20 wt% and less than or equal to 99 wt%, greater than or equal to 40 wt% and less than or equal to 99 wt%, greater than or equal to 60 wt% and less than or equal to 99 wt%, and greater than or equal to 80 wt% and less than or equal to 99 wt%. ≥90% by weight and ≤99% by weight, ≥95% by weight and ≤99% by weight, ≥0.1% by weight and ≤80% by weight, ≥1% by weight and ≤80% by weight, ≥5% by weight and ≤80% by weight, ≥10% by weight and ≤80% by weight, ≥20% by weight and ≤80% by weight, ≥40% by weight and ≤80% by weight, ≥60% by weight and ≤80% by weight, ≥0.1% by weight and ≤60% by weight %, greater than or equal to 1% by weight and less than or equal to 60% by weight, greater than or equal to 5% by weight and less than or equal to 60% by weight, greater than or equal to 10% by weight and less than or equal to 60% by weight, greater than or equal to 20% by weight and less than or equal to 60% by weight, greater than or equal to 40% by weight and less than or equal to 60% by weight, greater than or equal to 0.1% by weight and less than or equal to 40% by weight, greater than or equal to 1% by weight and less than or equal to 40% by weight, greater than or equal to 5% by weight and less than or equal to 40% by weight, greater than or equal to 10% by weight and less than or equal to 40% by weight, greater than or equal to 20% by weight and less than or equal to 40% by weight , greater than or equal to 0.1% by weight and less than or equal to 20% by weight, greater than or equal to 1% by weight and less than or equal to 20% by weight, greater than or equal to 5% by weight and less than or equal to 20% by weight, greater than or equal to 10% by weight and less than or equal to 20% by weight, greater than or equal to 0.1% by weight and less than or equal to 10% by weight, greater than or equal to 1% by weight and less than or equal to 10% by weight, greater than or equal to 0.1% by weight and less than or equal to 5% by weight, greater than or equal to 1% by weight and less than or equal to 5% by weight, or greater than or equal to 0.1% by weight and less than or equal to 3% by weight.

[0100] The delivery system of the implementation scheme may also include additives such as thickeners, stabilizers, emulsifiers, surfactants, plasticizers, binders, dispersants, etc., to enhance the performance of the label carrier. Surfactants and emulsifiers can control and stabilize the agglomeration or deagglomeration of the LiDAR reflective material in the delivery system. Thickeners and plasticizers can rheologically modulate the delivery system, thereby providing the desired processability, coverage, and stability of the LiDAR reflective label. Binders enable the delivery system to be applied to a surface and form a thin film of LiDAR reflective material adhered to the surface upon drying. Stabilizers can inhibit degradation and extend the label's lifetime. Dispersants can improve the formation of particles or droplets of LiDAR reflective material in the delivery system and maintain the separation of LiDAR reflective particles or droplets in the delivery system to prevent their sedimentation or agglomeration.

[0101] Non-limiting examples of thickeners include: palygorskite, fumed silica, hydroxyethyl cellulose, methyl cellulose, fibrillated cellulose, methyl methacrylate, 2-ethylhexyl methacrylate, butanediol diacrylate, vinyl acetate, methacrylate, polyethylene glycol, gum, alginate or ester, poly(butane), poly(ethylene oxide), and combinations thereof.

[0102] Non-limiting examples of stabilizers include: tris(2,4-di-tert-butylphenyl) phosphite, butylated hydroxytoluene, nickel phenolate, calcium stearate, calcium oxide, zinc oxide, magnesium oxide, isothiazolinone, benzophenone, benzotriazole, hydroxyphenyltriazine, oxaloylaniline, p-phenylenediamine, and combinations thereof.

[0103] Non-limiting examples of surfactants include: alcohol ethoxylates, sulfosuccinates, polyether siloxanes, ethynyl glycol, polyoxyethylene glycol octylphenol ether, polyoxyethylene glycol dehydrated sorbitol alkyl ester, polyethylene glycol, polypropylene glycol, perfluorooctane sulfonate, lignin sulfonate, sodium dioctyl sulfosuccinate, and combinations thereof.

[0104] Non-limiting examples of plasticizers include: diisodecyl phthalate, diisoundecyl phthalate, ditridecyl phthalate, bis(2-ethylhexyl) adipate, dibutyl sebacate, butyl benzyl phthalate, bis(2-ethylhexyl) phthalate, diisononyl phthalate, bis(2-propylheptyl) phthalate, polycarboxylate esters, and combinations thereof.

[0105] Non-limiting examples of adhesives include acrylic resins, alkyd resins, latexes, phenolic resins, urethane resins, epoxy resins, and combinations thereof.

[0106] Non-limiting examples of dispersants include: sodium pyrophosphate, sodium citrate, sodium tartrate, sodium succinate, sodium polyacrylate, sodium polysulfonate, ammonium polyacrylate, ammonium citrate, trioleic acid glyceride, phosphate ester, poly(acrylic acid), poly(methacrylic acid), poly(ethyleneimine), and combinations thereof.

[0107] The total weight percentage of additives in the delivery system is greater than or equal to 0.1% by weight and less than or equal to 20.0% by weight, such as greater than or equal to 0.5% by weight and less than or equal to 18.0% by weight, greater than or equal to 1.0% by weight and less than or equal to 15.0% by weight, greater than or equal to 1.5% by weight and less than or equal to 12.0% by weight, greater than or equal to 1.0% by weight and less than or equal to 10.0% by weight, greater than or equal to 2.5% by weight and less than or equal to 8.0% by weight, or greater than or equal to 3.0% by weight and less than or equal to 5.0% by weight.

[0108] The delivery system according to the implementation scheme may also include a propellant capable of pressurizing the delivery system and applying it in the form of an aerosol. Non-limiting examples of propellants include: methane, propane, n-butane, isobutene, ethanol, kerosene, hydrogen, oxygen, nitrogen, nitrous oxide, carbon dioxide, chlorofluorocarbons (CFCs), dichlorodifluoromethane, diesel fuel, gasoline, dimethyl ether, methyl ethyl ether, tetrafluoroethane, heptafluoropropane, hydrofluoroolefins, and combinations thereof.

[0109] The delivery system of the implementation scheme has a propellant weight ratio greater than or equal to 5% by weight and less than or equal to 30% by weight, such as greater than or equal to 5% by weight and less than or equal to 20% by weight, greater than or equal to 5% by weight and less than or equal to 10% by weight, greater than or equal to 10% by weight and less than or equal to 30% by weight, greater than or equal to 10% by weight and less than or equal to 20% by weight, or greater than or equal to 20% by weight and less than or equal to 30% by weight.

[0110] In one or more embodiments, the delivery system can be pressurized with an operating pressure greater than or equal to 1.5 atm and less than or equal to 8 atm, such as greater than or equal to 2 atm and less than or equal to 6 atm, or greater than or equal to 3 atm and less than or equal to 5 atm.

[0111] According to the implementation scheme, the delivery system may further include a regulator for adjusting the volume ratio of the LiDAR reflective material and the marker carrier, wherein the regulator comprises at least a gas, a fluid, or a combination thereof. In such an implementation scheme, the gas includes: argon, nitrogen, oxygen, difluorochloromethane, dimethyl ether, methyl ethyl ether, tetrafluoroethane, heptafluoropropane, hydrofluoroolefins, chlorofluorocarbons, low molecular weight hydrocarbons, butane, isobutylene, propane, nitrous oxide, carbon dioxide, and combinations thereof; and the fluid includes: water, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl pentyl ketone, isophorone, diacetone alcohol, diisobutyl ketone, ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, glycol ether esters, propylene glycol monomethyl ether acetate, ethanol, butanol, propanol, ethylene glycol monobutyl ether, ethylene glycol mono-n-propyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, and combinations thereof.

[0112] application

[0113] The method of applying the LiDAR reflective material to a surface disclosed herein includes: selecting a surface to be marked; and applying the LiDAR reflective material to the surface, wherein the LiDAR reflective material contains ≤10% reflectivity in the visible spectrum of electromagnetic radiation and ≥10% reflectivity in the near-infrared and LiDAR spectra of electromagnetic radiation. Specifically, embodiments of applying the LiDAR reflective material to a surface include applying a delivery system comprising the LiDAR reflective material and a marking carrier to the surface in such a manner as: using an applicator, by spraying, by bringing a film encapsulating the LiDAR reflective material into contact with the surface, wherein the film ruptures upon contact with the surface, or by a combination thereof. Non-limiting examples of application according to the embodiments for identification purposes include marking the surface using unique designs, patterns, images, or markings (such as fonts, barcodes, or QR codes), such as by using an applicator. One or more embodiments include marking a surface of a large, free-form area by spraying for economic and efficiency purposes, and marking the surface using a diaphragm encapsulating LiDAR reflective material, wherein the diaphragm breaks upon contact with the surface for the purpose of moving the marking.

[0114] An implementation scheme for applying a delivery system containing LiDAR reflective material and a marker carrier to a surface using an applicator will now be described.

[0115] According to the embodiments, the applicator can be at least one selected from the group consisting of: stamps, brushes, markers, writing pens, styluses, rollers, and needles. According to the embodiments, the applicator can be used to apply a delivery system containing LiDAR reflective material, wherein the delivery system is in the form of a solution, suspension, emulsion, gel, powder, film, fiber, filament, or a combination thereof.

[0116] The applicator can apply various forms of LiDAR reflective material. Non-limiting examples include applying powdered LiDAR reflective material to a surface using a brush, where the powder can be deposited onto the surface by adhesion or electrostatic force; applying solution-form LiDAR reflective material to an absorbent surface such as paper using a pen, where the LiDAR reflective material solute can be adsorbed onto the surface or subsurface as its solvent evaporates; applying concentrated suspension-form LiDAR reflective material to a semi-absorbent surface such as leather using a stamp with a unique pattern, where the LiDAR reflective material suspension can be deposited onto the semi-absorbent surface displaying a unique pattern; depositing LiDAR reflective material onto the surface in film form using a roller, where the film can be adhered to the surface using an adhesive or electrostatic force; or distributing viscous LiDAR reflective material onto a non-absorbent surface such as metal or plastic using a roller, where the viscous LiDAR reflective material can adhere to the surface. The applicator can also be used to apply unique markings to surfaces, such as lettering, barcodes, QR codes, etc., which can be scanned by a LiDAR detection device but are invisible to the naked eye if the surface is dark, such as the delivery system. This unique marker can provide covert identification information to users who scan it. In one implementation, the unique marker can link users who scan it using a LiDAR detection device to additional information about the surface, such as by linking a QR code to a website.

[0117] refer to Figure 1A , Figure 1B and Figure 1C These figures provide illustrations of marking the surface of a dark object 100 with LiDAR reflective markers 121 or LiDAR reflective unique patterns 141 for the purpose of enhanced LiDAR detection or identification. For example, as Figure 1A As shown, when viewed by the human eye, the cubic object 100 has a dark surface 110, corners 120, and edges 130. However, because the dark surface 110 absorbs LiDAR light and reduces the intensity of LiDAR reflection, the LiDAR sensor may mischaracterize the cubic object 100 and detect a blurry object 200 with surface 210, or may not detect the dark object 100 at all.

[0118] To provide or enhance LiDAR detection of cube 100, the corners 120 of cube 100 can be marked with LiDAR reflective markers 121 formed using a LiDAR reflective delivery system as disclosed herein, such as... Figure 1B As shown (left). The LiDAR reflective marker 121 reflects LiDAR radiation, thereby enabling the LiDAR detection device to identify the corner 220 of the detected object 200, such as... Figure 1B(See right). However, the marked corner 121 cannot be distinguished from the dark surface 110 by the human eye. Based on the surface 210 and corner 220 observed by the LiDAR detection device, the edge 230 of the detected object 200 can be predicted. By identifying its surface 210, corner 220, and edge 230, the LiDAR-detected object 200 accurately depicts the cubic object 100.

[0119] Furthermore, the surface 110 of the cubic object 100 can be marked with a unique LiDAR reflection pattern 141, such as... Figure 1C As shown. The unique LiDAR reflection pattern 141 has a unique pattern containing information. For example, but not limited to, the unique LiDAR reflection pattern 141 may be: an arrow indicating the orientation of object 100, a QR code indicating the content contained within object 100, a trademark, or other informational pattern that can be used by a LiDAR detection device to transmit messages to robots, autonomous vehicles, or other observers. It should be understood that, although Figure 1C The unique LiDAR reflection pattern (arrow) 141 shown is light-colored, but this is only for illustrative purposes, and the unique LiDAR reflection pattern 141 will not be discernible to the human eye from the dark surface 110. The unique LiDAR reflection pattern 141 reflects LiDAR light, thereby enabling the LiDAR sensor to identify the markings 240 on the surface 210 of the detected object 200 and the information contained therein.

[0120] Additionally, in the implementation scheme, the unique LiDAR reflective pattern 141 can be an information-encoded pattern, wherein the information is encoded by letters, images, barcodes, fonts, QR codes, or any other format. For example... Figure 1C As shown, the unique LiDAR reflective pattern 141 can provide information such as the orientation or marking of an object, and allows a LiDAR detection device to detect the orientation or marking of an object. An embodiment in which a delivery system comprising LiDAR reflective material and a marker carrier is applied to a surface by spraying will now be described.

[0121] Methods for spraying LiDAR reflective materials may also include introducing a propellant into a delivery system to adjust the volume ratio of the LiDAR reflective material to the marker carrier, pressurizing the delivery system, or combinations thereof. The spraying method is applicable to various forms of LiDAR reflective materials. Non-limiting examples include aerosol spraying of a fluid suspension of LiDAR reflective material or aerosol spraying of dry powder of LiDAR reflective material. Spraying LiDAR reflective materials enables large-area surface marking. Non-limiting examples include spraying LiDAR reflective material onto portions of the surface of a dark object (e.g., doors or body panels of a dark vehicle) to improve LiDAR detection and thus improve road safety, or spraying onto portions of the surface of structural or building materials (e.g., support columns or stiffeners) for non-contact or non-destructive structural health and fatigue monitoring, including surface cracks, deformation, erosion, etc.

[0122] Spraying can be performed using at least one of the following: air sprayers, electrostatic powder sprayers, powder sprayers, ultrasonic sprayers, plasma sprayers, and arc sprayers. For example, but not limited to, LiDAR reflective materials in fibrous form can be sprayed to form nonwoven fabrics. Furthermore, LiDAR reflective fibers can be sprayed onto the surface of textiles, followed by a flocking printing process to form LiDAR reflective fabrics.

[0123] An embodiment of applying LiDAR reflective material to a surface by contacting a membrane encapsulating the LiDAR reflective material will now be described, wherein the membrane ruptures upon contact with the surface. The encapsulated LiDAR reflective material may be in the form of a solution, suspension, emulsion, gel, powder, film, fiber, filament, or a combination thereof.

[0124] Contact between the diaphragm and the surface can be achieved by physical throwing or mechanical launching of the encapsulated LiDAR reflective material. Upon contact, the impact force causes the diaphragm to rupture and release the encapsulated LiDAR reflective material, thereby marking the contact surface. Mechanical launching can be achieved using a pressurized delivery device that allows marking of articles or surfaces from a distance using the LiDAR reflective material, or by using a sling, catapult, trebuchet, bow, etc.

[0125] The impact force required to rupture the diaphragm depends on the diaphragm's elasticity and brittleness, which can vary depending on the diaphragm's composition. As described above, in an embodiment, the diaphragm is selected from the group consisting of: gelatin, polyethylene terephthalate (PET), polystyrene, nylon, polycarbonate, epoxy resin, phenolic resin, urethane, polyester, vinyl ester, polyethylene, polypropylene, polyvinyl chloride, polymethyl methacrylate, acrylonitrile-butadiene-styrene (ABS), polydimethylsiloxane, polysulfides, and combinations thereof. Plasticizers can be used to improve the elasticity of these polymeric materials, including but not limited to: diisodecyl phthalate, diisoundecyl phthalate, ditridecyl phthalate, bis(2-ethylhexyl) adipate, dibutyl sebacate, butyl benzyl phthalate, bis(2-ethylhexyl) phthalate, diisononyl phthalate, bis(2-propylheptyl) phthalate, polycarboxylate esters, and combinations thereof.

[0126] Alternatively, the method of marking a surface with LiDAR reflective material may also include applying the LiDAR reflective material to the surface by printing it onto a sheet, wherein the printed LiDAR reflective mark has a unique design. The unique design may be: fonts, barcodes, QR codes (two-dimensional codes), or other informational patterns that can convey messages to robots, autonomous vehicles, or other observers. The sheet can be removed or dissolved by water. Upon removal of the sheet, the unique LiDAR reflective mark is transferred to the surface.

[0127] Furthermore, for safety purposes, dark LiDAR markings can be used by employing intricate designs on dark objects that are imperceptible to the naked eye but detectable by LiDAR detection devices. Similarly, artifacts or structures (such as trees, abandoned structures, and vehicles) can be marked using the systems disclosed herein and targeted by LiDAR detection devices (such as robots or drones). For example, a dark landing pad marked by the delivery system described herein can be detected by a drone using a LiDAR detection device.

[0128] Example

[0129] The implementation scheme will now be further illustrated through the following examples.

[0130] Example 1

[0131] The reflective behavior of paint samples containing dark pigments was compared. The samples included two types of CuO microcrystals: N-CuO-A with a crystal size of approximately 100 Å and a (111) / (-111) ratio close to 1; and N-CuO-C with a crystal size of approximately 204 Å and a (111) / (-111) ratio close to 1.1. HEUCODUR HD 910, a near-infrared (NIR) reflective black pigment based on ferrochromium oxide, was obtained from Heucotech LTD (referred to as "Cold Black"). MONARCH 900, a carbon black, was obtained from Cabot Corporation (referred to as "Carbon Black").

[0132] The crystallographic information of CuO nanoparticles was investigated using powder X-ray diffraction (XRD, Rigaku Miniflex 600, Japan) with Cu Kα radiation (λ = 0.1541 nm). The average crystallite size τ of the prepared particles was evaluated by measuring the width of their XRD diffraction curves using the Scherrer formula.

[0133]

[0134] Here, k is a dimensionless form factor with a value close to one. λ represents the wavelength of the X-ray radiation, β is the spectral line broadening at half maximum intensity (FWHM), and θ is the Bragg angle.

[0135] The optical properties of the coated panels were studied using a UV / Vis / NIR spectrophotometer (USA Agilent Cary 7000). The Kubelka-Munk function was used as the basis for the study. Bandgap calculations are performed, which involve the diffuse reflectance of the sample through the following relationship. :

[0136]

[0137] here, It is the absolute value of reflectivity. Equal to the absorption coefficient. Plotted relative to energy. To evaluate the indirect bandgap of the sample. Extrapolate the linear portion of the curve to... To obtain indirect bandgap energy.

[0138] The blackness M of the coated samples was evaluated using an X-Rite Ci7600 benchtop spectrophotometer (USA, X-Rite). y It is directly related to the reference value provided by the instrument.

[0139]

[0140] Where Y n=100.000 is one of the CIE white point values ​​under the D65 / 10 condition. Y is one of the CIE tristimulus values ​​of the measured sample.

[0141] Figure 2 The reflectance spectra depicted show that the coating sample containing N-CuO-A provides an elegant black with almost complete absorption in the visible light, similar to carbon black, but retaining NIR reflectance with a maximum peak close to 905 nm. Measurements of blackness show an M value as high as 135.5. y Value, such as Figure 3 As shown. In contrast, coatings containing carbon black exhibit very low reflectance (less than 1%) across the entire visible and NIR wavelength range, resulting in a high blackness value of approximately 135. Coatings with N-CuO-C selectively exhibit high NIR reflectance between 900 nm and 1000 nm, but they show discernible reflection in the visible wavelength range, particularly in red hues, resulting in a pronounced brownish tint and a blackness value of less than 130. Conversely, the "cool black" sample shows strong reflectance at the deeper end of the NIR spectrum above 905 nm, but lacks sufficient absorption in the visible wavelength range, resulting in a blackness value of 128. Figure 3 The inserted photographs reveal the differences in blackness among these original pigment samples, which is consistent with... Figure 3 The reflectance spectra of the coating samples shown are very consistent in the visible light range.

[0142] Example 2

[0143] N-CuO-A microcrystals were mixed with polyurethane resin at a powder / resin ratio of 1:4, and then applied to a steel plate surface with a wet film thickness of 200 μm (or 8 mils) via a doctor blade. The mixture had pre-coated semi-black (reflectivity—maximum 1%) and semi-white (reflectivity—minimum 78%) surfaces. A transparent, colorless coating with a dry film thickness of 60 μm was then applied over the sample, similar to an automotive coating system.

[0144] Example 3

[0145] To verify the LiDAR reflectivity of N-CuO-A microcrystals, a robotic car (model TurtleBot 3 Burger) equipped with a 905 nm 2D laser scanner was used to simulate an autonomous vehicle. The laser scanner is capable of sensing 360 degrees, collecting a set of data around the robot for SLAM (Simultaneous Localization and Mapping) and navigation, as well as for stopping upon obstacle detection. Figure 4AThe diagram illustrates the setup where the coated panel is placed in front of an autonomous robotic car each time, and an illustration shows the prepared N-CuO-A coated panel, which looks identical to the carbon black coating. When the distance and angle are fixed, the intensity of the LiDAR sensor reflected by the panel and recorded on the screen is only proportional to the panel's reflectivity intensity at 905 nm. When the tested panel is placed at a fixed distance of 6 inches and a fixed angle (8... o When placed in front of the robot car, Figure 4B The LiDAR intensity values ​​detected on the sensor were recorded via Bluetooth. This clearly revealed that the LiDAR intensity of the N-CuO-A coated panel was significantly higher (almost 1500%) than that of the coated panel made from carbon black. Therefore, the LiDAR reflectivity from the N-CuO-A coating sample was sufficient for the robotic car to detect and execute an automatic "stop," as... Figure 4D As shown; and due to near-complete absorption in the near-infrared wavelength, it will "collide" onto the carbon black panel, as... Figure 4C As shown.

[0146] While specific embodiments have been described and illustrated herein, it should be understood that various other changes and modifications may be made without departing from the spirit and scope of the claimed subject matter. Furthermore, although various aspects of the claimed subject matter have been described herein, these aspects need not be used in combination. Therefore, the appended claims are intended to cover all such changes and modifications within the scope of the claimed subject matter.

Claims

1. A method for marking a surface with a marking material, the method comprising: Select the surface to be marked; The marking material is applied to the surface, wherein The marking material comprises: LiDAR reflective materials; and marker carrier, and The LiDAR reflective material comprises: Average particle size from 5 nm to 15 nm; Blackness M, 130 to 170 y ; ≤10% reflectance in the visible spectrum of electromagnetic radiation; and ≥10% reflectance in the near-infrared and LiDAR spectra of electromagnetic radiation.

2. The method of claim 1, wherein applying the LiDAR reflective material to the surface comprises spraying the surface with the LiDAR reflective material.

3. The method of claim 1, wherein applying the LiDAR reflective material to the surface comprises applying the LiDAR reflective material to the surface using an applicator.

4. The method of claim 3, wherein the applicator is selected from at least one of the group consisting of a stamp, a brush, a marker, a writing pen, a stylus, a roller, and a needle.

5. The method of claim 1, wherein applying the LiDAR reflective material to the surface comprises: A diaphragm encapsulating the LiDAR reflective material is brought into contact with the surface, wherein the diaphragm is selected from the group consisting of: polyethylene terephthalate, polystyrene, gelatin, nylon, polycarbonate, epoxy resin, phenolic resin, urethane, polyester, vinyl ester, polyethylene, polypropylene, polyvinyl chloride, polymethyl methacrylate, acrylonitrile-butadiene-styrene, polydimethylsiloxane, polysulfide, or a combination of two or more thereof; and The diaphragm ruptures upon contact with the surface.

6. The method of claim 1, wherein the LiDAR reflective material is applied to the surface as a unique marking design.

7. The method of claim 6, wherein the unique marking design is a glyph, barcode, or QR code.

8. A labeling composition comprising: LiDAR reflective materials; and marker carrier, The LiDAR reflective material described herein comprises: Average particle size from 5 nm to 15 nm; Blackness M, 130 to 170 y ; ≤10% reflectance in the visible spectrum of electromagnetic radiation; and ≥10% reflectance in the near-infrared and LiDAR spectra of electromagnetic radiation.

9. The labeling composition of claim 8, wherein the labeling composition is encapsulated in a membrane selected from the group consisting of: polyethylene terephthalate, polystyrene, gelatin, nylon, polycarbonate, epoxy resin, phenolic resin, urethane, polyester, vinyl ester, polyethylene, polypropylene, polyvinyl chloride, polymethyl methacrylate, acrylonitrile-butadiene-styrene, polydimethylsiloxane, polysulfides, and combinations thereof.

10. The marking composition of claim 8, wherein the composition further comprises a propellant selected from the group consisting of: difluorochloromethane, dimethyl ether, methyl ethyl ether, tetrafluoroethane, heptafluoropropane, hydrofluoroolefins, low molecular weight hydrocarbons, butane, isobutylene, propane, nitrous oxide, carbon dioxide, nitrogen, and combinations thereof.

11. The labeling composition of claim 8, wherein the labeling carrier is a gas selected from the group consisting of argon, nitrogen, oxygen, difluorochloromethane, dimethyl ether, methyl ethyl ether, tetrafluoroethane, heptafluoropropane, hydrofluoroolefins, chlorofluorocarbons, low molecular weight hydrocarbons, butane, isobutylene, propane, nitrous oxide, carbon dioxide, and combinations thereof.

12. The marking composition of claim 11, wherein the LiDAR reflective material comprises a dark pigment selected from the group consisting of: CuO microcrystals, carbon black, ferrochrome oxide and its derivatives, or a combination of two or more thereof.

13. The marking composition of claim 12, wherein the dark pigment comprises CuO microcrystals having an (-111) / (111) intensity ratio of 0.5 to 1.

5.

14. The marking composition of claim 12, wherein the dark pigment comprises CuO microcrystals having an (-111) / (111) intensity ratio of 0.9 to 1.

1.

15. The labeling composition of claim 8, wherein the labeling carrier is a fluid selected from the group consisting of: water, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl pentyl ketone, isophorone, diacetone alcohol, diisobutyl ketone, ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, glycol ether ester, propylene glycol monomethyl ether acetate, ethanol, butanol, propanol, ethylene glycol monobutyl ether, ethylene glycol mono-n-propyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, and combinations thereof.

16. The labeling composition of claim 8, wherein the labeling carrier is a polymer selected from the group consisting of polyethylene terephthalate, polystyrene, gelatin, nylon, polycarbonate, epoxy resin, phenolic resin, urethane, polyester, vinyl ester, polyethylene, polypropylene, polyvinyl chloride, polymethyl methacrylate, acrylonitrile-butadiene-styrene, polydimethylsiloxane, polysulfides, and combinations thereof.

17. The labeling composition of claim 8, wherein the labeling carrier is a combination of gas and fluid, wherein The gas is selected from: argon, nitrogen, oxygen, dichlorofluoromethane, dimethyl ether, methyl ethyl ether, tetrafluoroethane, heptafluoropropane, hydrofluoroolefins, chlorofluorocarbons, low molecular weight hydrocarbons, butane, isobutylene, propane, nitrous oxide, carbon dioxide, and combinations thereof; and The fluid is selected from: water, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl pentyl ketone, isophorone, diacetone alcohol, diisobutyl ketone, ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, glycol ether ester, propylene glycol monomethyl ether acetate, ethanol, butanol, propanol, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, and combinations thereof.

18. The labeling composition of claim 8, wherein the labeling carrier is a combination of a fluid and a polymer, wherein The fluid is selected from: water, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, isophorone, diacetone alcohol, diisobutyl ketone, ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, glycol ether ester, propylene glycol monomethyl ether acetate, ethanol, butanol, propanol, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, and combinations thereof; and The polymers are selected from: polyethylene terephthalate, polystyrene, gelatin, nylon, polycarbonate, epoxy resin, phenolic resin, urethane, polyester, vinyl ester, polyethylene, polypropylene, polyvinyl chloride, polymethyl methacrylate, acrylonitrile-butadiene-styrene, polydimethylsiloxane, polysulfides, and combinations thereof.

19. The marking composition of claim 8, wherein the LiDAR reflective material comprises an average particle size of 8 nm to 12 nm.

20. The marking composition of claim 8, wherein the LiDAR reflective material comprises a blackness M of 150 to 170. y .

21. The marking composition of claim 8, wherein the LiDAR reflective material contains ≤5% reflectivity in the visible spectrum of electromagnetic radiation.

22. The marking composition of claim 8, wherein the LiDAR reflective material comprises ≥20% reflectivity in the near-infrared and LiDAR spectra of electromagnetic radiation.

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