CN111730209A - Method for making colored mark on object surface by using laser and application - Google Patents
Method for making colored mark on object surface by using laser and application Download PDFInfo
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- CN111730209A CN111730209A CN201910224729.XA CN201910224729A CN111730209A CN 111730209 A CN111730209 A CN 111730209A CN 201910224729 A CN201910224729 A CN 201910224729A CN 111730209 A CN111730209 A CN 111730209A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/36—Removing material
- B23K26/362—Laser etching
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Abstract
The basic principle of laser marking is that a laser generator generates high-energy continuous laser beams, the focused laser beams act on a printing material to instantly melt and even gasify surface materials, and a required graphic mark is formed by controlling the path of the laser beams on the surface of the material. For some materials, the absorption of laser light is poor, and some treatment is often needed on the surface of the materials. The invention relates to a method for making colored marks on the surface of an object by using laser, which is applied to the marking of laser colored marks on the surfaces of various materials. The invention relates to a method for making colored marks on the surface of an object by laser, which is characterized in that a laser colored marking material is attached to the surface of the object, the laser irradiation is carried out for local heating, a laser irradiation area generates a colored mark, the material at other parts is removed, and the colored mark is left on the surface of the object in the laser irradiation area.
Description
Technical Field
The invention relates to a method for making colored marks on the surface of an object by using laser and application thereof.
Background
The basic principle of laser marking is that a laser generator generates high-energy continuous laser beam, the focused laser acts on a printing material to melt or even gasify the surface material instantaneously, and a required image-text mark is formed by controlling the path of the laser on the surface of the material.
The laser marking technology has the characteristics of high speed, high efficiency, energy conservation, environmental protection and the like, is widely applied to industrial production, has unique advantages in the processing field of various materials, and particularly has the advantages of long service life, scratch resistance and the like of laser marking products compared with printing products, so the laser marking technology is mainly applied to the aspects of permanent marking on the surfaces of various materials, product anti-counterfeiting and the like. For some materials, the absorption of laser light is poor, and some treatments are often needed on the surface of the materials, such as: the plastic product is added with the auxiliary agents such as laser absorbent, laser marking additive and the like, and then laser marking is carried out, so that chromatic aberration (contrast) which can be distinguished by naked eyes can be formed; generally, the more pronounced the color difference (the higher the contrast), the better the marking.
The surfaces of inorganic non-metallic materials such as glass, ceramics and the like are smooth and hard, and the marks are not easy to be printed by common (or traditional) ink. In general, special glass ink or a special printing method is used in the industry, but the process is complicated and the cost is high. If the glass paper sticking mode is directly adopted, the glass paper sticking mode is difficult to permanently keep. Laser marking is popular because the process of laser marking is simple and convenient, and any pattern can be marked.
Inorganic nonmetallic materials such as glass, ceramic and the like have good absorption to CO2 laser (10640nm), ultraviolet (355nm) and deep ultraviolet (266nm) laser, and are relatively suitable for glass processing. In prior art, mainly adopt ultraviolet cold light source laser mark glass and ceramic glaze, can interior carving, also can carve glass and ceramic glaze surface, its principle is: the laser is used for gasifying glass and ceramic glaze surfaces to generate extremely small white spots, so that the transparent and smooth surfaces generate the effect similar to ground glass or frosted glass, but the marking effect cannot be clearly seen under the condition of small color difference.
For CO2 laser (10640nm), the thermal conductivity of glass and ceramic glaze is poor, and when the laser is applied, high thermal stress is generated along the processing route due to the small processing area, so that the material is cracked or broken. Glass, however, has a relatively high coefficient of linear expansion and is therefore more susceptible to breakage. Therefore, when the CO2 laser (10640nm) is used for processing glass, irregular cracks can be generated after surface glass is damaged, so that the marking effect is poor (such as irregular edges, surface burrs and the like), the marking requirement can not be basically met, and at present, only the dot matrix effect can basically meet the marking requirement of some industries.
The marking system adopting ultraviolet (355nm) and deep ultraviolet (266nm) lasers has a good processing effect on glass, but the application and popularization are limited due to the problems of low speed, low power, higher price of whole equipment, complex maintenance and the like at present. Glass and ceramic glaze surfaces do not basically absorb YAG (1064nm) laser, so that direct processing by using the YAG laser is difficult.
Aiming at various defects of the laser marking, the invention develops a method for marking the surface of an object with laser and application thereof, and the invention can be applied to the surfaces of all materials and has universality which cannot be realized by the traditional laser marking. .
Disclosure of Invention
Compared with the traditional marking process, the laser marking process has the obvious advantages that:
(1) can process various non-metal materials, and is especially suitable for processing high-hardness, high-melting point and brittle materials.
(2) The laser processing belongs to non-contact processing, does not damage products, has no cutter abrasion, no cutting force and good pattern quality.
(3) The laser beam is very thin, the loss of the processed material is very small, and the processing influence range is small.
(4) The processing efficiency is high, and the automation is easy to realize due to the adoption of computer control.
(5) Various bar codes, numbers, characters, patterns can be marked or engraved.
(6) It is used for preventing counterfeiting and is not easy to counterfeit.
However, some materials cannot be machined or marked with laser light because they absorb little or no laser radiation. The invention aims to provide a method for making colored marks on the surface of an object by using laser and application thereof, which solve the problem of universality of the traditional laser marking and are applied to the manufacture of laser colored marks on the surfaces of various materials of objects.
The invention provides a method for making colored marks on the surface of an object by using laser.
Further, the method is that a laser colored marking material is attached to the surface of an object, local heating is carried out through laser radiation, a laser radiation area generates a colored mark, the material at other parts is removed, and the colored mark is left on the surface of the object in the laser radiation area.
The invention provides the laser colored marking material.
Furthermore, the laser colored marking material can absorb laser energy, the substance elements can absorb laser radiation energy and convert the laser energy into heat energy, the temperature of the laser colored marking material is rapidly raised, the matrix material on the surface of the object and the sintering material in the laser colored marking material are melted, the sintered laser colored marking material is firmly combined with the surface of the object, and the non-volatile substance of the laser colored marking material after sintering enters the sintering part and develops color, so the patent protects the substance capable of generating the effect, namely the simple substance and all compounds containing the elements. In summary, the laser colored marking material of the invention is mainly prepared from the following raw materials in parts by weight:
(1) 0.1 to 99.9 portions of metal simple substance and compound thereof,
(2) 0.1 to 99.9 portions of nonmetal simple substance and compound thereof,
(3) 0.1 to 99.9 portions of dispersant,
(4) 0.1 to 99.9 portions of suspension stabilizer;
(5) 0.1 to 99.9 portions of sintering material,
(6) 0.1 to 99.9 portions of bonding agent
(7) 0.1 to 99.9 portions of other auxiliary agents
The raw materials of the invention comprise simple metal and compounds thereof.
Further, the elementary metal is elementary metal with various levels of sizes, and the elementary metal with various levels of sizes comprises any one or more of the following elements: aluminum, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tungsten, iridium, platinum, gold, thallium, lead, and some rare earth elements: lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.
In the present invention, the metal compound includes any one or more of the following: metal carbides, metal oxides, metal hydroxides, organic metal compounds, various metal salts, and the like.
Further, the metal carbide powder includes any one or more of: aluminum carbide, titanium carbide, vanadium carbide, chromium carbide, manganese carbide, zirconium carbide, niobium carbide, ruthenium carbide, rhodium carbide, tungsten carbide, and carbides of some rare earth elements: lanthanum carbide, cerium carbide.
Further, the metal oxide includes any one or more of the following: oxides of magnesium, calcium, strontium, barium, aluminum, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tungsten, iridium, platinum, gold, thallium, lead, and some rare earth elements: oxides of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium.
Further, the metal hydroxide includes any one or more of the following: lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, aluminum hydroxide, titanium hydroxide, chromium hydroxide, manganese hydroxide, iron hydroxide, cobalt hydroxide, nickel hydroxide, copper hydroxide, zinc hydroxide, zirconium hydroxide, niobium hydroxide, rhodium hydroxide, palladium hydroxide, cadmium hydroxide, indium hydroxide, tin hydroxide, gold hydroxide, thallium hydroxide, lead hydroxide, and hydroxides of some rare earth elements: lanthanum hydroxide, cerium hydroxide, neodymium hydroxide, samarium hydroxide, gadolinium hydroxide and ytterbium hydroxide.
Further, the organometallic compound powder includes any one or more of the following: lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tungsten, iridium, platinum, gold, thallium, lead, and also some rare earth elements: and the organic compound of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.
Further, the metal salt includes any one or more of the following: metal salts of lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tungsten, iridium, platinum, gold, thallium, lead, and some rare earth elements: metal salts of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium.
The raw materials of the invention are as follows: nonmetal simple substances and compounds thereof.
Further, the elemental non-metal powder comprises any one or more of the following: elementary substances of boron, carbon and silicon with different sizes.
The non-metallic simple substance compound in the raw material of the invention is any one or more of the following: compounds of boron of various sizes, compounds of silicon of various sizes, compounds of carbon of various sizes.
Further, the boron compound includes any one or more of the following: magnesium boride, calcium boride, strontium hexaboride, barium hexaboride, aluminum diboride, titanium boride, vanadium boride, chromium boride, manganese boride, iron boride, cobalt boride, nickel boride, zirconium boride, niobium boride, tungsten boride, and borides of some rare earth elements: lanthanum boride, cerium boride, praseodymium boride, neodymium boride, samarium boride, gadolinium boride, terbium boride, erbium tetraboride and ytterbium boride.
Further, the carbon compound includes any one or more of the following: boron carbide, silicon carbide, titanium carbonitride, silicon carbonitride, calcium carbonitride, zirconium carbonitride.
Further, the compound of silicon includes any one or more of the following: silicon nitride, silicon dioxide, silicic acid, iron silicide, organic compounds of silicon, magnesium silicide, strontium silicide, barium silicide, titanium silicide, vanadium silicide, chromium silicide, manganese silicide, iron silicide, cobalt silicide, nickel silicide, copper silicide, zirconium silicide, niobium silicide, tungsten silicide, and also including some rare earth element silicides: lanthanum silicide, cerium silicide, praseodymium silicide, neodymium silicide, europium silicide, gadolinium silicide, terbium silicide, holmium silicide, ytterbium silicide, lutetium silicide oxides.
The raw materials of the invention are as follows: a dispersant.
The dispersing agent can reduce the aggregation of solid or liquid particles in the dispersion system, promote the uniform dispersion of material particles in a medium, form a mixture for stabilizing a suspension and keep the dispersion system relatively stable.
Further, the dispersant includes any one or more of the following: sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate, PVP (polyvinylpyrrolidone) various surfactants (including detergents), polyacrylic acid sodium salt, polyvinyl alcohol triethylhexyl phosphoric acid, sodium dodecyl sulfate, methyl amyl alcohol, cellulose derivatives, polyacrylamide, Guel gum, glycerol, fatty acid polyglycol ester and water glass.
The raw materials of the invention are as follows: a suspension stabilizer.
The suspension stabilizer is a substance that keeps fine particles in a laser-colored marking material of the present invention in a suspended state. Has high dispersity, large surface area and high adsorption force. Can affect the surrounding water and other surrounding particles so that the particles do not sink rapidly, thereby maintaining the concentration of the glaze slip and ensuring that the thickness of the laser colored marking material attached to the surface of the object is uniform.
Further, the suspension stabilizer includes any one or more of the following: attapulgite, bentonite, sodium carboxymethylcellulose (CMC), polyvinyl butyral (PVB), sodium alginate, polyacrylamide and xanthan gum.
The raw materials of the invention are as follows: and (4) sintering the material.
The sintering material is formed by melting and sintering a substance element which can absorb laser energy in a laser colored marking material at a high temperature generated by the substance element after the substance element is acted by laser, the laser colored marking material can be firmly combined with the surface of an object after sintering, and the non-volatile substance enters a sintering part and develops color after the laser colored marking material is sintered.
Further, the sintering material comprises any one or more of the following materials: glass powder, frit powder for glaze, sodium silicate, silica gel and silicic acid.
The raw materials of the invention are as follows: a binding agent.
After the solvent is volatilized, the bonding agent ensures that the laser colored marking material has enough bonding strength with the surface of the object, so that the laser colored marking material is attached to the surface of the object.
Further, the binding agent includes any one or more of: xanthan gum, dextrin powder, arabic gum, paint, clay, bentonite, water glass, silica sol, phosphate, sulfate, polyaluminium chloride, organobentonite, syrup, pulp waste liquid, dextrin, starch, polyvinyl alcohol (PVA), polyvinyl acetate emulsion, water-soluble phenolic resin natural gum, polyacrylic acid, asphalt, coal tar, rosin, phenolic resin, tung oil, ethyl silicate, polyvinyl butyral (PVB), aluminum dihydrogen phosphate (Al (H2PO4) 3), or aluminum dihydrogen phosphate.
The raw materials of the invention are as follows: and (3) other auxiliary agents.
Other additives are special additives which need to be added in order to improve certain properties of the laser colored marking material. There are many kinds of additives, such as surfactants, tackifiers (coupling agents), defoamers, preservatives, moisture inhibitors, wetting agents, colorants, fragrances, and the like.
Further, the other auxiliary agents comprise any one or more of the following: n-butanol, n-pentanol, n-octanol, thymol (also known as thymol), chloronaphthol (also known as pentachlorophenol), sodium pentachlorophenol, sodium benzoate and industrial formaldehyde solution.
The invention provides a preparation method of a laser colored marking material, which mainly comprises two methods. These two forms of embodiments are described in further detail for the purpose of illustrating the invention, and it is not to be understood that the scope of the above-described subject matter is limited to the above-described embodiments, and that any method that allows the raw materials of the present invention to be uniformly mixed and ground is within the scope of the present invention.
The invention provides a first preparation method of a laser colored marking material, which comprises the following steps:
firstly, mixing metal simple substances and compounds (1) thereof, nonmetal simple substances and compounds (2) thereof and sintering materials (5) in the raw materials in proportion, and then carrying out ball milling or air flow milling, uniformly mixing and grinding to obtain mixed powder (8), wherein the fineness of the mixed powder can be automatically controlled according to the precision of laser identification, and the finer the fineness, the better the precision of the laser identification is. And secondly, mixing the dispersing agent (3), the suspension stabilizer (4), the bonding agent (6) and other additives (7) in the raw materials with the mixed powder (8) prepared in the first step, carrying out ball milling, and standing for later use after the ball milling is finished. If the ball-milled materials have agglomeration, a solvent can be added, then the agglomeration of the mixed powder is opened through ultrasonic treatment, and the mixed powder is used after the solvent is completely volatilized.
The invention provides a second preparation method of a laser colored marking material, which comprises the following steps:
the raw materials of the simple metal and the compound (1) thereof, the simple non-metal and the compound (2) thereof and the sintering material (5) of the claim 2 are uniformly mixed according to the proportion, then are melted at high temperature in a smelting furnace, are cooled, crushed and are milled into powder (8) through ball milling or jet milling, the fineness of the powder can be automatically controlled according to the precision of laser identification, and the finer the fineness is, the better the precision of the laser identification is. Mixing the raw material dispersing agent (3), the suspension stabilizer (4), the bonding agent (6) and other auxiliary agents (7) as described in claim 2 with the powder (8) prepared in the first step, performing ball milling, and standing for later use after the ball milling is finished. If the ball-milled materials have agglomeration, a solvent can be added, then the agglomeration of the mixed powder is opened through ultrasonic treatment, and the mixed powder is used after the solvent is completely volatilized.
The invention provides a solvent used in the preparation process of a laser colored marking material.
The solvent is a dispersion medium of the laser colored marking material, and the drying time is controlled. It should have sufficient volatility to ensure rapid drying, save process time for further laser irradiation, and should also be low in viscosity and compatible with other ingredients.
Further, selecting an organic solvent with the volatilization speed of 200-3000 as the solvent;
further, the solvent is preferably any one or more of the following: dichloromethane, acetone, methyl acetate, methanol, n-hexane, tetrahydrofuran, carbon tetrachloride, ethyl acetate, ethanol, butanone, cyclohexane, benzene, isopropanol, dichloroethane, trichloroethylene, n-heptane and toluene.
Further, ball milling includes dry milling without addition of a solvent or wet milling with addition of a solvent.
The invention provides five methods for attaching the laser colored marking material to the surface of an object. These five methods are further detailed for the content of the present invention. It should not be understood that the scope of the above-described subject matter of the present invention is limited to the above description. The technique of attaching laser colored marking material to the surface of an object is within the scope of the present invention.
Further, the first method is as follows: the laser color marking material is added with a solvent with a high volatilization rate, filled in a small spray can, directly sprayed on the surface of an object, and a coating is dried after the solvent is volatilized.
Further, the second method is: the laser color marking material is added into paint matrixes such as varnish, resin, paint and the like, and then is directly coated on the surface of an object by using technologies such as silk-screen printing, pad printing and the like, and the coating is dried.
A further third method is: the laser colored marking material is made into ink and is attached to the surface of an object by an ink-jet printer.
Further, the fourth method is: the laser colored marking material is made into an adhesive tape for use and is adhered to the surface of an object.
Further, the fifth method is: the laser colored marking material is printed on a film by screen printing, pad printing or ink-jet printing, and then the film is adhered on the surface of an object or cut into required size and adhered on the surface of the object.
The invention provides lasers of several lasers.
In general, the following basic rule exists when a laser beam heats a material:
firstly, when the laser action time is the same, the larger the absorbed actual energy is, the faster the temperature rise speed of the material is;
secondly, when the absorbed laser energy is the same, the smaller the specific heat capacity of the material is, the higher the temperature rise is;
thirdly, the smaller the thermal conductivity of the surface material of the object, the larger the temperature gradient between the laser beam application region and the adjacent region of the surface material of the object, under the same energy density and application time. In a laser pigmented marking material, very complex thermal processes occur upon laser irradiation, involving a number of interrelated problems, such as heat absorption and transfer, evolution of microstructures, fluid problems, mechanical problems, chemical problems, etc. In which it is important to understand the absorption of energy and the temperature distribution and evolution caused by the heat transfer process of a laser marking material in the whole laser radiation for the insight into the marking mechanism of a laser marking material. The laser marking process on the surface of the object is always accompanied by 3 heat transfer modes of heat conduction, heat convection and heat radiation. The laser marking device is characterized by comprising laser, a laser color marking material, a heat radiation device, a heat conduction device and a control device, wherein the laser is used for radiating heat of the laser color marking material, the heat conduction device is used for conducting heat between particles which are contacted with each other, the heat conduction device is used for conducting heat between gas-phase particles and solid-phase particles in pores, the heat radiation between the laser color marking material and external gas, convection and the.
The principle of the laser radiation on a laser colored marking material is determined, and a suitable laser can be selected as the laser radiation light source.
Further, the laser of the invention is the laser emitted by the following lasers: gas lasers, solid state lasers, semiconductor pump lasers, fiber lasers, excimer lasers, isotope lasers.
Obviously, many modifications, substitutions, and variations are possible in light of the above teachings of the invention, without departing from the basic technical spirit of the invention, as defined by the following claims.
The present invention will be described in further detail with reference to the following examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
[ description of the drawings ]
FIG. 1, Chinese characters with laser marked ceramic surface
FIG. 2, Chinese characters marked on the surface of glass bottle by laser
Figure 3, Chinese character table trademark with laser mark on metal surface
FIG. 4, Chinese characters of laser mark on surface of plastic bottle
FIG. 5, fine pattern of laser marking of ceramic surface
FIG. 6 is a schematic view of a laser marked hollow fine text on the surface of a ceramic
[ detailed description ] embodiments
Embodiment 1, method for making colored mark on object surface by using laser and application
1. Preparation of laser colored marking material
(1) 5 parts of zinc powder;
(2) 5 parts of carbon powder;
(3) 3 parts of sodium hydroxide;
(4) 5 parts of silver carbonate;
(5) 65 parts of anhydrous copper sulfate;
(6) 2 parts of glass powder;
(7) 5 parts of Arabic gum;
(8) 5 parts of dextrin powder, namely mixing the dextrin powder,
(9) 5 parts of glycerin
The zinc powder (1), the carbon powder (2), the sodium hydroxide (3), the silver carbonate (4), the anhydrous copper sulfate (5) and the glass powder (6) in the raw materials are mixed in proportion, and then are milled by ball milling to prepare the mixed powder (10), the fineness of the mixed powder can be automatically controlled according to the precision of laser identification, and the finer the fineness is, the better the precision of the laser identification is. And secondly, mixing the Arabic gum (7), the dextrin powder (8) and the glycerol (9) in the raw materials with the mixed powder (10) prepared in the first step, adding absolute ethyl alcohol for ball milling, adding the absolute ethyl alcohol after ball milling, opening agglomeration of the mixed powder through ultrasonic treatment, and standing for later use after the solvent is completely volatilized.
2. Method for making colored mark on object surface by using laser
Adding a solvent with a high volatilization rate into the laser colored marking material prepared in the last step, filling the laser colored marking material into a small spray can, directly spraying the laser colored marking material on the surface of an object, and drying a coating after the solvent is volatilized.
After the coating is dried, a 10640nm gas laser or a 1064nm solid laser is used for adjusting the power, the focal length and the processing speed, laser radiation is carried out on the area of the coating of the laser colored marking material to be marked, after radiation, the laser colored marking material which is not radiated is removed, and colored marks are left in the area of the laser colored marking material which is radiated by laser.
3. Application of method for making colored mark on object surface by using laser
The method for making coloured mark on the surface of object by using laser can be used for laser coloured mark on the surface of various material objects, in particular for laser marking on the surface of inorganic non-metal material of glass and ceramic, etc.
Embodiment 2, method for making colored mark on object surface by using laser and application
1. Preparation of laser colored marking material
(1) 2 parts of aluminum powder;
(2) 40 parts of carbon powder;
(3) 3 parts of ferric hydroxide;
(4) 5 parts of cobalt oxide;
(5) 30 parts of copper acetate;
(6) 5 parts of sodium silicate;
(7) 5 parts of polyvinyl alcohol (PVA);
(8) 5 parts of sodium tripolyphosphate and 5 parts of sodium tripolyphosphate,
(9) 5 parts of sodium benzoate
Mixing the aluminum powder (1), the carbon powder (2), the ferric hydroxide (3), the cobalt oxide (4), the copper acetate (5) and the sodium silicate (6) in the raw materials in proportion, and grinding by ball milling to prepare mixed powder (10), wherein the fineness of the mixed powder can be automatically controlled according to the precision of laser identification, and the finer the fineness, the better the precision of the laser identification is. And step two, mixing polyvinyl alcohol (PVA) (7), sodium tripolyphosphate (8) and sodium benzoate (9) in the raw materials with the mixed powder (10) prepared in the step one, adding ethyl acetate for ball milling, adding ethyl acetate after ball milling, opening agglomeration of the mixed powder through ultrasonic treatment, and standing for use after the solvent is completely volatilized.
2. Method for making colored mark on object surface by using laser
The ink regulating oil is added into the laser colored marking material prepared in the last step, and then the laser colored marking material is directly coated on the surface of an object by using a transfer printing technology and the coating is dried.
After the coating is dried, a 1064nm or 532nm solid laser is used for adjusting the power, the focal length and the processing speed, laser radiation is carried out on an area needing to be marked of the coating of the laser colored marking material, after radiation, the laser colored marking material which is not radiated is removed, and colored marks are left in the area of the laser colored marking material which is radiated by the laser.
3. Application of method for making colored mark on object surface by using laser
The method for making coloured mark on the surface of object by using laser can be used for laser coloured mark on the surface of various material objects, in particular for laser marking on the surface of inorganic non-metal material of glass and ceramic, etc.
Embodiment 3, method for making colored mark on object surface by using laser and application
1. Preparation of laser colored marking material
(1) 5 parts of silicon dioxide;
(2) 40 parts of titanium carbide;
(3) 3 parts of potassium hydroxide;
(4) 5 parts of nickel oxide;
(5) 3 parts of neodymium acetate;
(6) 32 parts of glaze frit powder;
(7) 5 parts of sodium carboxymethylcellulose (CMC);
(8) 2 parts of sodium pyrophosphate, namely sodium pyrophosphate, sodium pyrophosphate and sodium pyrophosphate,
(9) 3 parts of ethyl silicate, namely 3 parts of ethyl silicate,
(10) 2 portions of n-butyl alcohol
Mixing silicon dioxide (1), titanium carbide (2), potassium hydroxide (3), nickel oxide (4) and neodymium acetate (5) in the raw materials in proportion, and milling by ball milling to prepare mixed powder (11), wherein the fineness of the mixed powder can be automatically controlled according to the precision of laser identification, and the finer the fineness, the better the precision of the laser identification is. And secondly, mixing sodium carboxymethylcellulose (CMC) (7), sodium pyrophosphate (8), ethyl silicate (9) and n-butanol (10) in the raw materials with the mixed powder (11) prepared in the first step, adding methyl acetate for ball milling, adding the methyl acetate after ball milling, opening agglomeration of the mixed powder through ultrasonic treatment, and standing for later use after the solvent is completely volatilized.
2. Method for making colored mark on object surface by using laser
And adding varnish into the laser colored marking material prepared in the last step, directly coating the laser colored marking material on the surface of an object by using a screen printing technology, and drying the coating.
After the coating is dried, a 1064nm or 532nm solid laser is used for adjusting the power, the focal length and the processing speed, laser radiation is carried out on an area needing to be marked of the coating of the laser colored marking material, after radiation, the laser colored marking material which is not radiated is removed, and colored marks are left in the area of the laser colored marking material which is radiated by the laser.
3. Application of method for making colored mark on object surface by using laser
The method for making coloured mark on the surface of object by using laser can be used for laser coloured mark on the surface of various material objects, in particular for laser marking on the surface of inorganic non-metal material of glass and ceramic, etc.
Claims (10)
1. The method for making the colored mark on the surface of the object by using the laser is applied to marking the laser colored marks on the surfaces of various materials, and the used laser colored mark material has the advantages of simple raw material formula, simple preparation method, good marking effect, easy operation and control, safety, environmental protection, low energy consumption, good economic benefit and suitability for industrial large-scale production.
2. A method for making colored marks on the surface of an object by laser is characterized in that: the method for making colored marks on the surface of an object by laser comprises the steps of attaching a laser colored mark material to the surface of the object, locally heating the material through laser radiation, generating a colored mark in a laser radiation area, removing the material at other parts, and leaving the colored mark on the surface of the object in the laser radiation area.
3. A laser pigmented marking material according to claim 2 wherein: the laser acts on substance elements which can absorb laser energy in a laser colored marking material, the substance elements can absorb laser radiation energy and convert the laser energy into heat energy, the temperature of the substance elements is rapidly raised, a matrix material on the surface of a melt body and a sintering material in the laser colored marking material are melted, the sintered laser colored marking material is firmly combined with the surface of an object, and a non-volatile substance enters a sintering part after the laser colored marking material is sintered and develops color, so the patent protects a substance which can generate the effect, namely a simple substance and all compounds containing the elements.
4. The feedstock according to claim 2, characterized in that: the laser colored marking material is composed of one or more of a metal simple substance and a compound thereof, a nonmetal simple substance and a compound thereof, a dispersing agent, a suspension stabilizer, a sintering material, a bonding agent and other auxiliary agents, and the weight parts of each raw material are as follows:
(1) 0.1 to 99.9 portions of metal simple substance and compound thereof,
(2) 0.1 to 99.9 portions of nonmetal simple substance and compound thereof,
(3) 0.1 to 99.9 portions of dispersant,
(4) 0.1 to 99.9 portions of suspension stabilizer;
(5) 0.1 to 99.9 portions of sintering material,
(6) 0.1 to 99.9 portions of bonding agent
(7) 0.1 to 99.9 portions of other auxiliary agents.
5. The simple metal and the compound thereof are characterized in that: the metal simple substance and the metal compound comprise a metal simple substance and a compound containing the metal element;
the simple metal substance is characterized in that: the elementary metal with various sizes comprises any one or more of the following elements: aluminum, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tungsten, iridium, platinum, gold, thallium, lead, and some rare earth elements: lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium;
the metal compound is characterized by comprising any one or more of the following components: metal carbides, metal oxides, metal hydroxides, organic metal compounds, various metal salts, and the like;
the metal carbide is characterized in that the metal carbide powder comprises any one or more of the following components: aluminum carbide, titanium carbide, vanadium carbide, chromium carbide, manganese carbide, zirconium carbide, niobium carbide, ruthenium carbide, rhodium carbide, tungsten carbide, and carbides of some rare earth elements: lanthanum carbide, cerium carbide;
the metal oxide is characterized by comprising any one or more of the following components: oxides of magnesium, calcium, strontium, barium, aluminum, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tungsten, iridium, platinum, gold, thallium, lead, and some rare earth elements: oxides of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium;
the metal hydroxide is characterized in that the metal hydroxide comprises any one or more of the following components: lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, aluminum hydroxide, titanium hydroxide, chromium hydroxide, manganese hydroxide, iron hydroxide, cobalt hydroxide, nickel hydroxide, copper hydroxide, zinc hydroxide, zirconium hydroxide, niobium hydroxide, rhodium hydroxide, palladium hydroxide, cadmium hydroxide, indium hydroxide, tin hydroxide, gold hydroxide, thallium hydroxide, lead hydroxide, and hydroxides of some rare earth elements: lanthanum hydroxide, cerium hydroxide, neodymium hydroxide, samarium hydroxide, gadolinium hydroxide and ytterbium hydroxide;
the organic metal compound is characterized in that the organic metal compound powder comprises any one or more of the following components: lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tungsten, iridium, platinum, gold, thallium, lead, and also some rare earth elements: organic compounds of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium;
the metal salt is characterized by comprising any one or more of the following components: metal salts of lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tungsten, iridium, platinum, gold, thallium, lead, and some rare earth elements: metal salts of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium;
the simple metal substance is characterized in that the simple metal substance powder comprises any one or more of the following components: elementary substances of boron, carbon and silicon in all levels of sizes;
the nonmetal compound is characterized by comprising any one or more of the following components: compounds of boron of various sizes, compounds of silicon of various sizes, compounds of carbon of various sizes;
the boron compound is characterized by comprising any one or more of the following components: magnesium boride, calcium boride, strontium hexaboride, barium hexaboride, aluminum diboride, titanium boride, vanadium boride, chromium boride, manganese boride, iron boride, cobalt boride, nickel boride, zirconium boride, niobium boride, tungsten boride, and borides of some rare earth elements: lanthanum boride, cerium boride, praseodymium boride, neodymium boride, samarium boride, gadolinium boride, terbium boride, erbium tetraboride and ytterbium boride;
the carbon compound is characterized by comprising any one or more of the following components: boron carbide, silicon carbide, titanium carbonitride, silicon carbonitride, calcium carbonitride, zirconium carbonitride;
the silicon compound is characterized by comprising any one or more of the following components: silicon nitride, silicon dioxide, silicic acid, iron silicide, organic compounds of silicon, magnesium silicide, strontium silicide, barium silicide, titanium silicide, vanadium silicide, chromium silicide, manganese silicide, iron silicide, cobalt silicide, nickel silicide, copper silicide, zirconium silicide, niobium silicide, tungsten silicide, and also including some rare earth element silicides: oxides of lanthanum silicide, cerium silicide, praseodymium silicide, neodymium silicide, europium silicide, gadolinium silicide, terbium silicide, holmium silicide, ytterbium silicide, lutetium silicide;
the dispersant is characterized by comprising any one or more of the following components: sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate, PVP (polyvinylpyrrolidone) various surfactants (including detergents), polyacrylic acid sodium salt, polyvinyl alcohol triethylhexyl phosphoric acid, sodium dodecyl sulfate, methyl amyl alcohol, cellulose derivatives, polyacrylamide, Guel gum, glycerol, fatty acid polyglycol ester and water glass;
the suspension stabilizer is characterized by comprising any one or more of the following components: attapulgite, bentonite, sodium carboxymethylcellulose (CMC), polyvinyl butyral (PVB), sodium alginate, polyacrylamide and xanthan gum;
the sintered material is characterized by comprising any one or more of the following components: glass powder, frit powder for glaze, sodium silicate, silica gel and silicic acid;
the binding agent is characterized by comprising any one or more of the following components: xanthan gum, dextrin powder, arabic gum, paint, clay, bentonite, water glass, silica sol, phosphate, sulfate, polyaluminium chloride, organobentonite, syrup, pulp waste liquid, dextrin, starch, polyvinyl alcohol (PVA), polyvinyl acetate emulsion, water-soluble phenolic resin natural gum, polyacrylic acid, asphalt, coal tar, rosin, phenolic resin, tung oil, ethyl silicate, polyvinyl butyral (PVB), aluminum dihydrogen phosphate (Al (H2PO4) 3), or aluminum dihydrogen phosphate;
the other auxiliary agents are characterized by comprising any one or more of the following components: n-butanol, n-pentanol, n-octanol, thymol (also known as thymol), chloronaphthol (also known as pentachlorophenol), sodium pentachlorophenol, sodium benzoate and industrial formaldehyde solution.
6. The laser pigmented marking material of claim 2 wherein: the preparation methods of the laser colored marking material mainly comprise two methods;
the specific description of these two forms is only for the further detailed description of the present invention, and it should not be understood that the scope of the above-mentioned subject matter of the present invention is limited to the above-mentioned, and any method that can uniformly mix and mill the raw materials of the present invention is within the scope of the present invention;
the first preparation method of the laser colored marking material is characterized by comprising the following steps of: firstly, mixing the raw materials (1), (2) and (5) of claim 2 in proportion, uniformly mixing by ball milling or jet milling and grinding to prepare mixed powder (8), wherein the fineness of the mixed powder can be automatically controlled according to the precision of laser marks, and the finer the fineness, the better the precision of the laser marks; secondly, mixing the raw materials (3), (4), (6) and (7) of claim 2 with the mixed powder (8) prepared in the first step, carrying out ball milling, and standing for standby after the ball milling is finished; if the ball-milled materials are agglomerated, a solvent can be added, then the agglomeration of the mixed powder is opened through ultrasonic treatment, and the mixed powder is used after the solvent is completely volatilized;
the second preparation method of the laser colored marking material is characterized by comprising the following steps: the first step, the raw materials (1), (2) and (5) of claim 2 are mixed uniformly according to a proportion, then are melted at high temperature in a smelting furnace, are crushed after being cooled, and are milled to prepare powder (8) through ball milling or air flow milling, the fineness of the powder can be self-grasped according to the precision of laser marks, and the finer the fineness is, the better the precision of the laser marks is; secondly, mixing the raw materials (3), (4), (6) and (7) of claim 2 with the powder (8) prepared in the first step, carrying out ball milling, and standing for standby after finishing milling; if the ball-milled materials have agglomeration, a solvent can be added, then the agglomeration of the mixed powder is opened through ultrasonic treatment, and the mixed powder is used after the solvent is completely volatilized.
7. The solvent as claimed in claim 6 and claim 7, wherein the solvent is a dispersion medium of the laser marking material, and the drying time is controlled, and the solvent has enough volatility to ensure rapid drying, so as to save the time interval of the process flow for the next laser irradiation, and the solvent also has low viscosity and compatibility with other components, and has high volatilization rate, and is selected from organic solvents with volatilization speed of 200-3000; the solvent in the invention is preferably any one or more of the following: dichloromethane, acetone, methyl acetate, methanol, n-hexane, tetrahydrofuran, carbon tetrachloride, ethyl acetate, ethanol, butanone, cyclohexane, benzene, isopropanol, dichloroethane, trichloroethylene, n-heptane and toluene.
8. The ball mill of claim 6 and claim 7, characterized in that the ball mill comprises dry milling without or wet milling with the addition of the solvent.
9. There are a number of ways to attach a laser colored marking material to an object surface according to claim 2;
one of the above methods of attaching a laser marking material to a surface of an object is characterized in that: adding a solvent with a high volatilization rate into the laser colored marking material, filling the laser colored marking material into a small spray can, directly spraying the laser colored marking material on the surface of an object, and drying a coating after the solvent volatilizes;
the second method for attaching the laser colored marking material to the surface of the object is characterized in that: adding varnish, resin, paint and other coating matrixes into the laser colored marking material, directly coating the laser colored marking material on the surface of an object by using technologies such as silk-screen printing, pad printing and the like, and drying a coating;
the third method for attaching the laser colored marking material to the surface of the object is characterized in that: the laser colored marking material is made into ink and is attached to the surface of an object by an ink-jet printer;
the fourth method for attaching the laser colored marking material to the surface of the object is characterized in that: the laser colored marking material is made into an adhesive tape for use and is adhered to the surface of an object;
the fifth method for attaching the laser colored marking material to the surface of the object is characterized in that: printing a laser colored marking material on a film in a screen printing, pad printing or ink-jet printing mode, and then pasting the film on the surface of an object or cutting the film into a required size to be pasted on the surface of the object;
the method for attaching a laser marking material to a surface of an object is described in further detail, but it should not be understood that the scope of the subject matter of the present invention is limited to the above description, and any technique capable of attaching a laser marking material to a surface of an object is within the scope of the present invention.
10. The laser according to claim 2, characterized in that the laser of the invention is a laser emitted by the following lasers: gas lasers, solid state lasers, semiconductor pump lasers, fiber lasers, excimer lasers, isotope lasers.
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| CN114230173A (en) * | 2021-12-23 | 2022-03-25 | 亚细亚建筑材料股份有限公司 | Solid powder material for reducing glass melting temperature and preparation method thereof |
| CN114309927A (en) * | 2021-11-30 | 2022-04-12 | 清华大学 | Coal tar-based thin film electronic device and preparation method thereof |
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| CN116604120A (en) * | 2023-07-21 | 2023-08-18 | 中国科学院宁波材料技术与工程研究所 | Anti-counterfeiting mark welding method, device and application based on diamond substrate |
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