CN112176337A - Laser cladding biological metal ceramic pot and preparation method thereof - Google Patents

Laser cladding biological metal ceramic pot and preparation method thereof Download PDF

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Publication number
CN112176337A
CN112176337A CN202011069375.5A CN202011069375A CN112176337A CN 112176337 A CN112176337 A CN 112176337A CN 202011069375 A CN202011069375 A CN 202011069375A CN 112176337 A CN112176337 A CN 112176337A
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cladding layer
cladding
powder
layer
particles
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CN112176337B (en
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刘炳耀
陈健
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Sinotech Group Guangdong Technology Research Co ltd
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Sinotech Group Guangdong Technology Research Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
    • C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47J—KITCHEN EQUIPMENT; COFFEE MILLS; SPICE MILLS; APPARATUS FOR MAKING BEVERAGES
    • A47J27/00—Cooking-vessels
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47J—KITCHEN EQUIPMENT; COFFEE MILLS; SPICE MILLS; APPARATUS FOR MAKING BEVERAGES
    • A47J36/00—Parts, details or accessories of cooking-vessels
    • A47J36/02—Selection of specific materials, e.g. heavy bottoms with copper inlay or with insulating inlay
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/04—Alloys containing less than 50% by weight of each constituent containing tin or lead
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
    • C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
    • C22C32/0052—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only carbides
    • C22C32/0063—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only carbides based on SiC
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/02—Coating starting from inorganic powder by application of pressure only
    • C23C24/04—Impact or kinetic deposition of particles

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

Abstract

The invention discloses a laser cladding biological metal ceramic pot and a preparation method thereof, and relates to the technical field of non-stick pots. The inner surface of the non-stick pan body sequentially comprises a first cladding layer, a second cladding layer and a third cladding layer from inside to outside; wherein the first cladding layer is made of Othello (Odello) particles; the second cladding layer is formed by laser cladding of 80-90% of Othello (Odello) particles and 10-20% of ceramic particles; the third cladding layer is formed by laser cladding of 60-90% of Cu-Ag-Ti powder and 10-40% of ceramic particles; the Othello (Othello) particles consist of 20-40% of aluminum-coated nickel, 20-40% of stainless steel, 10-30% of silver-coated copper and 10-30% of titanium oxide by mass fraction, and the particle size is 10-60 mu m. The laser cladding biological metal ceramic pot provided by the invention has an antibacterial effect, and the hardness and the wear resistance of the pot can be further improved by adding the ceramic particles. The preparation method of the laser cladding biological metal ceramic pot provided by the invention is simple in process and suitable for industrial production.

Description

Laser cladding biological metal ceramic pot and preparation method thereof
Technical Field
The invention relates to the technical field of kitchenware, in particular to a laser cladding biological metal ceramic pot and a preparation method thereof.
Background
The hygiene of kitchen utensils is directly related to the health of people, and along with the increasing emphasis on the improvement of healthy life quality, the requirements on appliances in the kitchen utensils, such as cookware, which are in direct contact with the diet of people are higher and higher, so that the cooking function and the hygiene, such as the function in the aspect of antibiosis, are required to be met.
The pan has the advantages of antibiosis, wear resistance and good product quality with long service life, is the demand of consumers and is the aim of research and development of most manufacturers.
Disclosure of Invention
The invention aims to solve the technical problem of providing an anti-bacterial and wear-resistant non-stick pan.
In order to solve the above problems, the present invention proposes the following technical solutions:
the invention provides a laser cladding biological metal ceramic pot, which comprises a pot body,
the inner surface of the pot body sequentially comprises a first cladding layer, a second cladding layer and a third cladding layer from inside to outside;
the first cladding layer is made of Othello (Odello) particles;
the second cladding layer is formed by laser cladding of 80-90% of Othello (Oudero) particles and 10-20% of ceramic particles by mass fraction;
the third cladding layer is formed by laser cladding of 60-90% of Cu-Ag-Ti powder and 10-40% of ceramic particles by mass;
the Othello (Othello) particles consist of 20-40% of aluminum-coated nickel, 20-40% of stainless steel, 10-30% of silver-coated copper and 10-30% of titanium oxide by mass fraction, and the particle size is 10-60 mu m.
The aluminum-clad nickel takes nickel as a core part, and a layer of aluminum composite powder is uniformly and completely coated on the outer surface of the nickel; which consists of 80-95 percent of nickel and 5-20 percent of aluminum in percentage by mass.
The stainless steel is 304 stainless steel or 201 stainless steel.
The silver-coated copper takes copper as a core part, and a layer of silver composite powder is uniformly and completely coated on the outer surface of the copper; which consists of 70-95% of copper and 5-30% of silver by mass percentage.
The ceramic particles comprise aluminum oxide, zirconium dioxide and titanium dioxide.
Preferably, the ceramic particles used in the present invention are made of alumina Al2O3Zirconium dioxide ZrO2Titanium dioxide TiO2Is mixed according to the mass ratio, wherein, Al is2O3：ZrO2：TiO2＝0.8-1.2:0.8-1.2:0.8-1.2。
The further technical proposal is that the grain diameter of the ceramic particles is 10-60 μm, preferably 30-45 μm.
The further technical scheme is that the Cu-Ag-Ti powder is of a three-layer wrapping structure, and comprises Ti-6Al-4V, Cu and nano Cu-Ag from inside to outside; wherein the innermost layer is Ti-6Al-4V with the diameter of 10-50 μm, the middle layer is Cu with the thickness of 4-20 μm, and the outermost layer is nano Cu-Ag with the thickness of 4-10 μm; wherein, the nano Cu-Ag consists of 70-95 percent of Cu and 5-30 percent of Ag in percentage by mass.
Ti-6Al-4V is titanium hexa-aluminum tetra-vanadium and is titanium alloy metal spherical powder; wrapping Cu powder on the surface of Ti-6Al-4V to form Ti-6Al-4V-Cu spherical powder, and wrapping nano Cu-Ag powder on the surface of Ti-6Al-4V-Cu to finally obtain the Cu-Ag-Ti powder. The average diameter of the nano Cu-Ag powder is 40-60 nm.
The further technical proposal is that the outer surface of the pot body is provided with an energy-saving layer with the thickness of 50-150 μm.
The further technical scheme is that the energy-saving layer comprises the following components in percentage by mass:
8-30% of titanium powder; 5-22% of zirconium powder; 5-22% of iron powder; 8-20% of copper powder; 5-20% of antimony powder; 5-11% of tin powder; 0.5 to 1.5 percent of silicon carbide powder.
The further technical proposal is that the material of the pan body is any one of aluminum, iron, stainless steel, copper, titanium and ceramics.
The invention also provides a method for preparing the laser cladding biological metal ceramic pot, which comprises the following steps:
s1, performing sand blasting treatment on the clean pot body;
and (3) adopting a chemical degreasing method to purify the surface of the pot body to obtain a clean pot body. The chemical degreasing refers to cleaning degreasing by using an organic solvent or soaking degreasing by using an alkaline treatment agent.
Further, carrying out sand blasting treatment on the inner surface of the pot body by using brown fused alumina with 24 meshes, wherein the spraying pressure is 0.5-0.75 MPa, and the spraying speed is 1-2 m3The spray jet speed is 10kg/h, the treatment time is 45-60 s, the spray angle is 75-90 degrees, and the spray distance is 30-50 mm. The surface roughness of the pot body reaches Ra 5.0-12.0 μm; the roughness is beneficial to the first cladding layer to have the best adhesive force, and the bonding strength of the first cladding layer and the pot body is improved.
S2, heating the pot body to the temperature of 220 ℃ and 280 ℃, and carrying out laser cladding on the first cladding layer, the second cladding layer and the third cladding layer in sequence;
and S3, spraying an energy-saving layer.
The energy-saving layer can be sprayed by a cold spraying method.
The working principle of cold spraying is as follows: cold spraying is a spraying technique based on aerodynamic principles. The working process is a spraying mode that high-pressure gas is used for low-temperature heating, powder particles are carried, 1300m/s-1700m/s supersonic gas flow is generated through a Laval nozzle, metal powder axially impacts a base material at the speed of 500m/s-900m/s in a complete solid state, and the metal powder is deposited on the surface of the base material through strong plastic deformation to form a coating. The cold spraying mode can obtain simple substance or composite material coating with low oxygen content, low internal stress, large thickness and high density.
A further technical solution is that the step S2 specifically includes:
a first cladding layer: placing Othello particles on a cladding part on the inner surface of a pot body in advance, and then adopting laser beam irradiation scanning to melt the Othello particles so as to combine a first cladding layer with the inner surface of the pot body, wherein the thickness of the first cladding layer is 20-100 mu m;
a second cladding layer: mixing Othello particles and ceramic particles uniformly, placing the mixture on the surface of a first cladding layer, and then irradiating and scanning the Othello particles and the ceramic particles by using laser beams to combine a second cladding layer with the first cladding layer, wherein the thickness of the second cladding layer is 20-100 mu m;
a third cladding layer: and uniformly mixing Cu-Ag-Ti powder and ceramic particles, placing the mixture on the surface of a second cladding layer, and then irradiating and scanning the mixture by adopting laser beams to melt the Cu-Ag-Ti powder and the ceramic particles so as to combine a third cladding layer with the second cladding layer, wherein the thickness of the third cladding layer is 5-30 mu m.
The laser cladding method is that a laser cladding machine is adopted, argon is used as shielding gas, a fiber laser is used as a transmitting laser source, powder to be prepared is subjected to multi-channel lapping on a substrate in a conical powder beam coaxial powder feeding mode to be subjected to laser cladding, the laser power, the spot diameter, the scanning speed and the powder feeding speed of the laser cladding are controlled, and the lapping coefficient is 0.6.
The further technical scheme is that the laser cladding process parameters are as follows: the power is 400-900W, the diameter of a light spot is 1.2-4 mm, the scanning speed is 50-500 mm/s, and the powder feeding speed is 5-30 g/s.
Compared with the prior art, the invention can achieve the following technical effects:
according to the laser cladding biological metal ceramic pot provided by the invention, the inner surface of the pot body sequentially comprises a first cladding layer, a second cladding layer and a third cladding layer from inside to outside, wherein Othello (Odello) particles of the first cladding layer can be well combined with the pot bottom (especially a metal pot body); the second cladding layer contains a large amount of metal mixed particles (Othello particles) and a certain amount of ceramic particles, and the hardness of the pan is further improved by adding the ceramic particles while being combined with the first cladding layer; the third cladding layer is formed by laser cladding of Cu-Ag-Ti powder and ceramic particles, so that metal ions such as Cu ions, Ag ions, Ti ions and the like are contained on the surface of the pot, the metal ions can be directly contacted with the surface of bacteria to achieve the effects of sterilization and antibiosis, and the hardness of the pot can be further improved by adding the ceramic particles, and the wear resistance is improved.
The preparation method of the laser cladding biological metal ceramic pot provided by the invention is simple in process and suitable for industrial production.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a schematic coating diagram of a laser cladding bio-cermet pot according to an embodiment of the present invention;
FIG. 2 is a schematic structural diagram of Cu-Ag-Ti powder.
Reference numerals
The energy-saving pot comprises a pot body 1, a first cladding layer 2, a second cladding layer 3, a second cladding layer 4 and an energy-saving layer 5;
a Ti-6Al-4V layer 11, a Cu layer 12 and a nano Cu-Ag layer 13.
Detailed Description
The technical solutions in the embodiments will be described clearly and completely with reference to the accompanying drawings in the embodiments of the present invention, wherein like reference numerals represent like elements in the drawings. It is apparent that the embodiments to be described below are only a part of the embodiments of the present invention, and not all of them. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It is to be understood that the terminology used in the description of the embodiments of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the embodiments of the invention. As used in the description of embodiments of the present invention and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
Unless otherwise specified, the percentages in the present invention are mass percentages.
Referring to fig. 1, the embodiment of the invention provides a laser cladding biological metal ceramic pot, which comprises a pot body 1, wherein the inner surface of the pot body 1 sequentially comprises a first cladding layer 2, a second cladding layer 3 and a third cladding layer 4 from inside to outside;
the first cladding layer is formed by laser cladding of Othello (Oudero) particles;
the second cladding layer is formed by laser cladding of 80-90% of Othello (Oudero) particles and 10-20% of ceramic particles by mass fraction;
the third cladding layer is formed by laser cladding of 60-90% of Cu-Ag-Ti powder and 10-40% of ceramic particles by mass;
the Othello particles are metal-based composite powder and consist of 20-40% of aluminum-coated nickel, 20-40% of stainless steel, 10-30% of silver-coated copper and 10-30% of titanium oxide by mass, and the particle size is 10-60 mu m.
The aluminum-clad nickel takes nickel as a core part, and a layer of aluminum composite powder is uniformly and completely coated on the outer surface of the nickel; which consists of 80-95 percent of nickel and 5-20 percent of aluminum in percentage by mass.
The stainless steel is 304 stainless steel or 201 stainless steel.
The silver-coated copper takes copper as a core part, and a layer of silver composite powder is uniformly and completely coated on the outer surface of the copper; which consists of 70-95% of copper and 5-30% of silver by mass percentage.
Understandably, the Othello (Othello) particles of the first cladding layer can be well combined with the pan bottom (especially a metal pan body); the second cladding layer contains a large amount of metal mixed particles (Othello particles) and a certain amount of ceramic particles, and the hardness of the pan is further improved by adding the ceramic particles while being combined with the first cladding layer; the third cladding layer is formed by laser cladding of Cu-Ag-Ti powder and ceramic particles, so that metal ions such as Cu ions, Ag ions, Ti ions and the like are contained on the surface of the pot, the metal ions can be directly contacted with the surface of bacteria to achieve the effects of sterilization and antibiosis, and the hardness of the pot can be further improved by adding the ceramic particles, and the wear resistance is improved.
In one embodiment, the ceramic particles comprise aluminum oxide, zirconium dioxide, titanium dioxide.
Preferably, the ceramic particles used in the present invention are made of alumina Al2O3Zirconium dioxide ZrO2Titanium dioxide TiO2Is mixed according to the mass ratio, wherein, Al is2O3：ZrO2：TiO2＝0.8-1.2:0.8-1.2:0.8-1.2。
In a specific embodiment, the ceramic particles have a particle size of 10 to 60 μm, preferably 30 to 45 μm.
In one embodiment, the Cu-Ag-Ti powder is a three-layer wrapped structure, as shown in FIG. 2, a Ti-6Al-4V layer 11, a Cu layer 12 and a nano Cu-Ag layer 13 from inside to outside; wherein the diameter of Ti-6Al-4V is 10-50 μm, the thickness of the middle layer Cu is 4-20 μm, and the thickness of the outermost layer of nano Cu-Ag is 4-10 μm; wherein, the nano Cu-Ag consists of 70-95 percent of Cu and 5-30 percent of Ag in percentage by mass.
Ti-6Al-4V is titanium hexa-aluminum tetra-vanadium and is titanium alloy metal spherical powder; wrapping Cu powder on the surface of Ti-6Al-4V to form Ti-6Al-4V-Cu spherical powder, and wrapping nano Cu-Ag powder on the surface of Ti-6Al-4V-Cu to finally obtain the Cu-Ag-Ti powder. The average diameter of the nano Cu-Ag powder is 40-60 nm.
In one embodiment, the outer surface of the pot body is provided with an energy-saving layer.
The energy-saving layer comprises the following components in parts by weight:
8-30 parts of titanium powder; 5-22 parts of zirconium powder; 5-22 parts of iron powder; 8-20 parts of copper powder; 5-20 parts of antimony powder; 5-11 parts of tin powder; 0.5-1.5 parts of silicon carbide powder.
The energy-saving layer can achieve the technical effects of energy saving and magnetic conduction by matching the components. One skilled in the art can select a suitable ratio relationship as desired.
The metal powder of the energy saving layer can radiate far infrared waves. The coating has high radiation, and the radiation energy is transmitted in the form of far infrared waves, which are absorbed by the heated object when the far infrared waves are radiated to the heated object. The far infrared wave has strong penetrating power, can penetrate through the pot body and penetrate into food, so that the surface and the inside of the heated object are heated simultaneously, the heating time is further shortened, and the heating is uniform. If the pot body is an aluminum pot and can not be directly used on the induction cooker, the energy-saving layer can conduct magnetism and can be used on the induction cooker, and the application of the aluminum pot is expanded.
In other embodiments, the material of the pan body is any one of aluminum, iron, stainless steel, copper, titanium and ceramic.
The embodiment of the invention also provides a method for preparing the laser cladding biological metal ceramic pot, which comprises the following steps:
s1, performing sand blasting treatment on the clean pot body;
after the pot body is formed, the cleaning operation of oil removal and dust removal needs to be carried out on the pot body, and the clean pot body is beneficial to improving the binding force between the coating and the pot body. The surface of the pot body can be purified by adopting a chemical degreasing method to obtain a clean pot body.
The chemical degreasing refers to cleaning degreasing by using an organic solvent or soaking degreasing by using an alkaline treatment agent.
Further, carrying out sand blasting treatment on the inner surface of the pot body by using brown fused alumina with 24 meshes, wherein the spraying pressure is 0.5-0.75 MPa, and the spraying speed is 1-2 m3The spray jet speed is 10kg/h, the treatment time is 45-60 s, the spray angle is 75-90 degrees, and the spray distance is 30-50 mm. The surface roughness of the pot body reaches Ra 5.0-12.0 μm; the roughness is beneficial to the first cladding layer to have the best adhesive force, and the bonding strength of the first cladding layer and the pot body is improved.
S2, heating the pot body to the temperature of 220 ℃ and 280 ℃, and carrying out laser cladding on the first cladding layer, the second cladding layer and the third cladding layer in sequence; the method comprises the following specific steps:
a first cladding layer: placing Othello particles on a cladding part on the inner surface of a pot body in advance, and then adopting laser beam irradiation scanning to melt the Othello particles to ensure that a first cladding layer is tightly combined with the pot body, wherein the thickness of the first cladding layer is 20-100 mu m;
a second cladding layer: mixing Othello particles and ceramic particles uniformly, placing the mixture on the surface of a first cladding layer, and then scanning and melting the Othello particles and the ceramic particles by adopting laser beam irradiation to ensure that a second cladding layer is tightly combined with the first cladding layer, wherein the thickness of the second cladding layer is 20-100 mu m;
a third cladding layer: and uniformly mixing Cu-Ag-Ti powder and ceramic particles, placing the mixture on the surface of a second cladding layer, and then adopting laser beam irradiation scanning to melt the Cu-Ag-Ti powder and the ceramic particles so that a third cladding layer is tightly combined with the second cladding layer, wherein the thickness of the third cladding layer is 5-30 mu m.
And S3, spraying an energy-saving layer.
The energy-saving layer can be sprayed by a cold spraying method. The working principle of cold spraying is as follows: cold spraying is a spraying technique based on aerodynamic principles. The working process is a spraying mode that high-pressure gas is used for low-temperature heating, powder particles are carried, 1300m/s-1700m/s supersonic gas flow is generated through a Laval nozzle, metal powder axially impacts a base material at the speed of 500m/s-900m/s in a complete solid state, and the metal powder is deposited on the surface of the base material through strong plastic deformation to form a coating. The cold spraying mode can obtain simple substance or composite material coating with low oxygen content, low internal stress, large thickness and high density.
The laser cladding method is that a laser cladding machine is adopted, argon is used as shielding gas, a fiber laser is used as a transmitting laser source, powder to be prepared is subjected to multi-channel lapping on a substrate in a conical powder beam coaxial powder feeding mode to be subjected to laser cladding, the laser power, the spot diameter, the scanning speed and the powder feeding speed of the laser cladding are controlled, and the lapping coefficient is 0.6.
The laser cladding process parameters are as follows: the power is 400-900W, the diameter of a light spot is 1.2-4 mm, the scanning speed is 50-500 mm/s, and the powder feeding speed is 5-30 g/s.
Unless otherwise stated, the laser cladding bio-metal ceramic pots provided in the following examples are all prepared by the above method.
Example 1
The embodiment 1 of the invention provides a laser cladding biological metal ceramic pot, which comprises a pot body with the thickness of 500 mu m, wherein the inner surface of the pot body sequentially comprises a first cladding layer with the thickness of 30 mu m, a second cladding layer with the thickness of 50 mu m and a third cladding layer with the thickness of 30 mu m from inside to outside; the outer surface of the pot body is also provided with an energy-saving layer with the thickness of 110 mu m.
The material of the pan body is aluminum.
The first cladding layer is formed by laser cladding of Othello (Oudero) particles;
the second cladding layer is formed by laser cladding of 80% of Othello (Oudero) particles and 20% of ceramic particles by mass fraction;
the third cladding layer is formed by laser cladding of 70% of Cu-Ag-Ti powder and 30% of ceramic particles by mass.
The Othello (Othello) particles consist of 30 percent of aluminum-coated nickel, 30 percent of stainless steel, 20 percent of silver-coated copper and 20 percent of titanium oxide by mass fraction, and the particle size is 50 mu m;
wherein, the aluminum-coated nickel consists of 85 percent of nickel and 15 percent of aluminum in percentage by mass; the stainless steel is 304 stainless steel; the silver-coated copper consists of 75% of copper and 25% of silver in percentage by mass.
The ceramic particles are made of alumina Al2O3Zirconium dioxide ZrO2Titanium dioxide TiO2Is mixed according to the mass ratio, wherein, Al is2O3：ZrO2：TiO21:1: 1. The ceramic particles have a particle size of 40 μm.
In the Cu-Ag-Ti powder, the diameter of the innermost layer Ti-6Al-4V is 40 mu m, the thickness of the middle layer Cu is 10 mu m, and the thickness of the outermost layer nano Cu-Ag is 10 mu m; wherein, the nano Cu-Ag consists of 70 percent of Cu and 30 percent of Ag in percentage by mass.
The energy-saving layer consists of the following components:
30% of titanium powder; 10% of zirconium powder; 19.5 percent of iron powder; 20% of copper powder; 10% of antimony powder; 10% of tin powder; 0.5 percent of silicon carbide powder.
Example 2
The embodiment 2 of the invention provides a laser cladding biological metal ceramic pot, which comprises a pot body with the thickness of 500 mu m, wherein the inner surface of the pot body sequentially comprises a first cladding layer with the thickness of 40 mu m, a second cladding layer with the thickness of 60 mu m and a third cladding layer with the thickness of 20 mu m from inside to outside; the outer surface of the pot body is also provided with an energy-saving layer with the thickness of 80 mu m.
The material of the pan body is aluminum.
The first cladding layer is formed by laser cladding of Othello (Oudero) particles;
the second cladding layer is formed by laser cladding of 90% of Othello (Oudero) particles and 10% of ceramic particles by mass fraction;
the third cladding layer is formed by laser cladding of 70% of Cu-Ag-Ti powder and 30% of ceramic particles by mass.
The Othello (Othello) particles consist of 30 percent of aluminum-coated nickel, 30 percent of stainless steel, 20 percent of silver-coated copper and 20 percent of titanium oxide by mass fraction, and the particle size is 50 mu m;
wherein, the aluminum-coated nickel consists of 92 percent of nickel and 8 percent of aluminum in percentage by mass; the stainless steel is 201 stainless steel; the silver-coated copper consists of 85 mass percent of copper and 15 mass percent of silver.
The ceramic particles are made of alumina Al2O3Zirconium dioxide ZrO2Titanium dioxide TiO2Is mixed according to the mass ratio, wherein, Al is2O3：ZrO2：TiO21:1: 1. The ceramic particles have a particle size of 40 μm.
In the Cu-Ag-Ti powder, the diameter of the innermost layer Ti-6Al-4V is 40 mu m, the thickness of the middle layer Cu is 10 mu m, and the thickness of the outermost layer nano Cu-Ag is 10 mu m; wherein, the nano Cu-Ag consists of 85 percent of Cu and 15 percent of Ag in percentage by mass.
The energy-saving layer consists of the following components:
30% of titanium powder; 15% of zirconium powder; 9.5 percent of iron powder; 10% of copper powder; 15% of antimony powder; 20% of tin powder; 0.5 percent of silicon carbide powder.
Example 3
The embodiment 3 of the invention provides a laser cladding biological metal ceramic pot, which comprises a pot body with the thickness of 500 mu m, wherein the inner surface of the pot body sequentially comprises a first cladding layer with the thickness of 80 mu m, a second cladding layer with the thickness of 80 mu m and a third cladding layer with the thickness of 10 mu m from inside to outside; the outer surface of the pot body is also provided with an energy-saving layer with the thickness of 100 mu m.
The material of the pan body is aluminum.
The first cladding layer is formed by laser cladding of Othello (Oudero) particles;
the second cladding layer is formed by laser cladding of 90% of Othello (Oudero) particles and 10% of ceramic particles by mass fraction;
the third cladding layer is formed by laser cladding of 90% of Cu-Ag-Ti powder and 10% of ceramic particles by mass.
The Othello (Othello) particles consist of 40 percent of aluminum-coated nickel, 20 percent of stainless steel, 20 percent of silver-coated copper and 20 percent of titanium oxide by mass fraction, and the particle size is 50 mu m;
wherein, the aluminum-coated nickel consists of 81 percent of nickel and 19 percent of aluminum in percentage by mass; the stainless steel is 201 stainless steel; the silver-coated copper consists of 91 percent of copper and 9 percent of silver in percentage by mass.
The ceramic particles are made of alumina Al2O3Zirconium dioxide ZrO2Titanium dioxide TiO2Is mixed according to the mass ratio, wherein, Al is2O3：ZrO2：TiO21.2:1: 1. The ceramic particles have a particle size of 40 μm.
In the Cu-Ag-Ti powder, the diameter of the innermost layer Ti-6Al-4V is 45 mu m, the thickness of the middle layer Cu is 15 mu m, and the thickness of the outermost layer nano Cu-Ag is 10 mu m; wherein, the nano Cu-Ag consists of 85 percent of Cu and 15 percent of Ag in percentage by mass.
The energy-saving layer consists of the following components:
30% of titanium powder; 15% of zirconium powder; 9.5 percent of iron powder; 10% of copper powder; 15% of antimony powder; 20% of tin powder; 0.5 percent of silicon carbide powder.
Example 4
The embodiment 4 of the invention provides a laser cladding biological metal ceramic pot, which comprises a pot body with the thickness of 500 mu m, wherein the inner surface of the pot body sequentially comprises a first cladding layer with the thickness of 50 mu m, a second cladding layer with the thickness of 50 mu m and a third cladding layer with the thickness of 30 mu m from inside to outside; the outer surface of the pot body is also provided with an energy-saving layer with the thickness of 110 mu m.
The material of the pan body is aluminum.
The first cladding layer is formed by laser cladding of Othello (Oudero) particles;
the second cladding layer is formed by laser cladding of 90% of Othello (Oudero) particles and 10% of ceramic particles by mass fraction;
the third cladding layer is formed by laser cladding of 60% of Cu-Ag-Ti powder and 40% of ceramic particles by mass.
The Othello (Othello) particles consist of 30 mass percent of nickel-in-aluminum, 30 mass percent of stainless steel, 20 mass percent of copper-in-silver and 20 mass percent of titanium oxide, and the particle size is 50 mu m. Wherein, the aluminum-coated nickel consists of 85 percent of nickel and 15 percent of aluminum in percentage by mass; the stainless steel is 304 stainless steel; the silver-coated copper consists of 75% of copper and 25% of silver in percentage by mass.
The ceramic particles are made of alumina Al2O3Zirconium dioxide ZrO2Titanium dioxide TiO2Is mixed according to the mass ratio, wherein, Al is2O3：ZrO2：TiO21:1.2: 0.8. The ceramic particles have a particle size of 40 μm.
In the Cu-Ag-Ti powder, the diameter of the innermost layer Ti-6Al-4V is 40 mu m, the thickness of the middle layer Cu is 10 mu m, and the thickness of the outermost layer nano Cu-Ag is 10 mu m; wherein, the nano Cu-Ag consists of 85 percent of Cu and 15 percent of Ag in percentage by mass.
The energy-saving layer consists of the following components:
30% of titanium powder; 15% of zirconium powder; 9.5 percent of iron powder; 10% of copper powder; 15% of antimony powder; 20% of tin powder; 0.5 percent of silicon carbide powder.
Example 5
The embodiment 5 of the invention provides a laser cladding biological metal ceramic pot, which comprises a pot body with the thickness of 500 mu m, wherein the inner surface of the pot body sequentially comprises a first cladding layer with the thickness of 30 mu m, a second cladding layer with the thickness of 60 mu m and a third cladding layer with the thickness of 30 mu m from inside to outside; the outer surface of the pot body is also provided with an energy-saving layer with the thickness of 110 mu m.
The material of the pan body is aluminum.
The first cladding layer is formed by laser cladding of Othello (Oudero) particles;
the second cladding layer is formed by laser cladding of 88% of Othello (Oudero) particles and 12% of ceramic particles by mass fraction;
the third cladding layer is formed by laser cladding of 80% of Cu-Ag-Ti powder and 20% of ceramic particles by mass.
The Othello particles consist of 36 mass percent of nickel-in-aluminum, 35 mass percent of stainless steel, 18 mass percent of copper-in-silver and 11 mass percent of titanium oxide, and the particle size is 45 mu m. Wherein, the aluminum-coated nickel consists of 85 percent of nickel and 15 percent of aluminum in percentage by mass; the stainless steel is 304 stainless steel; the silver-coated copper consists of 75% of copper and 25% of silver in percentage by mass.
The ceramic particles are made of alumina Al2O3Zirconium dioxide ZrO2Titanium dioxide TiO2Is mixed according to the mass ratio, wherein, Al is2O3：ZrO2：TiO21:1.2: 0.8. The ceramic particles have a particle size of 40 μm.
In the Cu-Ag-Ti powder, the diameter of the innermost layer Ti-6Al-4V is 40 mu m, the thickness of the middle layer Cu is 10 mu m, and the thickness of the outermost layer nano Cu-Ag is 10 mu m; wherein, the nano Cu-Ag consists of 85 percent of Cu and 15 percent of Ag in percentage by mass.
The energy-saving layer consists of the following components:
30% of titanium powder; 15% of zirconium powder; 9.5 percent of iron powder; 10% of copper powder; 15% of antimony powder; 20% of tin powder; 0.5 percent of silicon carbide powder.
Comparative example 1: the difference from example 1 is that comparative example 1 lacks the third cladding layer and the pot body thickness is 530 μm.
Comparative example 2: the difference from example 1 is that the third cladding layer of comparative example 2 does not contain ceramic particles.
Comparative example 3: the difference from example 1 is that the third cladding layer of comparative example 3 was formed by laser cladding of 50% Cu-Ag-Ti powder and 50% ceramic particles.
Abrasion resistance and thermal efficiency test
The nonstick pans provided in examples 1-2 and comparative examples 1-3 were subjected to abrasion resistance and thermal efficiency tests.
The wear-resisting test method is that 3kg of static vertical pressure is applied to the upper part of the pot body by using 3M-7447 scouring pad, the back and forth rubbing is carried out, a cycle is carried out, the scouring pad is replaced every 1000 times, and the cycle times are recorded.
The thermal efficiency testing method comprises the steps of turning on the intelligent program-controlled variable-frequency power supply instrument, setting the voltage to be 220V, pressing the starting switch and pressing the display screen power supply switch. 500ml of clean water at normal temperature is added into the sample. And switching on a power supply of the induction cooker, adjusting to the maximum power level for heating until water is boiled, recording the power and time during boiling, and calculating the thermal efficiency.
The results of the abrasion resistance and the thermal efficiency are shown in table 1 below.
TABLE 1 abrasion resistance and thermal efficiency test results
Test items Example 1 Example 2 Comparative example 1 Comparative example 2 Comparative example 3
Abrasion resistance test 280000 274000 120000 180000 277000
Thermal efficiency% 89.50 92.1 91.50 89.50 59.40
And (3) testing antibacterial performance:
sample preparation: example 1;
and (3) comparison: plastic film without antibacterial properties, supplied by SGS laboratories.
The test method refers to GB/T21510-2008, appendix C;
test strains: candida albicans ATCC 10231, Staphylococcus aureus ATCC 6538, Escherichia coli ATCC 25922.
The test results are shown in Table 2.
Table 2 shows the results of the antibacterial property test of example 1
Figure BDA0002712758040000131
The comparative example was changed to stainless steel according to the antibacterial test method, and the antibacterial performance test results are shown in table 3.
Table 3 results of antibacterial property test of example 1 and stainless steel
Figure BDA0002712758040000132
As can be seen from the results in Table 3, stainless steel is not resistant to Candida albicans but only to Staphylococcus aureus and Escherichia coli.
Antimicrobial grading test was performed on the antimicrobial pots provided in examples 1 to 2
Sample preparation: examples 1-2, comparative examples 1-3;
the test method refers to GB/T21551.2-2010, appendix C antifungal performance test method 3 and effect evaluation;
test strains: aspergillus niger ATCC 6275, Aspergillus terreus AS 3.3935, Paecilomyces variotii AS 3.4253, Penicillium funiculosum AS 3.3875, Aureobasidium pullulans AS 3.3984, and Chaetomium globosum ATCC 6205.
Grade evaluation criteria:
grade 0-no-length, i.e., no growth observed under microscope (50 x magnification);
level 1-trace growth, i.e. growth visible to the naked eye, but growth coverage area is less than 10%;
level 2-growth coverage is less than 30%; but not less than 10% (mild growth);
level 2-growth coverage is less than 60%; but not less than 30% (moderate growth);
grade 4-growth coverage area greater than 60% to full coverage (severe growth).
The test results are shown in Table 4.
TABLE 4 antimicrobial ratings of examples 1-2, comparative examples 1-3
Figure BDA0002712758040000141
The results in Table 4 show that the laser cladding biological metal ceramic pot provided by the invention has good antibacterial performance which is obviously superior to that of comparative examples 1-3.
In the above embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.
While the invention has been described with reference to specific embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (10)

1. A laser cladding biological metal ceramic pot comprises a pot body, and is characterized in that the inner surface of the pot body sequentially comprises a first cladding layer, a second cladding layer and a third cladding layer from inside to outside;
the first cladding layer is made of Othello particles;
the second cladding layer is formed by laser cladding of 80-90% by mass of Othello particles and 10-20% by mass of ceramic particles;
the third cladding layer is formed by laser cladding of 60-90% of Cu-Ag-Ti powder and 10-40% of ceramic particles by mass;
the Othello particles consist of 20-40% of aluminum-coated nickel, 20-40% of stainless steel, 10-30% of silver-coated copper and 10-30% of titanium oxide by mass fraction, and the particle size is 10-60 mu m;
wherein, the aluminum-coated nickel consists of 80 to 95 mass percent of nickel and 5 to 20 mass percent of aluminum; the stainless steel is 304 stainless steel or 201 stainless steel; the silver-coated copper consists of 70-95% of copper and 5-30% of silver in percentage by mass.
2. The laser cladding bioceramic pot of claim 1, wherein the ceramic particles comprise aluminum oxide, zirconium dioxide, titanium dioxide.
3. The laser cladding bio-cermet pot of claim 1, wherein the ceramic particles have a particle size of 10-60 μ ι η.
4. The laser cladding biological metal ceramic pot of claim 1, wherein the Cu-Ag-Ti powder is a three-layer wrapped structure, from inside to outside, Ti-6Al-4V, Cu and nano Cu-Ag; wherein the diameter of Ti-6Al-4V is 10-50 μm, the thickness of the middle layer Cu is 4-20 μm, and the thickness of the outermost layer of nano Cu-Ag is 4-10 μm; wherein, the nano Cu-Ag consists of 70-95 percent of Cu and 5-30 percent of Ag in percentage by mass.
5. The laser cladding bio-cermet pot of claim 1, wherein an energy saving layer is disposed on an outer surface of the pot body, and the thickness is 50-150 μm.
6. The laser cladding bio-cermet pot of claim 5, wherein the energy saving layer consists of the following components in percentage by mass:
8-30% of titanium powder; 5-22% of zirconium powder; 5-22% of iron powder; 8-20% of copper powder; 5-20% of antimony powder; 5-11% of tin powder; 0.5 to 1.5 percent of silicon carbide powder.
7. The laser cladding bio-cermet pot of claim 1, wherein the pot body is made of any one of aluminum, iron, stainless steel, copper, titanium, and ceramic.
8. Method for preparing a laser cladding bio-cermet pot according to any of claims 1-7, characterized in that it comprises the following steps:
s1, preparing materials, and performing sand blasting treatment on the clean pot body;
s2, heating the pot body to the temperature of 220 ℃ and 280 ℃, and carrying out laser cladding on the first cladding layer, the second cladding layer and the third cladding layer in sequence;
and S3, spraying an energy-saving layer.
9. The preparation method of the laser cladding biological metal ceramic pot according to claim 8, wherein the step S2 specifically includes:
a first cladding layer: placing Othello particles on a cladding part on the inner surface of a pot body in advance, and then adopting laser beam irradiation scanning to melt the Othello particles so as to combine a first cladding layer with the pot body, wherein the thickness of the first cladding layer is 20-100 mu m;
a second cladding layer: mixing Othello particles and ceramic particles uniformly, placing the mixture on the surface of a first cladding layer, and then adopting laser beam irradiation scanning to melt the Othello particles and the ceramic particles so as to combine a second cladding layer with the first cladding layer, wherein the thickness of the second cladding layer is 20-100 mu m;
a third cladding layer: and uniformly mixing Cu-Ag-Ti powder and ceramic particles, placing the mixture on the surface of a second cladding layer, and then irradiating and scanning the mixture by adopting laser beams to melt the Cu-Ag-Ti powder and the ceramic particles so as to combine a third cladding layer with the second cladding layer, wherein the thickness of the third cladding layer is 5-30 mu m.
10. The preparation method of the laser cladding biological metal ceramic pot of claim 9, wherein the laser cladding process parameters are as follows: the power is 400-900W, the diameter of a light spot is 1.2-4 mm, the scanning speed is 50-500 mm/s, and the powder feeding speed is 5-30 g/s.
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