A kind of preparation method of metal ceramic wear-resisting coating non-stick pan
The present invention is application number: 201210374979X, the applying date: 2012-09-29, invention name
Claim: a kind of wear-resistant coating non-stick pan, divisional application.
Technical field
The present invention relates to a kind of non-stick pan, specifically, relate to a kind of substrate be rustless steel, aluminum,
Wear-resistant unsticky pot of aluminium alloy, cast iron or steel and preparation method thereof.
Background technology
People use traditional metal pan (cast iron, rustless steel, aluminum and aluminum always for a long time
Alloy) cooking food, but often occur food to glue pot phenomenon in cooking process.This is not only
Destroy food profile, and the food of viscous pot be susceptible to be charred, and even produces harmful substance,
Affect health.In addition too increase cooker and scrub difficulty, make troubles to culinary art.Therefore
Non-stick pan since invention just as its easy cleaning, can easily decoct, cooked food and non-stick pan, energy
Reduce oil smoke to greatest extent, meet modern people and pursue pollution-free food, low fat, low in calories
The performance of needs and enjoy liking of masses.
But the non-stick pan of existing market main flow is all dependent at surface spraying one strata fluororesin
The non-viscous paint of class, relies on the characteristic of its strong-hydrophobicity and low-friction coefficient, realizes food not
Gluing, it really can meet in people's cooking process and not occur food to glue the requirement of pot, but it
There is also many defects.First the intensity being polytetrafluorethylecoatings coatings is poor, easily comes off and damages
Bad, and cooking process can soften, can only can not cook harder food with wood shovel
Thing;The most this non-stick pan also should not cook acidic food, otherwise can affect the use of non-stick pan
Life-span;In addition the use temperature of polytetrafluorethylecoatings coatings the most not can exceed that 250 DEG C, Ren Men
It is difficult to during use strictly control, easily damages because of dry combustion method.Polytetrafluorethylecoatings coatings is not glued
Whether pot in use exists harm and there is dispute the most always health, constantly causes
Controversial issue;And once non-viscous paint comes off, may result in being substantially reduced of non-adhesion behavior.
Along with the rise of China's kitchen guarding's revolution, " safe and healthy, energy-conservation, green, environmental protection "
Consumer's extensive concern and the main flow of 2l century kitchen guarding revolution development is enjoyed etc. becoming.Kitchen water,
The improvement of the auxiliary facilities such as electricity, gas, safety and environmental protection cooker development oneself become the bright of cooker industry
Point and focus.Seeing on the whole, in current China family kitchen, non-stick pan market has still been in just
Starting stage.According to investigations, the owning rate of urban family is the lowest, less than l%, rural area base
Blank it is on Ben.Therefore, the energy-saving of cooker product, automatization, intellectuality, attractive in appearanceization
To be the another development trend of cooker industry.
Ceramic material has in fields such as national defence, machinery, chemical industry, metallurgy, electronics to be used widely
Place.Wherein, it is high that titanium carbide TiC pottery has fusing point, good heat conductivity, and hardness is big, chemistry
Stablizing, do not hydrolyze, high-temperature oxidation resistance is good, and thermal coefficient of expansion is little, anti-thermal shock and chemically-resistant
The advantages such as corrosivity is strong, the always focus of countries in the world material scholar research.In recent years, right
The ceramic coating of non-stick pan gets along with the most greatly, has had and titanium oxide or nitride ceramics has been used for not
The report of viscous pot, and achieved with considerable economic and social benefit (such as Arcopal, Vision
Etc. brand).
Based on the demand, the present invention provides the wear-resistant coating of a kind of carborundum metalloid pottery not
Viscous pot.
Summary of the invention
It is an object of the invention to provide a kind of titanium carbide metalloid ceramic wear-resistant coating non-stick pan and
Its preparation method.
Wear-resistant coating non-stick pan of the present invention includes pot and is positioned at the stone of pot inner surface
Layer of ink and metal-cermic coating, the thickness of graphite linings is 5-8 μm, described metal-cermic coating
Thickness is 10-30 μm, including titanium carbide ceramic coating.
Described metal-cermic coating also includes that titanium boride, the weight of described titanium boride are ceramic metal
The 4-30% of coating;.
Titanium carbide ceramic hardness is big, and has good mechanical property, is extraordinary wear-resisting material
Material, but in recent years, owing to aluminium sesquioxide is the most stable, the base material of non-stick pan usually aluminium
Or aluminium alloy, and during carbon-thermal reduction, carbon likely reacts with aluminum generation aluminium carbide,
The existence of aluminium carbide can be substantially reduced mechanical property and the chemical stability of material.Therefore, this
A person of good sense, before spraying composite ceramic powder, first coats one layer of graphite at the bottom of a pan matrix, on the one hand
Raw material can be provided for the preparation of composite ceramic powder, on the other hand be also prevented from carbon in spraying process
Contact combination with aluminum and generate aluminium carbide.
It addition, the existence that inventor also finds titanium boride will suppress the generation of aluminium carbide significantly, for
Ensure the performance of the bottom of a pan of the present invention wear-resistant coating, wear-resistant coating of the present invention also wraps
Include titanium boride;
Titanium boride (TiB2) be boron and the most stable of compound of titanium, pure powders of titanium boride be Lycoperdon polymorphum Vitt or
Grey black, there is the crystal structure of six sides (AlB2), this boron atomic layer being similar to graphite
Shape structure and Ti outer-shell electron determine TiB2There is good electric conductivity and metallic luster, and
Between boron atomic plane and titanium atom face, Ti-B key determines the high rigidity of this material and fragility
Feature.Therefore, its content in metal-cermic coating is difficult to too high, preferably 4-10%;
Coating material of the present invention can use method commonly used in the art to be coated, as etc.
Plasma spray, flame-spraying etc..Spraying raw material may select titanium carbide, silicon dioxide and silicate
Deng, boron powder;Spraying raw material can be commercial, it is possible to by method self-control commonly used in the art, such as
Titanium carbide powder is generally by TiO2With white carbon black in the carbon shirt-circuiting furnace of logical hydrogen or frequency modulation vacuum
In stove, under 1600 DEG C of-1800 DEG C of high temperature, reaction prepares.
Particularly, the present invention provides the preparation method of a kind of above-mentioned metal ceramic wear-resisting coating.
The preparation method of described metal ceramic wear-resisting coating non-stick pan, comprises the steps:
1) pot molding: select metallic plate to make a pot embryo;
2) matrix surface processes: above-mentioned pot embryo is put into sand slinger or sandblasting machine, uses carbonization
Silicon pottery, stainless shot are shot-peening or sandblasting, carry out ramming or sandblasting roughening treatment, make the bottom of a pan
The inner surface of matrix forms rough bulge-structure, then carries out oil removal treatment, and carries out
Clean;
3) graphite powder is configured to slurry, is coated in the bottom of a pan inner surface;
4) configuration hydrated titanium dioxide and graphite powder mixed uniformly mixed powder slurry, simultaneously
Configuration teos hydrolysis solution, then mixes above-mentioned mixed powder slurry and hydrating solution
Close, and be coated onto on the inner surface of the bottom of a pan matrix;
5) in an inert atmosphere, molten bath is formed as thermal source at matrix surface irradiation using laser,
Make mixed slurry generation carbon-thermal reduction, the inner surface of the bottom of a pan matrix generates titanium carbide metal pottery
Porcelain coating.
Step 2) in, the carborundum used by throwing, sandblasting or the granularity of the granule of rustless steel steel ball
It is 20 mesh~50 mesh;Described oil removing and cleaning can use method commonly used in the art to carry out.
Step 3) in, graphite powder can be mixed to get by described graphite slurry with common solvent, as
Water, ethanol etc.;Graphite can be arbitrary proportion with the ratio of solvent, as long as ensureing that graphite is slurry
?;
Step 3) and 4) in, described coating can use conventional method to carry out, as smeared,
Spray gun spraying etc.;Described coating can be divided into and repeatedly carrying out;
Described coating can coat whole thes bottom of a pan inner surface, it is possible to coated portion the bottom of a pan inner surface;Excellent
Choosing coating 20-80% the bottom of a pan inner surface;
Step 4) in, described mixed powder slurry configures as follows: first configure the dispersed of graphite
Suspension, then metatitanic acid fourth fat, metatitanic acid isopropyl ester or isopropyl titanate are added dropwise to graphite suspend
In liquid, and stir, obtain hydrated titanium dioxide after ball milling and graphite powder is mixed uniformly mixed
Close powder body;Wherein, the rubbing of hydrated titanium dioxide and graphite powder in described step mixed powder slurry
Your amount ratio is l:2~8;
Solvent can be selected for solvent commonly used in the art, such as water, ethanol etc., preferably dehydrated alcohol and
The ethanol solution that distilled water mixes according to the weight ratio of 1-3:1;
Step 4) in, described teos hydrolysis solution configures by the following method: by positive silicic acid
Ethyl ester, dehydrated alcohol and distilled water are according to (80-100): (20-40): the weight ratio of (20-40) is mixed
Close, be sufficiently stirred for being configured to hydrating solution;
Preferably, described metal ceramic wear-resisting coating can be divided into repeatedly, obtains the most in three times,
Spraying oil and spray-coating surface oil in base oil, spraying respectively, the thickness of spraying base oil is 3~8 μm,
In spraying, the thickness of oil is 3~8 μm, and the thickness of spray-coating surface oil is 7~10 μm, namely
Say, by step 4) and 5) it is repeated in three times with the metal ceramic wear-resisting obtaining ideal thickness
Coating, the coating so obtained is the most easy to crack, surfacing, and service life is long.
Described step 5) in, described inert atmosphere can be selected for argon etc. and do not occurs with reactant anti-
The atmosphere answered;Preferably argon, its argon flow amount is 15~20L/min.
Described step 5) in, use pulse Nd:YAG laser to step 4) prepare coating
Carrying out intensive treatment, electric current is 200~280A, and pulsewidth is 2~4ms, frequency 15~40Hz,
Sweep speed is 30~60mm/min.
In addition, it should be noted that above-mentioned steps 1) pot molding select metallic plate, adopt
Form cooker structure with the moulding technique of spinning, casting, punching press, then repair burr,
Cooker pan embryo is formed after cleaning;Substrate may select non-stick pan and commonly uses material, as rustless steel, aluminum,
Aluminium alloy, cast iron or steel etc., preferably aluminum or aluminum alloy;
Above-mentioned steps 2) in, the air of sandblasting needs through purified treatment, thick to after sandblasting
The measurement of rugosity uses roughness tester, and the test in production then uses roughness standards sample block
Comparative measurements.
The inner surface of the wear-resistant unsticky pot of the present invention is provided with rough bulge-structure, makes the bottom of a pan
Reduce with the contact area of food;It addition, stable in properties under titanium-based metal ceramic high temperature, and right
Food is pollution-free, and meltallizing granule and base material are tightly combined, and adhesive force is high, and wearability is good, thus
Reach a high temperature the purpose of food pot the most easy to stick in cooking process, may replace existing Teflon and does not glues
Coating.Present invention process method is simple, is suitable for large-scale production.Gold pottery prepared by the present invention
Wear-resistant coating non-stick pan is that a kind of design is ingenious, function admirable, the non-stick pan of asepsis environment-protecting, more
Add meet current international environment tissue and country proposed " safe and healthy, energy-conservation, green,
Environmental protection " requirement.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described further.As nothing specializes,
Raw material used by the present invention is commercial.
Embodiment 1
It is prepared as follows metal ceramic wear-resisting coating non-stick pan of the present invention:
1) pot molding: select aluminium alloy plate, uses spinning mode to form cooker structure, so
Rear repairing burr, form cooker pan embryo after cleaning;
2) matrix surface processes: above-mentioned pot embryo is put into sand slinger, with 20 mesh~50 mesh
Silicon carbide ceramics be shot-peening, carry out sandblasting roughening treatment, blasting treatment 30 minutes, make pot
The inner surface of base body forms rough bulge-structure, then carries out pickling, washing;
3) take the ethanol of 50%, graphite powder is configured to the volume ratio of slurry, ethanol and graphite
For 1:1, ball milling 1h, it is then coated with at the bottom of a pan inner surface;
4) volume ratio taking the ethanol of 50%, ethanol and graphite is 10:1, first configures graphite
Homodisperse suspension, then metatitanic acid fourth fat is added dropwise in graphite suspension, and stir,
Hydrated titanium dioxide and the mixed uniformly mixed powder of graphite powder is obtained after ball milling;Wherein, mixing
In powdery pulp, the mole of hydrated titanium dioxide and graphite powder is than for l:3.5;
Configuration teos hydrolysis solution: tetraethyl orthosilicate, dehydrated alcohol and distilled water are pressed
Weight ratio according to 100:20:40 mixes, and is sufficiently stirred for being configured to hydrating solution;
Then above-mentioned mixed powder slurry and hydrating solution are mixed, and be coated onto the bottom of a pan base
On whole inner surfacies of body;
5) argon flow amount is 15L/min, in argon gas atmosphere, uses pulse Nd:YAG to swash
Light is to step 4) prepare coating carry out intensive treatment, electric current is 200A, and pulsewidth is 2ms,
Frequency 15Hz, sweep speed is 30mm/min, makes mixed slurry generation carbon-thermal reduction, at pot
Titanium carbide ceramic coating is generated on the inner surface of base body.
Step 4) and 5) it is repeated in three times with the metal ceramic wear-resisting painting obtaining ideal thickness
Layer, sprays oil and spray-coating surface oil in base oil, spraying respectively, and the thickness of spraying base oil is 3 μm,
In spraying, the thickness of oil is 8 μm, and the thickness of spray-coating surface oil is 7 μm,
The thickness of graphite linings is 5 μm, and described metal-cermic coating thickness is 18 μm.Coating
Smooth, color, covering power are substantially uniform with gloss consistent, and bubble-free does not falls off.Meet not
Viscous pot standard.
Embodiment 2
It is prepared as follows metal ceramic wear-resisting coating non-stick pan of the present invention:
1) pot molding: select corrosion resistant plate, uses spinning mode to form cooker structure, so
Rear repairing burr, form cooker pan embryo after cleaning;
2) matrix surface processes: above-mentioned pot embryo is put into sand slinger, with 20 mesh~50 mesh
Silicon carbide ceramics be shot-peening, carry out sandblasting roughening treatment, blasting treatment 30 minutes, make pot
The inner surface of base body forms rough bulge-structure, then carries out pickling, washing;
3) take the ethanol of 75%, graphite powder is configured to the volume ratio of slurry, ethanol and graphite
For 2:1, ball milling 3h, it is then coated with at the bottom of a pan inner surface;
4) taking the ethanol of 75%, the volume ratio of ethanol and graphite, diboron trioxide is 15:1:
1, first configuration graphite and the homodisperse suspension of diboron trioxide, then by metatitanic acid isopropyl ester
It is added dropwise in suspension, and stirs, after ball milling 3h, obtain hydrated titanium dioxide, three oxygen
Change two boron and the mixed uniformly mixed powder of graphite powder;Wherein, hydrated titanium dioxide, graphite powder
With the mole of diboron trioxide than for l:8:1;
Configuration teos hydrolysis solution: tetraethyl orthosilicate, dehydrated alcohol and distilled water are pressed
Weight ratio according to 100:40:40 mixes, and is sufficiently stirred for being configured to hydrating solution;
Then above-mentioned mixed powder slurry and hydrating solution are mixed, and be coated onto the bottom of a pan base
On whole inner surfacies of body;Described coating can inner surface at the bottom of coated pan 80%,
5) argon flow amount is 20L/min, in argon gas atmosphere, uses pulse Nd:YAG to swash
Light is to step 4) prepare coating carry out intensive treatment, electric current is 280A, and pulsewidth is 4ms,
Frequency 40Hz, sweep speed is 60mm/min, makes mixed slurry generation carbon-thermal reduction, at pot
Titanium carbide ceramic coating is generated on the inner surface of base body.
Step 4) and 5) it is repeated in three times with the metal ceramic wear-resisting painting obtaining ideal thickness
Layer, sprays oil and spray-coating surface oil in base oil, spraying respectively, and the thickness of spraying base oil is 8 μm,
In spraying, the thickness of oil is 8 μm, and the thickness of spray-coating surface oil is 10 μm,
The thickness of graphite linings is 8 μm, and described metal-cermic coating thickness is 26 μm.Coating
Smooth, color, covering power are substantially uniform with gloss consistent, and bubble-free does not falls off.Meet not
Viscous pot standard.
Embodiment 3
It is prepared as follows metal ceramic wear-resisting coating non-stick pan of the present invention:
1) pot molding: cast iron forms cooker structure, then repairs burr, after cleaning
Form cooker pan embryo;
2) matrix surface processes: above-mentioned pot embryo is put into sand slinger, with 20 mesh~50 mesh
Silicon carbide ceramics be sandblasting, carry out sandblasting roughening treatment, blasting treatment 30 minutes, make pot
The inner surface of base body forms rough bulge-structure, then carries out pickling, washing;
3) take the ethanol of 50%, graphite powder is configured to the volume ratio of slurry, ethanol and graphite
For 0.5:1, ball milling 1h, it is then coated with at the bottom of a pan inner surface;
4) taking the ethanol of 75%, the volume ratio of ethanol and graphite, diboron trioxide is 15:1:
2, first configuration graphite and the homodisperse suspension of diboron trioxide, then isopropyl titanate is dripped
Add in suspension, and stir, after ball milling 3h, obtain hydrated titanium dioxide, three oxidations
Two boron and the mixed uniformly mixed powder of graphite powder;Wherein, hydrated titanium dioxide, graphite powder with
The mole of diboron trioxide is than for 2:4:1;
Configuration teos hydrolysis solution: tetraethyl orthosilicate, dehydrated alcohol and distilled water are pressed
Weight ratio according to 80:30:30 mixes, and is sufficiently stirred for being configured to hydrating solution;
Then above-mentioned mixed powder slurry and hydrating solution are mixed, and be coated onto the bottom of a pan base
On the inner surface of body 60%;
5) argon flow amount is 15L/min, in argon gas atmosphere, uses pulse Nd:YAG to swash
Light is to step 4) prepare coating carry out intensive treatment, electric current is 250A, and pulsewidth is 3ms,
Frequency 30Hz, sweep speed is 40mm/min, makes mixed slurry generation carbon-thermal reduction, at pot
Titanium carbide ceramic coating is generated on the inner surface of base body.
Step 4) and 5) it is repeated in three times with the metal ceramic wear-resisting painting obtaining ideal thickness
Layer, sprays oil and spray-coating surface oil in base oil, spraying respectively, and the thickness of spraying base oil is 5 μm,
In spraying, the thickness of oil is 5 μm, and the thickness of spray-coating surface oil is 10 μm,
The thickness of graphite linings is 6 μm, and described metal-cermic coating thickness is 20 μm.Coating
Smooth, color, covering power are substantially uniform with gloss consistent, and bubble-free does not falls off.Meet not
Viscous pot standard.
Metal ceramic wear-resisting coating embodiment 1-3 prepared detects, and the results are shown in Table 1.
Table l, performance detection table
Project |
Linear expansion coefficient 10-6/℃ |
Water absorption rate % |
Coefficient of friction |
Rockwell hardness |
Embodiment 1 |
3.8 |
0.6 |
0.3 |
88 |
Embodiment 2 |
4.0 |
0.2 |
0.3 |
87 |
Embodiment 3 |
4.1 |
0.6 |
0.27 |
93 |
Obviously, metal ceramic wear-resisting coating material prepared by the preparation method of the present invention is utilized not only
Having good mechanical property, intensity is high, and the most scratch-resistant, antibacterial, asepsis environment-protecting more conforms to
" safe and healthy, energy-conservation, green, the environmental protection " that current international environment tissue and country are proposed
Requirement.