CN102352142B - High-temperature nano-grade anti-carburizing material and coating, and application thereof - Google Patents
High-temperature nano-grade anti-carburizing material and coating, and application thereof Download PDFInfo
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Abstract
The invention discloses a high-temperature nano-grade anti-carburizing material, a coating formed with the material, and an application thereof. The material is formulated slurry. The slurry is sprayed and/or painted on a work-piece, such that a coating is formed. The coating is characterized in high-temperature carburization resisting, high thermal conductivity, and good bonding strength with substrate parts. When the coating is imbibed with molten iron, air gaps can be removed. When the coating is applied on the surface of a low-carbon steel part such as a cooling pipe of a cast iron cooling stave in a steel plant, carburization of the low-carbon steel part in a high-temperature carbon atmosphere is avoided. A main application scope of the material coating is that: slurry with the high-temperature nano-grade anti-carburizing material formulation can be sprayed and/or painted on surfaces of equipments/cooling pipes of cast iron cooling staves, and compact high-efficiency long-life anti-carburizing coatings are formed after curing; the slurry can be sprayed and/or painted on surfaces of large steel parts/forging dies, and decarbonization resisting coatings are formed after curing.
Description
Technical field
The present invention discloses a kind of high-temperature nano-grade anti-carburizing material, coating and application thereof, belong to high temperature material technical field.
background technology
Blast-furnace cast iron cooling stave belongs to blast furnace cooling apparatus, and it is configured to the ironcasting of pre-buried low-carbon (LC) weldless steel tube, and it undertakes the vital task of cooling body of heater to protect furnace shell and steel construction, support refractory materials and to safeguard reasonable stove shape.The cooling principle of blast-furnace cast iron cooling stave is that furnace heat is passed to refractory liner, cooling stave cast iron matrix, weldless steel tube wall successively, outside final recirculated cooling water in steel pipe is come out of the stove heat band.As can be seen here, the main task of blast-furnace cast iron cooling stave has been cooling heat dissipation effect.
In cast-iron cooling wall casting cycle, carbon atom in cast iron at high temperature tends to enter in the tube wall of water coolant steel pipe of cooling stave by diffusion process, water-cooled tube is to be generally made with soft steel, after water-cooled tube carburizing, content of pearlite in alloy increases, and there will be free state carbide, as shown in Figure 1 when serious, Fig. 1-a shows be cooling stave water-cooled tube without the original metallographic structure of carburizing, Fig. 1-b is the metallograph that shows the perlite increase after carburizing.After water-cooled tube carburizing, along with the progressively increase of content of pearlite in alloy, toughness declines gradually, causes resisting under cooling stave working order the ability variation of heat fluctuation, shortens its work-ing life.
At present, solve this plant issue and mainly contain following several aspect:
(a) Low Carbon Steel Pipe is simply changed into high-grade stainless steel material;
(b) by thermospray, on cooling stave water pipe, spray one deck alloy material or oxide compound;
(c) brushing one coating is to prevent carburizing.
In three kinds of solutions described above, (a) is the best way certainly, is also the most expensive, and wherein (b) is also technical feasible, but involves great expense equally, and solution (c) is most economical, and coating need to meet following condition:
After paint solidification, become coating and want there is good bonding force with cooling stave water-cooled tube;
The surface of coating also wants to infiltrate reaching good heat-conducting effect with molten iron fusion simultaneously;
Coating has good thermal conductivity;
Coating can have anti-carburizing effect.
The product that can see on the market at present has the coating that KC-202 coating and zirconium English powder are body material etc.In these business coating, take the effect of KC-202 coating as best and the most extensive, other anti-carburizing effect is all poor.The more successful coating that Shi Lin company is used is at present also KC-202 coating.The application the earliest of this coating be take anti-oxidant anti-decarburization as master develops, and extends to afterwards anti-carburizing application.If the zirconium white of its composition, aluminum oxide etc. are all the very poor materials of thermal conductivity, affected the cooling performance of cooling stave.Except thermal conductivity can not meet application requiring, this coating is also very poor with the bonding force of matrix after changing into coating, often causes the phenomenon of Paint Falling.The part that the surface of coating contacts with molten iron also exists poor wetting property, has caused like this functional quality of this coating products poor, causes the problems such as the bad mechanical property of cooling stave and application life be short.
In cast-iron cooling wall molten iron casting and cast iron process of cooling, cooling stave cast iron matrix and steel pipe, because the gap of the different generations of the condition of expanding with heat and contract with cold is greater than 0.1mm, are referred to as air gap in industry.By doing the hot experiment of cooling stave and thermal conduction study computational analysis, the thermal resistance that 0.1mm air gap produces is greater than the cast iron body that 1850mm is thick, therefore, high furnace heat can not pass by water coolant effectively, and the long term operation of cooling stave hot side is under the condition of high temperature, cause cooling stave mechanical property greatly to decline, cooling stave cast iron matrix is damaged, and water-cooled tube is under the effect of high temperature alternating thermal stress simultaneously, and cracking leaks, cause cooling stave equipment failure, affect blast furnace continuous direct motion in 24 hours and produce.
In addition, the Forge Heating of large-scale steel-iron components/forging die, thermal treatment heating, because of its heating period long, can cause steel-iron components/forging die oxidation and decarbonization phenomenon, affect performance, when oxidation and decarbonization is serious, can produces and scrap.The measure that current factory with good conditionsi takes is controlled atmosphere heating, but heating cost is higher; Have and adopt business KC-202 coating, but the zirconium white of its composition, aluminum oxide etc. are all the very poor materials of thermal conductivity as mentioned above, impact heating heat transfer efficiency.
Shortcoming based on above-mentioned existing anti-carburizing/anti-decarburizing coating product, and the expensive high in cost of production problem of other substitute products and technique, the invention of Low-cost coating material and application thereof is necessary.
summary of the invention
The present invention is a kind of high-temperature nano-grade anti-carburizing material, coating and application thereof, is used for improving the deficiency of current anti-carburizing tech.For protection blast-furnace cast iron cooling stave water-cooled tube not by carburizing, adapt to harsh Working environment and increase its work-ing life; utilize nanotechnology to succeed in developing serial high-temperature nano-grade anti-carburizing material and coating thereof cheaply, mainly solve carburizing that cooling stave water-cooled tube occurs in cooling stave casting cycle, do not infiltrate and produce the subject matter of air gap with molten iron.The coating forming after spraying and/or brushing high-temperature nano masking paste solidify in steel tube surface, under high-temperature situation, forms fine and close high-efficiency long-life anti-carburization coating on the surface of steel pipe.
The present invention is embodied in four aspects, comprising: the material prescription of nanometer masking paste, utilize this formula to make that slurry forms nanometer anti-carburization coating by the method for spraying or brushing, the composition and structure of coating is organized can be also that a kind of gradient cladding that contains duplex coating and this invention anti-carburization coating are in the application of equipment/cooling stave.
First embodiment of the present invention is to have formed new formulation for coating material, and formula comprises the composition of following several necessity:
(a) the first part's material composition in slurry has anti-carburizing function;
(b) the second section material composition in slurry has high heat conductance function;
(c) supplementary additive in slurry provides low temperature and high-temperature agglomerant function;
(d) the second supplementary additive material composition in slurry has the function that infiltrates elimination air gap with molten iron.
First part's material composition in described slurry is to select to derive from one or more the compound of a group, and compound comprises aluminum oxide, chromic oxide, zirconium white, silicon oxide, calcium oxide, yttrium oxide, cerium oxide, Scium trioxide, magnesium oxide; And/or the nickel of metal, chromium, nickel-aluminium alloy, nickel-chromium alloy, nickel-aluminium-chromium-iron alloy; And/or the combination of said two devices, the weight percent of the carbon functional material composition of this antiseepage in slurry is from 15% to 90 ﹪;
Second section material composition in described slurry is to select to derive from a kind of, but is not limited to a kind of compound, and compound comprises silicon carbide, silicon nitride, aluminium nitride, titanium nitride, boron nitride, chromium nitride; And/or the aluminium of metal, nickel-aluminium alloy, nickel-chromium alloy; And/or the combination of said two devices, the weight percent of the material composition of this high heat conductance in slurry is from 5% to 70%
Supplementary additive composition in described slurry is to select to derive from a kind of, but after being not limited to a kind of low-temperature curing and within the usage period, has the high polymer binder of attachment function, and binding agent comprises PVA, PVP; And/or high-temperature agglomerant comprises Starso, boride and silicic acid sylvite; And/or the combination of said two devices; the weight percent of the material composition of this binding agent in slurry be from 0.1% to 20% attachment function additive component be select to derive from a kind of; but the high polymer binder after being not limited to a kind of low-temperature curing and within the usage period with attachment function, comprises polyvinyl alcohol, PVA, PVP; And/or high-temperature agglomerant comprises Starso, boride and silicic acid sylvite; And/or the combination of said two devices, the ratio of the material composition of this binding agent in slurry is from 0.1% to 20% weight ratio.
Described and molten iron infiltrates the second supplementary additive composition of elimination air gap function and at least selects to derive from a kind of glaze, nickel-aluminium alloy, nickel-chromium alloy, aluminium, copper or iron, but be not limited to a kind of, or above-mentioned two or more combination, the material composition that should infiltrate eliminate air gap with molten iron per-cent by weight in slurry is greater than 0 and is less than 50%.
Based on above-mentioned requirements, coating has comprised that effective constituent contains antiseepage carbon component and high thermal conductivity composition.Wherein these two kinds of compositions all can meet the high-intensity bonding force with matrix/cooling stave water-cooled tube, and the while also can meet good infiltration elimination air gap effect between its coatingsurface and molten iron.
Antiseepage carbon component is to derive from least one, but is not limited to a kind of compound, and compound comprises aluminum oxide, chromic oxide, zirconium white, silicon oxide, yttrium oxide, cerium oxide, Scium trioxide, magnesium oxide; And/or the nickel of metal, chromium, nickel-aluminium alloy, nickel-chromium alloy, nickel-aluminium-chromium-iron alloy; And/or the combination of said two devices, the weight percent of this antiseepage carbon component in coating is from 15% to 90 ﹪.
High heat conductance composition is to derive from least one, but is not limited to a kind of compound, and compound comprises silicon carbide, silicon nitride, aluminium nitride, titanium nitride, boron nitride, chromium nitride; And/or the aluminium of metal, nickel-aluminium alloy, nickel-chromium alloy; And/or the combination of said two devices, the weight percent of this high heat conductance composition in coating is from 5% to 70 ﹪.
Infiltrating elimination air gap composition with molten iron is to derive from least one, but be not limited to a kind of glaze, nickel-aluminium alloy, nickel-chromium alloy, aluminium, copper, iron of low melting point, or their combination, should infiltrate eliminate air gap composition per-cent by weight in coating with molten iron and be greater than 0 and be less than 50%.
The antiseepage carbon component of described the first layer coating is to derive from least one, but is not limited to a kind of compound, and compound comprises aluminum oxide, chromic oxide, zirconium white, silicon oxide, yttrium oxide, cerium oxide, Scium trioxide, magnesium oxide; And/or the nickel of metal, chromium, nickel-aluminium alloy, nickel-chromium alloy, nickel-aluminium-chromium-iron alloy; And/or the combination of said two devices, the weight percent of the antiseepage carbon component of the first layer coating in coating is from 15% to 90 ﹪;
The first layer coating high heat conductance composition of described coating is to derive from least one, but is not limited to a kind of compound, and compound comprises silicon carbide, silicon nitride, aluminium nitride, titanium nitride, boron nitride, chromium nitride; And/or metallic aluminium, nickel-aluminium alloy, nickel-chromium alloy; And/or the combination of said two devices, the weight percent of the first layer coating high heat conductance composition in coating is from 5% to 70 ﹪.
The high heat conductance composition of described second layer coating is to derive from least one, but is not limited to a kind of compound, and compound comprises silicon carbide, silicon nitride, aluminium nitride, titanium nitride, boron nitride, chromium nitride; And/or metallic aluminium, nickel-aluminium alloy, nickel-chromium alloy; And/or the combination of said two devices, the weight percent of second layer coating high heat conductance composition in coating is from 5% to 70 ﹪;
It is to derive from least one that described second layer coating and molten iron infiltrate elimination air gap composition, but be not limited to a kind of glaze, nickel-aluminium alloy, nickel-chromium alloy, aluminium, copper, iron of low melting point, or their combination, second layer coating infiltrate to eliminate the weight percent of air gap composition in coating with molten iron be from 1% to 50%.
Beneficial effect of the present invention is embodied in the aspects such as anti-carburizing stable, high heat conductance reliable for effect, elimination air gap thermal resistance, easy construction, cost are low, and cooling performance improves more than 2 times than traditional anti-carburized material and coating thereof.
accompanying drawing explanation
Fig. 1 is the schematic diagram of individual layer function nano anti-carburization coating and matrix part relation;
Fig. 2 is the schematic diagram of multilayer function nano anti-carburization coating and matrix part relation;
Fig. 3 is the metallograph after steel pipe cementation test;
Fig. 4 is that steel pipe is brushed anti-decarburizing coating metallograph after heat in resistance furnace.
Embodiment
The form of high-temperature nano-grade anti-carburizing material of the present invention is a kind of coating (slurry), and the surface by spraying/brushing to workpiece substrate/steel pipe forms anti-carburization coating/anticreep carbon coating after overcuring.This coating has superior anti-carburizing/effect of preventing decarburization, good thermal conductivity, has good bonding force with matrix, as anti-carburization coating, can infiltrate preferably and eliminate air gap ability with molten iron interface formation.
High-temperature nano-grade anti-carburizing material the key technical indexes sees the following form.
high-temperature nano-grade anti-carburizing material the key technical indexes
| Project name | Unit | Technical indicator |
| Coating unit weight | g/cm 3 | 1.1 ～ 1.2 |
| Coating is sedimentation time not | d | ≥60 |
| Coating suspension | h | ≥48 |
| Coating pH value | pH | 9 ～ 11 |
| Baking density | g/cm 3 | 1.4 ～ 1.6 |
| Binding strength of coating | MPa | ≥1 |
| Minimum film-forming temperature | ℃ | -7 |
| The anti-molten iron of coating washes away | ? | Meet the requirement of molten iron casting process |
| Coating refractoriness | ℃ | Max.1800 |
| The anti-carburizing performance of coating | ? | In the 1mm depth range of steel pipe walls surface, relative average carbon increasing amount≤0.1% of steel pipe matrix |
| The coated thread coefficient of expansion | 1.0×10 -6℃ | 1350℃，6 ～ 10 |
| Coat-thickness | mm | ≤0.3 |
| Water-cooled tube and this body space of cast-iron cooling wall (containing coat-thickness) | mm | ≤0.2 |
| Water-cooled tube and cast-iron cooling wall body air gap | mm | ≤0.02 |
| Entire thermal resistance | ℃/W | ≤0.02 |
According to aim of the present invention, in the first of the present invention embodies, be that required composition system is made into a kind of masking paste.In actual process process, the coating of anti-carburized material (slurry) is made according to the following steps:
1. by formula rate, weigh each main raw composition weight;
2. weigh the weight of various additives and by its mixing;
3. additive is mixed with main raw composition, mechanically mixing first, then with the wet ball mill certain hour of milling.Sometimes, mechanical milling process is optional;
From ball milling or the slurry obtaining in mixture can store, standby.
The system component design of anti-carburized material should have two kinds of possibilities.Its formula one is to contain antiseepage carbon component (phase) and high heat conductance composition (phase), and after this formula slurry curing, becoming the molten iron interface that should contact with it after coating has good infiltration and eliminate air gap ability.
Its formula two be contain high heat conductance composition (phase) and with the infiltration composition (phase) at molten iron interface.This formula slurry is normally used as the approaching coating of the second layer and molten iron, and after solidifying, becoming the molten iron interface that coating should contact with it has good infiltration elimination air gap ability.
It is that formulation for coating material is converted into anti-carburization coating that the second of this invention embodies.The coating structure obtaining can be nanostructure, also micrometer structure.Here, the definition of nanometer (nm, nanometer) structure refers to that it is to be less than 100 nanometers that the grain-size of anti-carburized material has at least its size of a kind of composition (or phase) to have a direction at least.The definition of micron (μ m, micrometer) structure refers to that it is to be greater than 100 nanometers that the grain-size of anti-carburized material has at least its size of a kind of composition (or phase) to have a direction at least.
Based on above-mentioned requirements, material and the coating of invention have as shown in fig. 1.Coating has comprised that effective constituent contains antiseepage carbon component and high thermal conductivity composition.Wherein these two kinds of compositions all can meet the high-intensity bonding force with matrix/cooling stave water-cooled tube, and the while also can meet good infiltration elimination air gap effect between its coatingsurface and molten iron.
In of the present invention the third embodies, the making method embodying according to above-mentioned the second is converted into formulation for coating material a kind of duplex coating of gradient, as shown in Figure 2.This gradient cladding is in the first layer coating contacting with workpiece substrate, to contain antiseepage carbon component and high heat conductance composition and second layer coating contain high heat conductance composition and infiltrate and eliminate air gap composition with molten iron.
The 4th kind of embodiment of the present invention is its applied range, comprises that spraying/brushing is on large-scale steel-iron components/forging die surface, after solidifying, forms anticreep carbon coating.
Patent of the present invention is further set forth explanation by the example by below.
embodiment 1: high-temperature nano-grade anti-carburizing material (slip) formula
High-temperature nano-grade anti-carburizing material (slip) formula 1 and 2, respectively in Table 1, table 2.
table 1high-temperature nano-grade anti-carburizing material (slip) formula 1
| Material name | Specification (mm) | Content (%) | Actual weighing (g) | Remarks |
| Aluminum oxide | 0.005 | 9.86 | 49.3 | ? |
| Chromic oxide | 0.021 | 12.33 | 61.65 | ? |
| D01 powder | Nano level | 27.85 | 139.25 | ? |
| Titanium dioxide | Nano level | 0.74 | 3.7 | ? |
| Silicon powder | Nano level | 12.33 | 61.65 | ? |
| Liquid glass | Technical grade | 20 | 129.6 | ? |
| Tripoly phosphate sodium STPP | Technical grade | 0.75 | 3.7 | ? |
| Alcohol ester-12 | Technical grade | 13.32 | 66.6 | ? |
| Propylene glycol | Technical grade | 3.82 | 19.1 | ? |
| Total amount | ? | 100 | 500 | ? |
Note: in table, " D01 powder " refers to one of series product " D00 powder " of being produced by generation woods (Luohe) metallurgical equipment company." D00 powder " material composition (phase) is to select to derive from least one, but is not limited to a kind of compound silicon carbide, silicon nitride, aluminium nitride, titanium nitride, boron nitride or metallic aluminium, copper, nickel-aluminium alloy, nickel-chromium alloy etc., or their combination;
In table, " D01 powder " is that weight ratio is 650 order silicon carbide and the 800 object aluminium powder mixed powders of 1:1, adopts nanometer/ultrafining treatment, makes crystal grain reach nano-scale.
table 2high-temperature nano-grade anti-carburizing material (slip) formula 2
| Material name | Specification (mm) | Content (%) | Actual weighing (g) | Remarks |
| Glaze | 0.019 | 2.45 | 12.25 | ? |
| Ferric oxide | 0.013 | 3.68 | 18.4 | ? |
| Chromic oxide | 0.021 | 6.87 | 34.35 | ? |
| D02 powder | Nano level | 32.27 | 161.35 | ? |
| Titanium dioxide | Nano level | 0.74 | 3.7 | ? |
| Silicon powder | Nano level | 14.72 | 23.6 | ? |
| Liquid glass | Technical grade | 20 | 108.6 | ? |
| Tripoly phosphate sodium STPP | Technical grade | 0.74 | 3.7 | ? |
| Alcohol ester-12 | Technical grade | 13.13 | 65.65 | ? |
| Propylene glycol | Technical grade | 5.4 | 27 | ? |
| Total amount | ? | 100 | 500 | ? |
Note: in table, " D02 powder " refers to one of series product " D00 powder " of being produced by generation woods (Luohe) metallurgical equipment company, that weight ratio is 800 order boron nitride and the 1100 object copper powder mixed powders of 1:1, adopt nanometer/ultrafining treatment, make crystal grain reach nano-scale.
By adjusting high-temperature nano-grade anti-carburizing material (slip) component, must fill a prescription 3,4,5,6 and 7, in Table 3.
table 3high-temperature nano-grade anti-carburizing material (slip) formula (Wt. %)
embodiment 2: nanometer masking paste manufacturing process steps
Nanometer masking paste manufacturing process steps is as follows:
Press 500g dosage, according to actual the weighing of above-described embodiment 1 formula table proportioning 1 ~ proportioning 7, take the powder part in various raw materials;
Be added in prototype version atomizer mill, and then to add diameter be the zirconia ball of 20mm, the discharging after 8 hours of energising ball milling, the powder specification that it mixes is >=600 orders;
Mixed powder with take in proportion liquid glass, tripoly phosphate sodium STPP, alcohol ester-12 and propylene glycol, put into respectively agitation vat, utilize adjustable agitator to be uniformly mixed 30 minutes, nanometer masking paste, then packing tank into can use.
embodiment 3: the making of nanometer anti-carburization coating
1, single coating is made
Coating is made: press above-described embodiment 1 formula table proportioning 1 and embodiment 2 coating manufacture crafts, make coating 500g;
Brush flow process: thick-110 ℃ * 2h oven dry of steel pipe blanking-sandblast-brush coating 0.1mm, this test specimen is nanometer 1#.
2, two coatings are made
Coating is made: press respectively above-described embodiment 1 formula table proportioning 1, proportioning 2 and embodiment 2 coating manufacture crafts, make each 500g of coating;
Brush flow process: steel pipe blanking-sandblast-brushings proportioning 1 coating-3 ~ 5h dries-brush proportioning 2 coating-110 ℃ * 2h oven dry naturally, and this test specimen is nanometer 2#.
3, anti-carburizing experiment
Dress case hardening box-enter heating by electric cooker carburizing-test block-metallographicobservation.
4, metallographic experimental result
Anti-carburizing test-results is shown in Fig. 3: 3-a is without metallographic after coated steel pipe high temperature; 3-b is for adopting business coating KC-202 high-temperature metallography; 3-c is metallographic after nanometer 1# test specimen high temperature, and anti-carburizing effect is suitable with KC-202; 3-d is metallographic after nanometer 2# test specimen high temperature, and anti-carburizing effect is better than KC-202.
embodiment 4: making and the experiment of nanometer anticreep carbon coating
1, coating is made
Coating is made: press above-described embodiment 1 formula table proportioning 1 and embodiment 2 coating manufacture crafts, make coating 500g;
Brush flow process: thick-110 ℃ * 2h of steel pipe blanking-sandblast-brush coating 0.1mm is dried, one group of 3 test specimen 1#, 2#, 3#.
2, anti-decarburization experiment
Pack 900 ℃ * 5h-test block-metallographicobservation of heating by electric cooker into.
4, metallographic experimental result
Anti-decarburization experimental result is shown in Fig. 4, and 3 test block surfaces are all without decarburization phenomenon, surface and heart portion either pearlite occurred indifference.
embodiment 5: the test of nanometer anti-carburization coating thermal conductivity
Adopt hot test, measure test block thermal conductivity:
1, cooling stave test block is prepared
The 3 cooling stave test blocks of casting, water-cooled tube surface is respectively 1# nano paint (table 1 proportioning), 2#KC-202 coating and 3# without coating; Bore thermocouple hole, place thermopair.
2, testing apparatus
The cooling performance that can measure cooling stave under different furnace temperature, different water speed in test, whole pilot system is mainly divided into three parts: cooling stave hot test stove, waterworks and test instrumentation system.Coke can provide for testing whole process the thermal source of stable and uniform; Waterworks provides sufficient water source for cooling stave; Test macro is mainly metrical instrument, mainly contains thermopair, compensating lead wire, under meter etc.
3, before on-test, to carry out water circuit system inspection, instrument inspection, then according to following steps, test:
(1) connect the general supply of equipment;
(2) open inlet valve and flowing water Valve, connect pump power, water pipe is supplied water;
(3) regulating water inlet valve door, makes the stable 3.5m/s that reaches of water coolant flow velocity;
(4) open the data display program of temperature measurement module, observe furnace temperature;
(5) share out the work personnel full-time writing time, cooling water intakeoutfall water temperature, respectively under the condition of 900 ℃ of left and right, 1100 ℃ of left and right, 1200 ℃ of left and right, test the heat transfer property of cooling stave under three kinds of different water speed, water speed is respectively 3.5 m/s, 2.0 m/s, 1.0 m/s, and records corresponding data;
(6) after being completed, furnace temperature is naturally cooled to after 300 ℃, close water coolant.
4, interpretation
By this hot test, analyze the thermal conductivity of different anti-carburization coatings and the difference of fusion performance, mainly from following three aspects:
(1) furnace temperature and electric thermo-couple temperature change curve; By the gentle electric thermo-couple temperature of analytical furnace, cooling stave water pipe and cast iron fusion performance are poorer, and cast iron temperature is higher, draws the relation of the anti-carburization coating of test block 1,2,3, are followed successively by: test block 3, test block 1, test block 2 by good to poor;
(2) calculate heat flow density.Under test block specification and the identical condition of experiment condition, the heat flow density of different test blocks is contrasted, the larger thermal conductivity of heat flow density is better; In test block 1,2,3 design variable situation identical with experiment condition, experiment calculation show that heat flow density is in Table 4;
Table 4 test block heat flow density
| Test block |
| 1# | 2# | 3# | |
| Furnace temperature (℃) | 1150 | 1224 | 1219 |
| Heat flow density (kW/m 2) | 63 | 57 | 97 |
(3) calculate thermal resistance.By thermal resistance analysis, judge between water-cooled tube and matrix, whether there is air gap, thereby judge that different anti-carburization coatings are in the quality of thermal conductivity and fusion aspect of performance, thermal resistance is large, air gap is thick, poor thermal conductivity.Thermal resistance, air gap are thick in 5.
Table 5 test block thermal resistance and air gap
| Test block |
| 1# | 2# | 3# | |
| Entire thermal resistance R (℃/W) | 0.01783 | 0.0495 | 0.0091 |
| Air gap thickness (mm) | 0.02 | 0.104 | 0.003 |
(4) by analyzing the thermal resistance between electric thermo-couple temperature curve, heat flow density and water-cooled tube and cast iron, draw the difference of different anti-carburization coating thermal conductivity and fusion performance, three kinds of analytical procedure acquired results are consistent, and the reliability of conclusion has been described from different perspectives.
High-temperature nano-grade anti-carburizing material performance index measured value is in Table 5.
Table 5 high-temperature nano-grade anti-carburizing material measurement technology performance index
embodiment 6: industrial test application one
By proportioning in the table 1 of embodiment 1, take the powder part in various raw materials, be added in atomizer mill, and then to add diameter be the zirconia ball of 20mm, the discharging after 24 hours of energising ball milling, the powder specification that it mixes is >=600 orders.
According to industrial application amount needs, mixed powder with take in proportion liquid glass, tripoly phosphate sodium STPP, alcohol ester-12 and propylene glycol, put into respectively agitation vat, utilize adjustable agitator to be uniformly mixed 30 minutes, nanometer masking paste, then packing tank into can use.This coating is applicable on cooling stave water-cooled tube outside surface.
embodiment 7: industrial test application two
By proportioning in embodiment 1 table 2, take after the powder part in various raw materials, be added in atomizer mill, and then to add diameter be the zirconia ball of 20mm.The discharging after 24 hours of energising ball milling, the powder specification that it mixes is >=600 orders.
According to industrial application amount needs, mixed powder with take in proportion liquid glass, tripoly phosphate sodium STPP, alcohol ester-12 and propylene glycol, put into respectively agitation vat, utilize adjustable agitator to be uniformly mixed 30 minutes, nanometer masking paste, then packing tank into can use.This coating is applicable on hot-forging die outside surface, prevents decarburization when quenching heating.
Concrete application flow is: forging die electrochemical deoiling, and------110 ℃ * 2h of preheating---brushing nanometer masking paste---can enter stove heating after 2h, during quenching, coating is from stripping in mechanical rust removal.
Claims (11)
1. a high-temperature nano-grade anti-carburizing material, its formula is slurry through batching, and this formula comprises:
(a) the first part's material composition in slurry has anti-carburizing function; This material composition is to select to derive from one or more the compound of a group, and compound comprises aluminum oxide, chromic oxide, zirconium white, silicon oxide, calcium oxide, yttrium oxide, cerium oxide, Scium trioxide, magnesium oxide; And/or the nickel of metal, chromium, nickel-aluminium alloy, nickel-chromium alloy, nickel-aluminium-chromium-iron alloy; And/or the combination of said two devices, the weight percent of the carbon functional material composition of this antiseepage in slurry is from 15% to 90 ﹪;
(b) the second section material composition in slurry has high heat conductance function; This material composition is to select to derive from a kind of, but is not limited to a kind of compound, and compound comprises silicon carbide, silicon nitride, aluminium nitride, titanium nitride, boron nitride, chromium nitride; And/or the aluminium of metal, nickel-aluminium alloy, nickel-chromium alloy; And/or the combination of said two devices, the weight percent of the material composition of this high heat conductance in slurry is from 5% to 70%;
(c) supplementary additive in slurry provides low temperature and high-temperature agglomerant function; This supplementary additive composition is to select to derive from a kind of, but after being not limited to a kind of low-temperature curing and within the usage period, has the high polymer binder of attachment function, and binding agent comprises PVA, PVP; And/or high-temperature agglomerant comprises Starso, boride and silicic acid sylvite; And/or the combination of said two devices, the weight percent of the material composition of this binding agent in slurry is from 0.1% to 20%;
(d) the second supplementary additive material composition in slurry has the function that infiltrates elimination air gap with molten iron; Described and molten iron infiltrate glaze, nickel-aluminium alloy, nickel-chromium alloy, aluminium, copper or the iron that the second supplementary additive composition of eliminating air gap function at least selects to derive from one or more, should infiltrate material composition per-cent by weight in slurry of eliminating air gap with molten iron and be greater than 0 and be less than 50%.
2. a high-temperature nano anti-carburization coating, is slurry spraying high-temperature nano-grade anti-carburizing material formula claimed in claim 1/or brush in cast-iron cooling wall water coolant steel tube surface, after solidifying, forms anti-carburization coating.
3. according to high-temperature nano anti-carburization coating claimed in claim 2, it is characterized in that: described high-temperature nano anti-carburization coating is nanostructure.
4. according to high-temperature nano anti-carburization coating claimed in claim 2, it is characterized in that: described high-temperature nano anti-carburization coating has anti-carburizing function, high heat conductance function and infiltrates with molten iron material composition and the structure organization of eliminating air gap function.
5. according to high-temperature nano anti-carburization coating claimed in claim 4, it is characterized in that: antiseepage carbon component is to derive from least one, but be not limited to a kind of compound, compound comprises aluminum oxide, chromic oxide, zirconium white, silicon oxide, yttrium oxide, cerium oxide, Scium trioxide, magnesium oxide; And/or the nickel of metal, chromium, nickel-aluminium alloy, nickel-chromium alloy, nickel-aluminium-chromium-iron alloy; And/or the combination of said two devices, the weight percent of this antiseepage carbon component in coating is from 15% to 90 ﹪.
6. according to high-temperature nano anti-carburization coating claimed in claim 4, it is characterized in that: high heat conductance composition is to derive from least one, but be not limited to a kind of compound, compound comprises silicon carbide, silicon nitride, aluminium nitride, titanium nitride, boron nitride, chromium nitride; And/or the aluminium of metal, nickel-aluminium alloy, nickel-chromium alloy; And/or the combination of said two devices, the weight percent of this high heat conductance composition in coating is from 5% to 70 ﹪.
7. according to high-temperature nano anti-carburization coating claimed in claim 6, it is characterized in that: it is to derive from least one that molten iron infiltrates elimination air gap composition, but be not limited to a kind of glaze, nickel-aluminium alloy, nickel-chromium alloy, aluminium, copper, iron of low melting point, or their combination, should infiltrate eliminate air gap composition per-cent by weight in coating with molten iron and be greater than 0 and be less than 50%.
8. according to high-temperature nano anti-carburization coating claimed in claim 2, it is characterized in that: described coated component and structure organization are a kind of duplex coatings, that is:
In the first layer coating contacting with workpiece substrate, containing antiseepage carbon component and high heat conductance composition and second layer coating contains high heat conductance composition and infiltrates and eliminate air gap composition with molten iron.
9. according to high-temperature nano anti-carburization coating claimed in claim 8, it is characterized in that: the antiseepage carbon component of described the first layer coating is to derive from least one, but be not limited to a kind of compound, compound comprises aluminum oxide, chromic oxide, zirconium white, silicon oxide, yttrium oxide, cerium oxide, Scium trioxide, magnesium oxide; And/or the nickel of metal, chromium, nickel-aluminium alloy, nickel-chromium alloy, nickel-aluminium-chromium-iron alloy; And/or the combination of said two devices, the weight percent of the antiseepage carbon component of the first layer coating in coating is from 15% to 90 ﹪;
The first layer coating high heat conductance composition of described coating is to derive from least one, but is not limited to a kind of compound, and compound comprises silicon carbide, silicon nitride, aluminium nitride, titanium nitride, boron nitride, chromium nitride; And/or metallic aluminium, nickel-aluminium alloy, nickel-chromium alloy; And/or the combination of said two devices, the weight percent of the first layer coating high heat conductance composition in coating is from 5% to 70 ﹪.
10. according to high-temperature nano anti-carburization coating claimed in claim 8, it is characterized in that: the high heat conductance composition of described second layer coating is to derive from least one, but be not limited to a kind of compound, compound comprises silicon carbide, silicon nitride, aluminium nitride, titanium nitride, boron nitride, chromium nitride; And/or metallic aluminium, nickel-aluminium alloy, nickel-chromium alloy; And/or the combination of said two devices, the weight percent of second layer coating high heat conductance composition in coating is from 5% to 70 ﹪;
It is to derive from least one that described second layer coating and molten iron infiltrate elimination air gap composition, but be not limited to a kind of glaze, nickel-aluminium alloy, nickel-chromium alloy, aluminium, copper, iron of low melting point, or their combination, second layer coating infiltrate to eliminate the weight percent of air gap composition in coating with molten iron be from 1% to 50%.
11. according to high-temperature nano anti-carburization coating claimed in claim 6, and its range of application comprises and spraying/or brush on large-scale steel-iron components/forging die surface forms anticreep carbon coating after solidifying.
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