CN103265264A - Ceramic paint and preparation method thereof as well as heating furnace tube - Google Patents
Ceramic paint and preparation method thereof as well as heating furnace tube Download PDFInfo
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- CN103265264A CN103265264A CN 201310206460 CN201310206460A CN103265264A CN 103265264 A CN103265264 A CN 103265264A CN 201310206460 CN201310206460 CN 201310206460 CN 201310206460 A CN201310206460 A CN 201310206460A CN 103265264 A CN103265264 A CN 103265264A
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Abstract
The invention relates to ceramic paint and a preparation method thereof. The ceramic paint contains ceramic powder, transition metal oxide, rare earth metal oxide and an adhesive. Relative to 100 parts by weight of the ceramic powder, the ceramic paint comprises 20-150 parts by weight of the transition metal oxide, 5-50 parts by weight of the rare earth metal oxide and 5-80 parts by weight of the adhesive, wherein the ceramic powder is a compound of calcium hydrogen phosphate and calcium carbonate; and the rare earth metal oxide is a combination of yttrium oxide, lanthanum oxide and cerium oxide. The invention also relates to a heating furnace tube with a ceramic coating formed by the ceramic paint. The ceramic coating formed by the ceramic paint has obviously improved wear resistance, corrosion resistance and fouling and slag-bonding resistance, a high thermal radiation rate and better thermal shock resistance stability.
Description
Technical field
The present invention relates to a kind of ceramic coating, the preparation method of this ceramic coating, and the heating furnace tube that comprises the ceramic coating that is formed by this ceramic coating.
Background technology
The Global climate change profound influence human survival and development, and low carbon technique becomes international focus and trend day by day.Low carbonization will drive real economy from two aspects, and the one, accelerate new forms of energy industry developments such as sun power, wind energy, the 2nd, to the low carbonization upgrading of conventional industries, the two all be unable to do without the support of relevant new material industry.
Sinopec's industry accounts for 20% of industrial economy total amount, and is extremely important to national economy.Petroleum chemical industry comprises petroleum and petrochemical industry and two major parts of chemical industry.Various process furnace and Reaktionsofen are that petrochemical enterprise is mainly produced and energy consumption equipment; these stoves expend a large amount of energy in process of production, discharge obnoxious flavoures such as a large amount of carbonic acid gas, oxynitride; havoc and influence ecological environment have increased immense pressure to China's joint source reduction of discharging, environment protection.
In recent years, high temperature resistant reinforcement absorbs nanometer metal ceramic coating and has obtained approval widely in the application of process furnace and Reaktionsofen, but in actual use, because the cohesive strength of coated material and body material is lower, wear resistance and the erosion resistance of coated material are relatively poor, make to cause easily that in use the coating be full of cracks comes off or corrosion failure, thereby influenced result of use and work-ing life.On the other hand, the physics of heating surface piping material and refractory materials and chemical property directly influence safe, energy-conservation, throughput and the environmental-protecting performance of the operation of the various stoves of petroleum chemical industry.Heating surface stains the slagging scorification meeting increases slin emissivity (blackness) decline, thermal conduction resistance, cause that furnace thermal efficiency decline, portative power deficiency, fire box temperature level are too high, the problem of aspects such as a series of safe, energy-conservation, production capacities such as heating surface local overheating, oxynitride (NOx mainly is heating power nitrogen) discharging increase and environmental protection.
Summary of the invention
The objective of the invention is in order to overcome the defective that the coating that is formed by existing nanometer metal ceramic coating exists wear resistance, erosion resistance and anti-contamination slagging scorification poor-performing, a kind of new ceramic coating and preparation method thereof and the heating furnace tube that comprises the ceramic coating that is formed by this ceramic coating are provided.
The invention provides a kind of ceramic coating, wherein, this ceramic coating contains ceramics powder, transition metal oxide, rare-earth oxide and tackiness agent, described ceramics powder with respect to 100 weight parts, the content of described transition metal oxide is the 20-150 weight part, the content of described rare-earth oxide is the 5-50 weight part, the content of described tackiness agent is the 5-80 weight part, wherein, described ceramics powder is the mixture of secondary calcium phosphate and calcium carbonate, described transition metal oxide is selected from titanium oxide, vanadium oxide, chromic oxide, manganese oxide, ferric oxide, cobalt oxide, nickel oxide, at least a in cupric oxide and the zinc oxide, described rare-earth oxide is yttrium oxide, the combination of lanthanum trioxide and cerium oxide.
The present invention also provides the preparation method of above-mentioned ceramic coating, this method comprises: described ceramics powder is mixed with described rare-earth oxide and grind, the described high heat conductance functional materials that first mixed powder that will obtain again and described transition metal oxide and selectivity add and described titanium alloy mix and grind, and second mixed powder that will obtain then mixes with described tackiness agent.
The present invention also provides a kind of heating furnace tube, has ceramic coating on the outside surface of described heating furnace tube, and wherein, described ceramic coating is formed by above-mentioned ceramic coating.
In described ceramic coating provided by the invention, by specific ceramics powder, transition metal oxide and rare-earth oxide are cooperated with predetermined ratio, make the coating that is formed by described ceramic coating have wear resistance, erosion resistance and the anti-contamination slagging scorification performance of obvious improvement.
And the coating that is formed by described ceramic coating has higher thermal emissivity rate, makes to comprise that the heating furnace tube of the ceramic coating that is formed by ceramic coating of the present invention in use has higher heat utilization efficiency.
Other features and advantages of the present invention will partly be described in detail in embodiment subsequently.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that embodiment described herein only is used for description and interpretation the present invention, is not limited to the present invention.
The invention provides a kind of ceramic coating, wherein, this ceramic coating contains ceramics powder, transition metal oxide, rare-earth oxide and tackiness agent, described ceramics powder with respect to 100 weight parts, the content of described transition metal oxide is the 20-150 weight part, the content of described rare-earth oxide is the 5-50 weight part, the content of described tackiness agent is the 5-80 weight part, wherein, described ceramics powder is the mixture of secondary calcium phosphate and calcium carbonate, described transition metal oxide is selected from titanium oxide, vanadium oxide, chromic oxide, manganese oxide, ferric oxide, cobalt oxide, nickel oxide, at least a in cupric oxide and the zinc oxide, described rare-earth oxide is yttrium oxide, the combination of lanthanum trioxide and cerium oxide.
In the preferred case, for making described ceramic coating have wear resistance, erosion resistance and the anti-contamination slagging scorification performance of further improvement, in described ceramic coating, described ceramics powder with respect to 100 weight parts, the content of described transition metal oxide is the 40-90 weight part, the content of described rare-earth oxide is the 10-40 weight part, and the content of described tackiness agent is the 10-40 weight part.
In described ceramic coating of the present invention, be introduced as yttrium oxide, lanthanum trioxide and the cerium oxide of rare-earth oxide, mainly be crystal grain thinning, increase crystal boundary, make the coating structure that is formed by described ceramic coating finer and close, thereby reach the purpose of improving anti-contamination slagging scorification performance and wear resistance.Therefore, in the present invention, the ratio between yttrium oxide, lanthanum trioxide and the cerium oxide three does not have strict restriction, as long as the three is used.Under the preferable case, in described rare-earth oxide, the weight ratio of yttrium oxide, lanthanum trioxide and cerium oxide is 1: 0.1-5: 0.1-5, more preferably 1: 0.5-3: 0.5-3, more preferably 1: 1.1-1.5: 1.2-2.When the ratio between yttrium oxide, lanthanum trioxide and the cerium oxide three met above-mentioned scope, anti-contamination slagging scorification performance and the wear resistance of the coating that is formed by this ceramic coating can be largely increased.
Ceramic coating according to the present invention, in described ceramics powder, the weight ratio of secondary calcium phosphate and calcium carbonate can be 0.5-20: 1, be preferably 6-10: 1.When the secondary calcium phosphate in the described ceramics powder and calcium carbonate were used with above-mentioned weight ratio, erosion resistance and the anti-contamination slagging scorification performance of the coating that is formed by this ceramic coating can be further improved.In the present invention, described secondary calcium phosphate can use with the form that contains crystal water, i.e. CaHPO
42H
2O.
Ceramic coating according to the present invention, described transition metal oxide are selected from least a in titanium oxide, vanadium oxide, chromic oxide, manganese oxide, ferric oxide, cobalt oxide, nickel oxide, cupric oxide and the zinc oxide.Preferably, in order to impel described transition metal oxide to form good mating reaction with described rare-earth oxide, thereby reach the purpose of abrasion property, erosion resistance and anti-contamination slagging scorification performance that obvious improvement forms by ceramic coating, described transition metal oxide is selected titanium oxide, chromic oxide, zinc oxide and vanadium oxide for use and is selected from least a combination in manganese oxide, ferric oxide, cobalt oxide, nickel oxide and the cupric oxide.Further preferably, the described transition metal oxide combination that is titanium oxide, chromic oxide, zinc oxide, vanadium oxide, manganese oxide and ferric oxide.Still more preferably, the described transition metal oxide combination that is 100 parts by weight of titanium oxide, 30-150 weight part chromic oxide, 20-100 part by weight of zinc oxide, 1-50 weight part vanadium oxide, 1-50 weight part manganese oxide and 1-50 weight part ferric oxide.Most preferably, described transition metal oxide is the combination of 100 parts by weight of titanium oxide, 60-120 weight part chromic oxide, 40-80 part by weight of zinc oxide, 10-30 weight part vanadium oxide, 5-20 weight part manganese oxide and 5-20 weight part ferric oxide.
Ceramic coating according to the present invention, described tackiness agent can be the conventional various tackiness agents that use in this area, for example can be conventional organic polymer binding agent and/or the mineral binder bond that uses in this area.Described organic polymer binding agent is preferably at least a in polyvinyl alcohol and the polyvinylpyrrolidone.Described mineral binder bond is preferably at least a in aluminium dihydrogen phosphate, water glass, Starso and the potassium silicate.In embodiment more preferably, in order further to improve bounding force between described ceramic coating and the body material, make the coating that is formed by described ceramic coating have higher wear resistance, described tackiness agent is selected the combination of polyvinyl alcohol and/or polyvinylpyrrolidone, aluminium dihydrogen phosphate and water glass for use.Most preferably, described tackiness agent is the combination of 100 weight account polyethylene alcohol and/or polyvinylpyrrolidone, 30-150 weight part aluminium dihydrogen phosphate and 30-100 weight part water glass.
Ceramic coating according to the present invention, in order further to improve coating abrasion performance, erosion resistance and the anti-contamination slagging scorification performance that is formed by described ceramic coating, and the suitable thermal emissivity rate that improves the coating that is formed by described ceramic coating, described ceramic coating preferably also contains the high heat conductance functional materials.Preferably, with respect to the described ceramics powder of 100 weight parts, the content of described high heat conductance functional materials is the 1-80 weight part, more preferably the 10-50 weight part.
In the present invention, described high heat conductance functional materials is preferably at least a in silicon carbide, silicon nitride, aluminium nitride, titanium nitride, boron nitride, chromium nitride, nickel-aluminium alloy and the nickel-chromium alloy, is preferably at least a in silicon carbide, silicon nitride, aluminium nitride, titanium nitride, boron nitride and the chromium nitride.
Ceramic coating according to the present invention, in order further to improve coating abrasion performance, erosion resistance and the anti-contamination slagging scorification performance that is formed by described ceramic coating, described ceramic coating preferably also contains titanium alloy.Preferably, with respect to the described ceramics powder of 100 weight parts, the content of described titanium alloy is the 1-50 weight part, more preferably the 10-40 weight part.
In the present invention, described titanium alloy is preferably at least a in titanium-aluminum-vanadium alloys, titanium-aluminum-tin alloy, titanium-aluminum-zirconium alloy, titanium-molybdenum alloy, titanium-molybdenum-nickelalloy and the titanium-lead alloy.
In one embodiment, have higher wear resistance, erosion resistance and anti-contamination slagging scorification performance for making the coating that is formed by described ceramic coating, have higher thermal emissivity rate simultaneously, described ceramic coating preferably contains following component:
100 weight part ceramics powders, described ceramics powder are the mixture of secondary calcium phosphate and calcium carbonate, and the weight ratio of secondary calcium phosphate and calcium carbonate is 6-10: 1;
40-90 weight part transition metal oxide, described transition metal oxide is the combination of titanium oxide, chromic oxide, zinc oxide, vanadium oxide, manganese oxide and ferric oxide, and the weight ratio of titanium oxide, chromic oxide, zinc oxide, vanadium oxide, manganese oxide and ferric oxide is 100: (30-150): (20-100): (1-50): (1-50): (1-50), be preferably 100: (60-120): (40-80): (10-30): (5-20): (5-20);
10-40 weight part rare-earth oxide, described rare-earth oxide is the combination of yttrium oxide, lanthanum trioxide and cerium oxide, and the weight ratio of yttrium oxide, lanthanum trioxide and cerium oxide is 1: (0.1-5): (0.1-5), be preferably 1: (0.5-3): (0.5-3), more preferably 1: (1.1-1.5): (1.2-2);
10-40 weight part tackiness agent;
10-50 weight part high heat conductance functional materials; And
Selectivity contains 1-50 weight part (preferred 10-40 weight part) titanium alloy.
In most preferred embodiments, described ceramic coating preferably contains following component:
100 weight part ceramics powders, described ceramics powder are the mixture of secondary calcium phosphate and calcium carbonate, and the weight ratio of secondary calcium phosphate and calcium carbonate is 6-10: 1;
40-90 weight part transition metal oxide, described transition metal oxide is the combination of titanium oxide, chromic oxide, zinc oxide, vanadium oxide, manganese oxide and ferric oxide, and the weight ratio of titanium oxide, chromic oxide, zinc oxide, vanadium oxide, manganese oxide and ferric oxide is 100: (60-120): (40-80): (10-30): (5-20): (5-20);
10-40 weight part rare-earth oxide, described rare-earth oxide are the combination of yttrium oxide, lanthanum trioxide and cerium oxide, and the weight ratio of yttrium oxide, lanthanum trioxide and cerium oxide is 1: (1.1-1.5): (1.2-2);
10-40 weight part tackiness agent, described tackiness agent are the combination of polyvinylpyrrolidone, aluminium dihydrogen phosphate and water glass, and the weight ratio of polyvinylpyrrolidone, aluminium dihydrogen phosphate and water glass is 100: (30-150): (30-100);
10-50 weight part high heat conductance functional materials, described high heat conductance functional materials are at least a in silicon carbide, silicon nitride, aluminium nitride, titanium nitride, boron nitride and the chromium nitride; And
10-40 weight part titanium alloy, described titanium alloy are at least a in titanium-aluminum-vanadium alloys, titanium-aluminum-tin alloy, titanium-aluminum-zirconium alloy, titanium-molybdenum alloy, titanium-molybdenum-nickelalloy and the titanium-lead alloy.
Ceramic coating according to the present invention, in actual use, water or organic solvent dilute described ceramic coating as required, to reach the degree of being convenient to spray; Perhaps also can be directly come into the market as finished product with the diluted state of the moisture or organic solvent of respective concentration.
Ceramic coating according to the present invention can be prepared according to the method for routine, for example each component directly can be mixed and grind evenly, thereby make.
In the preferred case, have better comprehensive performance in order to ensure described ceramic coating, the preparation method of described ceramic coating may further comprise the steps:
(1) described ceramics powder is mixed with described rare-earth oxide and grind, obtain first mixed powder;
(2) the described high heat conductance functional materials that described first mixed powder and described transition metal oxide and selectivity are added and described titanium alloy mix and grind, and obtain second mixed powder;
(3) described second mixed powder is mixed with described tackiness agent.
In aforesaid method, the described high heat conductance functional materials that described ceramics powder, described rare-earth oxide, described transition metal oxide, described tackiness agent and selectivity add and the consumption of described titanium alloy and substance classes make the ceramic coating of final preparation satisfy basic embodiment, preferred implementation or the most preferred embodiment of aforementioned ceramic coating of the present invention.
In aforesaid method, preferably, process of lapping by step (1) and step (2), the size of at least part of particle reaches below the 100nm in the ceramic coating of feasible final preparation, more preferably make the size of 50% above particle reach below the 100nm, further preferably make the size of 80% above particle reach below the 100nm.
The present invention also provides a kind of heating furnace tube, has ceramic coating on the outside surface of described heating furnace tube, and wherein, described ceramic coating is formed by ceramic coating of the present invention.
In described heating furnace tube, there is no particular limitation for the thickness of described ceramic coating, can be the conventional thickness of this area, for example can be 0.05-0.1mm.
In described heating furnace tube, the material of boiler tube matrix can be the material of various routines, for example can be carbon steel, steel alloy, refractory materials etc.
The invention will be further described by the following examples.
Embodiment 1
Present embodiment is used for explanation described ceramic coating provided by the invention and preparation method thereof.
CaHPO with 86 weight parts
42H
2The calcium carbonate of O and 14 weight parts mixes the ceramics powder that obtains 100 weight parts.The rare-earth oxide (be made up of yttrium oxide, lanthanum trioxide and cerium oxide, and the weight ratio of yttrium oxide, lanthanum trioxide and cerium oxide being 1: 1.3: 1.6) of described ceramics powder and 30 weight parts is mixed, and wet ball grinding 5 hours; The transition metal oxide that then adds 60 weight parts (is made up of titanium oxide, chromic oxide, zinc oxide, vanadium oxide, manganese oxide and ferric oxide, and the weight ratio of titanium oxide, chromic oxide, zinc oxide, vanadium oxide, manganese oxide and ferric oxide is 100: 100: 60: 20: 10: 15), the titanium-molybdenum alloy (available from the sensible bimetal company limited in Wenzhou City) of the silicon carbide of 30 weight parts and 20 weight parts, and wet ball grinding 8 hours again, make that wherein about 80% particle is of a size of below the 100nm; Then, to the polyvinylpyrrolidone that wherein adds 10 weight parts (available from Hangzhou scientific and technological development company limited of green section), the aluminium dihydrogen phosphate of 10 weight parts and the water glass of 10 weight parts, namely get ceramic coating A1 after mixing.
Embodiment 2
Present embodiment is used for explanation described ceramic coating provided by the invention and preparation method thereof.
CaHPO with 88 weight parts
42H
2The calcium carbonate of O and 12 weight parts mixes the ceramics powder that obtains 100 weight parts.The rare-earth oxide (be made up of yttrium oxide, lanthanum trioxide and cerium oxide, and the weight ratio of yttrium oxide, lanthanum trioxide and cerium oxide being 1: 1.1: 2) of described ceramics powder and 40 weight parts is mixed, and wet ball grinding 5 hours; The transition metal oxide that then adds 40 weight parts (is made up of titanium oxide, chromic oxide, zinc oxide, vanadium oxide, manganese oxide and ferric oxide, and the weight ratio of titanium oxide, chromic oxide, zinc oxide, vanadium oxide, manganese oxide and ferric oxide is 100: 120: 40: 10: 20: 5), the titanium-lead alloy (available from the logical special alloy company limited of Jinan Xin Hai) of the silicon nitride of 10 weight parts and 40 weight parts, and wet ball grinding 8 hours again, make that wherein about 80% particle is of a size of below the 100nm; Then, to the polyvinylpyrrolidone that wherein adds 14 weight parts (available from Hangzhou scientific and technological development company limited of green section), the aluminium dihydrogen phosphate of 21 weight parts and the water glass of 5 weight parts, namely get ceramic coating A2 after mixing.
Embodiment 3
Present embodiment is used for explanation described ceramic coating provided by the invention and preparation method thereof.
CaHPO with 90.5 weight parts
42H
2The calcium carbonate of O and 9.5 weight parts mixes the ceramics powder that obtains 100 weight parts.The rare-earth oxide (be made up of yttrium oxide, lanthanum trioxide and cerium oxide, and the weight ratio of yttrium oxide, lanthanum trioxide and cerium oxide being 1: 1.5: 1.2) of described ceramics powder and 10 weight parts is mixed, and wet ball grinding 5 hours; The transition metal oxide that then adds 90 weight parts (is made up of titanium oxide, chromic oxide, zinc oxide, vanadium oxide, manganese oxide and ferric oxide, and the weight ratio of titanium oxide, chromic oxide, zinc oxide, vanadium oxide, manganese oxide and ferric oxide is 100: 60: 80: 30: 5: 20), the titanium nitride of 50 weight parts and the titanium-aluminum-vanadium alloys (available from Xi'an Tianrui novel material company limited) of 10 weight parts, and wet ball grinding 8 hours again, make that wherein about 80% particle is of a size of below the 100nm; Then, to the polyvinyl alcohol that wherein adds 4.3 weight parts (available from the huge chemical reagent of Tianjin Dongli District factory), the aluminium dihydrogen phosphate of 1.4 weight parts and the water glass of 4.3 weight parts, namely get ceramic coating A3 after mixing.
Embodiment 4
Present embodiment is used for explanation described ceramic coating provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares ceramic coating, and difference is that in described rare-earth oxide, the weight ratio of yttrium oxide, lanthanum trioxide and cerium oxide is 1: 0.1: 5, thereby makes ceramic coating A4.
Embodiment 5
Present embodiment is used for explanation described ceramic coating provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares ceramic coating, and difference is that in described rare-earth oxide, the weight ratio of yttrium oxide, lanthanum trioxide and cerium oxide is 1: 5: 0.1, thereby makes ceramic coating A5.
Embodiment 6
Present embodiment is used for explanation described ceramic coating provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares ceramic coating, and difference is that in described rare-earth oxide, the weight ratio of yttrium oxide, lanthanum trioxide and cerium oxide is 1: 0.05: 6, thereby makes ceramic coating A6.
Embodiment 7
Present embodiment is used for explanation described ceramic coating provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares ceramic coating, and difference is that in described rare-earth oxide, the weight ratio of yttrium oxide, lanthanum trioxide and cerium oxide is 1: 5.5: 0.08, thereby makes ceramic coating A7.
Embodiment 8
Present embodiment is used for explanation described ceramic coating provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares ceramic coating, and difference is, in described ceramics powder, and CaHPO
42H
2The weight ratio of O and calcium carbonate is 0.5: 1, thereby makes ceramic coating A8.
Embodiment 9
Present embodiment is used for explanation described ceramic coating provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares ceramic coating, and difference is, in described ceramics powder, and CaHPO
42H
2The weight ratio of O and calcium carbonate is 20: 1, thereby makes ceramic coating A9.
Embodiment 10
Present embodiment is used for explanation described ceramic coating provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares ceramic coating, and difference is, in described ceramics powder, and CaHPO
42H
2The weight ratio of O and calcium carbonate is 0.3: 1, thereby makes ceramic coating A10.
Embodiment 11
Present embodiment is used for explanation described ceramic coating provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares ceramic coating, and difference is, in described ceramics powder, and CaHPO
42H
2The weight ratio of O and calcium carbonate is 22: 1, thereby makes ceramic coating A11.
Embodiment 12
Present embodiment is used for explanation described ceramic coating provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares ceramic coating, difference is, the transition metal oxide that adds is made up of titanium oxide, zinc oxide, manganese oxide and ferric oxide, and the weight ratio of titanium oxide, zinc oxide, manganese oxide and ferric oxide is 100: 60: 10: 15, thus make ceramic coating A12.
Embodiment 13
Present embodiment is used for explanation described ceramic coating provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares ceramic coating, and difference is, oxygen-free vanadium in the transition metal oxide of adding, thus make ceramic coating A13.
Embodiment 14
Present embodiment is used for explanation described ceramic coating provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares ceramic coating, and difference is, oxygen-free chromium in the transition metal oxide of adding, thus make ceramic coating A14.
Embodiment 15
Present embodiment is used for explanation described ceramic coating provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares ceramic coating, and difference is not add silicon carbide, thereby make ceramic coating A15.
Embodiment 16
Present embodiment is used for explanation described ceramic coating provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares ceramic coating, and difference is not add titanium-molybdenum alloy, thereby make ceramic coating A16.
Embodiment 17
Present embodiment is used for explanation described ceramic coating provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares ceramic coating, and difference is not add silicon carbide and titanium-molybdenum alloy, thereby make ceramic coating A17.
Embodiment 18
Present embodiment is used for explanation described ceramic coating provided by the invention and preparation method thereof.
CaHPO with 86 weight parts
42H
2The calcium carbonate of O and 14 weight parts mixes the ceramics powder that obtains 100 weight parts.With the rare-earth oxide of described ceramics powder and 30 weight parts (by yttrium oxide, lanthanum trioxide and cerium oxide are formed, and yttrium oxide, the weight ratio of lanthanum trioxide and cerium oxide is 1: 1.3: 1.6), the transition metal oxide of 60 weight parts is (by titanium oxide, chromic oxide, zinc oxide, vanadium oxide, manganese oxide and ferric oxide are formed, and titanium oxide, chromic oxide, zinc oxide, vanadium oxide, the weight ratio of manganese oxide and ferric oxide is 100: 100: 60: 20: 10: 15), the silicon carbide of 30 weight parts, titanium-the molybdenum alloy of 20 weight parts (available from the sensible bimetal company limited in Wenzhou City), the polyvinylpyrrolidone of 10 weight parts (available from Hangzhou scientific and technological development company limited of green section), the water glass of the aluminium dihydrogen phosphate of 10 weight parts and 10 weight parts, ball milling is 13 hours then, make that wherein about 80% particle is of a size of below the 100nm, thereby make ceramic coating A18.
Comparative Examples 1
Method according to embodiment 1 prepares ceramic coating, and difference is, the rare-earth oxide of adding is made up of yttrium oxide and cerium oxide, and the weight ratio of yttrium oxide and cerium oxide is 1: 1.6, thereby makes ceramic coating D1.
Comparative Examples 2
Method according to embodiment 1 prepares ceramic coating, and difference is, the rare-earth oxide of adding is made up of yttrium oxide and lanthanum trioxide, and the weight ratio of yttrium oxide and lanthanum trioxide is 1: 1.3, thereby makes ceramic coating D2.
Comparative Examples 3
Method according to embodiment 1 prepares ceramic coating, and difference is, the rare-earth oxide of adding is made up of lanthanum trioxide and cerium oxide, and the weight ratio of lanthanum trioxide and cerium oxide is 1: 1.23, thereby makes ceramic coating D3.
Comparative Examples 4
Method according to embodiment 1 prepares ceramic coating, and difference is with the aluminum oxide replacement ceramics powder of identical weight, thereby to make ceramic coating D4.
Comparative Examples 5
Method according to embodiment 1 prepares ceramic coating, and difference is that with respect to the ceramics powder of 100 weight parts, the add-on of described rare-earth oxide is 3 weight parts, thereby makes ceramic coating D5.
Comparative Examples 6
Method according to embodiment 1 prepares ceramic coating, and difference is that with respect to the ceramics powder of 100 weight parts, the add-on of described rare-earth oxide is 60 weight parts, thereby makes ceramic coating D6.
Comparative Examples 7
Method according to embodiment 1 prepares ceramic coating, and difference is that with respect to the ceramics powder of 100 weight parts, the add-on of described transition metal oxide is 15 weight parts, thereby makes ceramic coating D7.
Comparative Examples 8
Method according to embodiment 1 prepares ceramic coating, and difference is that with respect to the ceramics powder of 100 weight parts, the add-on of described transition metal oxide is 160 weight parts, thereby makes ceramic coating D8.
Embodiment 19-36 and Comparative Examples 9-16
Present embodiment is used for explanation heating furnace tube provided by the invention.
Spray to form ceramic coating respectively with the ceramic coating for preparing among embodiment 1-18 and the Comparative Examples 1-8.The heating furnace tube that use is made by 304 stainless steels is as body material.Before spraying, body material is carried out sandblasting.Air plasma spraying equipment is used in spraying, and spray parameters is: argon gas 40L/min, and hydrogen 10L/min, voltage 68V, electric current 650A, coat-thickness are 0.1mm.
Test case
(1) detect the thermal emissivity rate of the coating on each boiler tube according to the method for GJB2502.3-2006, the result is as shown in table 1 below.
(2) detect the thermal shock resistance of the coating on each boiler tube according to the method for JB/T3648.1-1994, the result is as shown in table 1 below.
(3) abrasion property on the boiler tube detects according to following method:
Adopt high temperature wear experimental machine (making finite process department available from Xuanhua section China trier) to carry out the wear test test, experiment condition is: plus load 1000g, and wearing-in period 40 minutes, the wearing and tearing radius is made as 5mm, rotating speed is made as 280r/min, and the mill material is adopted the GCr15 rapid steel.Show wear resistance with the relative wear scale, concrete calculating formula is as follows:
ε＝M
0/M
1
Wherein, ε represents relative wear amount, M
0Expression does not form the wear weight loss of the boiler tube of ceramic coating, M
1Expression is formed with the wear weight loss of the boiler tube of ceramic coating, and calculation result is as shown in table 1 below.The more big wear resistance of then representing of ε value is more good.
(4) the erosion resistance detection method of the coating on the boiler tube: be that the hydrochloric acid of 20 weight %, the NaOH of 20 weight % and the NaCl of 15 weight % at room temperature corroded 48 hours with concentration, and calculate etching extent with the weightlessness on the unit surface that concrete calculating formula is as follows respectively:
δ＝Δm/S
Wherein, Δ m represents the weightless quality (mg) of coating sample corrosion front and back; S represents the coated surface area (mm of coating sample
2); δ represents etching extent (mg/mm
2).Calculation result is as shown in table 1 below.
(5) according to the anti-contamination slagging scorification performance of the coating on the method detection boiler tube of GB9780-88, its result is as shown in table 1 below.
Table 1
By last table 1 as can be seen, the ceramic coating that is formed by described ceramic coating of the present invention has wear resistance, erosion resistance and the anti-contamination slagging scorification performance of obvious improvement, also has higher preferably thermal emissivity rate and anti-thermal shock stability simultaneously.
Claims (10)
1. ceramic coating, it is characterized in that, this ceramic coating contains ceramics powder, transition metal oxide, rare-earth oxide and tackiness agent, described ceramics powder with respect to 100 weight parts, the content of described transition metal oxide is the 20-150 weight part, the content of described rare-earth oxide is the 5-50 weight part, the content of described tackiness agent is the 5-80 weight part, wherein, described ceramics powder is the mixture of secondary calcium phosphate and calcium carbonate, described transition metal oxide is selected from titanium oxide, vanadium oxide, chromic oxide, manganese oxide, ferric oxide, cobalt oxide, nickel oxide, at least a in cupric oxide and the zinc oxide, described rare-earth oxide is yttrium oxide, the combination of lanthanum trioxide and cerium oxide.
2. ceramic coating according to claim 1, wherein, with respect to the described ceramics powder of 100 weight parts, the content of described transition metal oxide is the 40-90 weight part, the content of described rare-earth oxide is the 10-40 weight part, and the content of described tackiness agent is the 10-40 weight part.
3. ceramic coating according to claim 1 and 2, wherein, in described rare-earth oxide, the weight ratio of yttrium oxide, lanthanum trioxide and cerium oxide is 1: 0.1-5: 0.1-5 is preferably 1: 0.5-3: 0.5-3, more preferably 1: 1.1-1.5: 1.2-2.
4. ceramic coating according to claim 1 and 2, wherein, in described ceramics powder, the weight ratio of secondary calcium phosphate and calcium carbonate is 0.5-20: 1, be preferably 6-10: 1.
5. ceramic coating according to claim 1 and 2, wherein, described transition metal oxide is titanium oxide, chromic oxide, zinc oxide and vanadium oxide and be selected from manganese oxide, ferric oxide, cobalt oxide, at least a in nickel oxide and the cupric oxide, be preferably titanium oxide, chromic oxide, zinc oxide, vanadium oxide, the combination of manganese oxide and ferric oxide, 100 parts by weight of titanium oxide more preferably, 30-150 weight part chromic oxide, the 20-100 part by weight of zinc oxide, 1-50 weight part vanadium oxide, the combination of 1-50 weight part manganese oxide and 1-50 weight part ferric oxide further is preferably 100 parts by weight of titanium oxide, 60-120 weight part chromic oxide, the 40-80 part by weight of zinc oxide, 10-30 weight part vanadium oxide, the combination of 5-20 weight part manganese oxide and 5-20 weight part ferric oxide.
6. ceramic coating according to claim 1 and 2, wherein, described tackiness agent is organic polymer binding agent and/or mineral binder bond, described organic polymer binding agent is at least a in polyvinyl alcohol and the polyvinylpyrrolidone, and described mineral binder bond is at least a in aluminium dihydrogen phosphate, water glass, Starso and the potassium silicate; Preferably, described tackiness agent is the combination of polyvinyl alcohol and/or polyvinylpyrrolidone, aluminium dihydrogen phosphate and water glass, more preferably the combination of 100 weight account polyethylene alcohol and/or polyvinylpyrrolidone, 30-150 weight part aluminium dihydrogen phosphate and 30-100 weight part water glass.
7. ceramic coating according to claim 1 and 2, wherein, described ceramic coating also contains the high heat conductance functional materials, and with respect to the described ceramics powder of 100 weight parts, the content of described high heat conductance functional materials is the 1-80 weight part, is preferably the 10-50 weight part; Preferably, described high heat conductance functional materials is at least a in silicon carbide, silicon nitride, aluminium nitride, titanium nitride, boron nitride, chromium nitride, nickel-aluminium alloy and the nickel-chromium alloy.
8. ceramic coating according to claim 1 and 2, wherein, described ceramic coating also contains titanium alloy, and with respect to the described ceramics powder of 100 weight parts, the content of described titanium alloy is the 1-50 weight part, is preferably the 10-40 weight part; Preferably, described titanium alloy is at least a in titanium-aluminum-vanadium alloys, titanium-aluminum-tin alloy, titanium-aluminum-zirconium alloy, titanium-molybdenum alloy, titanium-molybdenum-nickelalloy and the titanium-lead alloy.
9. the preparation method of any described ceramic coating among the claim 1-8, this method may further comprise the steps:
(1) described ceramics powder is mixed with described rare-earth oxide and grind, obtain first mixed powder;
(2) the described high heat conductance functional materials that described first mixed powder and described transition metal oxide and selectivity are added and described titanium alloy mix and grind, and obtain second mixed powder;
(3) described second mixed powder is mixed with described tackiness agent.
10. a heating furnace tube has ceramic coating on the outside surface of described heating furnace tube, it is characterized in that, described ceramic coating is formed by any described ceramic coating among the claim 1-8.
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Application publication date: 20130828 |