CN104164129A - Oily titanium ingot high-temperature-oxidation-resistant coating, applications thereof and titanium ingot producing method - Google Patents

Oily titanium ingot high-temperature-oxidation-resistant coating, applications thereof and titanium ingot producing method Download PDF

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CN104164129A
CN104164129A CN201410312412.9A CN201410312412A CN104164129A CN 104164129 A CN104164129 A CN 104164129A CN 201410312412 A CN201410312412 A CN 201410312412A CN 104164129 A CN104164129 A CN 104164129A
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titanium ingot
powder
oiliness
resistant coating
oxidation resistant
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CN104164129B (en
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许哲峰
王莹
彭琳
肖聪
李军
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Pangang Group Panzhihua Iron and Steel Research Institute Co Ltd
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Pangang Group Panzhihua Iron and Steel Research Institute Co Ltd
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Abstract

Oily titanium ingot high-temperature-oxidation-resistant coating is disclosed. The coating is prepared by uniformly mixing a raw material mixture. The raw material mixture comprises an oxidation protective agent and an oily film forming agent. The oxidation protective agent comprises Al powder, Zn powder, Sn powder and Cu powder. The weight ratio of the Al powder, the Zn powder, the Sn powder and the Cu powder is 1:0.01-0.1:0.01-0.1:0.01-0.1. Applications of the coating in titanium ingot production and a titanium ingot producing method are also disclosed. The coating can ensure that surfaces of titanium ingots are not oxidized or cracked after the titanium ingots are disposed at a constant high temperature of 1000 DEG C for 8 h, and largely reduce formation of oxygen dissolving layers. The coating is environmental friendly and simple in preparation process, and can adopt a plurality of coating manners. The titanium ingot producing method has a wide popularization and application prospect in production of titanium plates and titanium tubes.

Description

The production method of oiliness titanium ingot high-temperature oxidation resistant coating and application thereof and titanium ingot
Technical field
The present invention relates to high-temperature-resistant coating for metal field, particularly, relate to a kind of oiliness titanium ingot high-temperature oxidation resistant coating, and the application of this oiliness titanium ingot high-temperature oxidation resistant coating in titanium ingot is produced, and a kind of production method of titanium ingot.
Background technology
Titanium ingot is generally wanted annealed processing in process of production, annealing generally will be carried out under the high temperature of 900 ℃ of left and right, and at high temperature, oxygen can enter titanium ingot surface, forming hard dissolved oxygen layer, will there is the deep torn grain of degree of depth 20mm left and right at 900 ℃ of heating 4h with upper surface in titanium ingot.For guaranteeing the follow-up rolling of titanium pipe and the surface quality of hot rolling titanium plate, in the operation of rolling, need titanium ingot to cut and grinding process, to remove crackle and dissolved oxygen layer, loss is larger like this.Because titanium ingot is to be made by titanium sponge reaction, cracking part and the dissolved oxygen layer of titanium ingot in heat-processed are removed, have a strong impact on cost and the lumber recovery of titanium material, therefore need to carry out high temperature protection to titanium ingot.
Titanium ingot is carried out to high temperature protection, according to the study titanium surface platinum ion electroplate can protect titanium 650 ℃ not oxidized, but can not meet the high temperature requirement of annealing far away; The MCrAlY alloy with outstanding oxidation-resistance by spray or evaporation coating to titanium matrix, but this also exist form with titanium that congruent melting compound increases and titanium production heat-processed in the formation problem of phase diffusion layer; When traditional anti-oxidation protection Paint Boron silicate glass base coating applies to titanium, the formation of oxide compound is had certain effect, but can not reach the object that prevents that dissolved oxygen layer from forming.Current useful aluminium, as the aluminium base oxidation protection coating of oxidation inhibitor, for titanium, the formation of oxide compound and dissolved oxygen layer is had certain effect, but effect is still undesirable, and because viscosity is lower, during use, can only be sprayed, and can not brush, and has limited its application.
Therefore, need to a kind ofly can effectively prevent that titanium ingot surface dissolved oxygen layer and crackle from forming, thereby greatly reduce the high temp. protective coating of titanium ingot production cost.
Summary of the invention
The object of the invention is, in order to overcome existing high temp. protective coating to the dissatisfactory defect of the protection of titanium ingot, provides the production method of a kind of new oiliness titanium ingot high-temperature oxidation resistant coating and application and titanium ingot.
The present inventor finds under study for action, contain Al powder, Zn powder, Sn powder and Cu powder are as oxidation protection agent, and Al powder, Zn powder, the weight ratio of Sn powder and Cu powder is 1:0.01-0.1:0.01-0.1:0.01-0.1, the oiliness titanium ingot high-temperature oxidation resistant coating obtaining after the raw mixture that contains this oxidation protection agent and oiliness membrane-forming agent mixes, can guarantee titanium ingot not oxidized cracking in constant temperature 8h surface under 1000 ℃ of high temperature, and can greatly reduce the formation of dissolved oxygen layer, can effectively reduce production costs and improve productivity effect, and this oiliness titanium ingot high-temperature oxidation resistant coating can adopt pneumatic spraying, vacuum spraying, the multiple coating methods such as brushing, easy to use.
Therefore, to achieve these goals, on the one hand, the invention provides a kind of oiliness titanium ingot high-temperature oxidation resistant coating, after described oiliness titanium ingot high-temperature oxidation resistant coating is mixed by a kind of raw mixture, obtain, described raw mixture contains oxidation protection agent and oiliness membrane-forming agent; Described oxidation protection agent contains Al powder, Zn powder, Sn powder and Cu powder, and the weight ratio of Al powder, Zn powder, Sn powder and Cu powder is 1:0.01-0.1:0.01-0.1:0.01-0.1.
Preferably, the weight ratio of Al powder, Zn powder, Sn powder and Cu powder is 1:0.02-0.04:0.02-0.04:0.02-0.04.
Second aspect, the invention provides the application of oiliness titanium ingot high-temperature oxidation resistant coating as above in titanium ingot is produced.
The third aspect, the invention provides a kind of production method of titanium ingot, described method is included in titanium ingot carries out before anneal, and at the surface-coated oiliness titanium ingot high-temperature oxidation resistant coating of titanium ingot, described oiliness titanium ingot high-temperature oxidation resistant coating is oiliness titanium ingot high-temperature oxidation resistant coating as above.
Oiliness titanium ingot high-temperature oxidation resistant coating of the present invention, can guarantee titanium ingot not oxidized cracking in constant temperature 8h surface under 1000 ℃ of high temperature, and can greatly reduce the formation of dissolved oxygen layer, can effectively reduce production costs, and improves lumber recovery and the production efficiency of titanium material.For example, take and climb steel as example, rolling titanium section product, 10,000 tons of production capacities are produced in design per year, with 7.5 tons of calculating of each titanium ingot (semifinished product), will produce every year the titanium billet of 1300 left and right, and each titanium ingot is of a size of: thickness 0.28m, length 7.5m, width 1.25m; Each titanium ingot gross area is about 25m 2, the annual 32500m that approximately produces 2, the coat-thickness of oiliness titanium ingot high-temperature oxidation resistant coating of the present invention is 0.2-0.4mm; Every square meter is approximately used 200-400g, annual approximately 6.5 tons-13 tons of the coating that use of accumulative total.With each titanium ingot, there is zone of oxidation cracking 20mm depth calculation, each titanium ingot will machine away 100-200 kilogram, with 80000 yuan/ton of calculating of titanium ingot, each titanium ingot, because oxidation cutting tip is lost between 8000-16000 unit, meanwhile, also will spend a large amount of human and material resources and cut, extra increase production cost and production time, and adopt oiliness titanium ingot high-temperature oxidation resistant coating of the present invention, the price of coating to calculate by 200 yuan/Kg, will save every year approximately 13,650,000 yuan of production costs.
Oiliness titanium ingot high-temperature oxidation resistant coating of the present invention, does not contain the harmful element limiting in RoHS quality in coating, meanwhile, this oiliness titanium ingot high-temperature oxidation resistant coating does not have toxic substance volatilization in air, does not affect the environmental protection effect of construction environment etc.
Oiliness titanium ingot high-temperature oxidation resistant coating preparation technology of the present invention is simple, on-the-spot preparation in the time of can using, and the preparation time is short, simple possible; Also can prepare after production, at room temperature store, coating is stablized shelf-stability and can be reached more than 6 months, there will be precipitation, demixing phenomenon, and still, during use, shaking up or re-start stirring can use.
Oiliness titanium ingot high-temperature oxidation resistant coating of the present invention, can adopt the multiple coating methods such as pneumatic spraying, vacuum spraying, brushing, easy to use.
The production method of titanium ingot of the present invention has good economic benefit and social benefit, in titanium plate and titanium pipe production industry, has comparatively wide popularizing application prospect.
Other features and advantages of the present invention partly in detail are described the embodiment subsequently.
Accompanying drawing explanation
Fig. 1 is the photo of titanium ingot surface after embodiment 1 rolling.
Fig. 2 is the photo of titanium ingot surface after comparative example 1 rolling.
Fig. 3 is the photo of titanium ingot surface after comparative example 2 rollings.
Fig. 4 is the Hardness Distribution of titanium ingot surface after each embodiment and comparative example rolling.
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
On the one hand, the invention provides a kind of oiliness titanium ingot high-temperature oxidation resistant coating, after this oiliness titanium ingot high-temperature oxidation resistant coating is mixed by a kind of raw mixture, obtain, raw mixture contains oxidation protection agent and oiliness membrane-forming agent; Oxidation protection agent contains Al powder, Zn powder, Sn powder and Cu powder, and the weight ratio of Al powder, Zn powder, Sn powder and Cu powder is 1:0.01-0.1:0.01-0.1:0.01-0.1.
According to the present invention, although this oiliness titanium ingot high-temperature oxidation resistant coating obtains after being mixed by a kind of raw mixture, raw mixture contains oxidation protection agent and oiliness membrane-forming agent; Oxidation protection agent contains Al powder, Zn powder, Sn powder and Cu powder; the weight ratio of Al powder, Zn powder, Sn powder and Cu powder is 1:0.01-0.1:0.01-0.1:0.01-0.1; can realize object of the present invention; can guarantee titanium ingot not oxidized cracking in constant temperature 8h surface under 1000 ℃ of high temperature; greatly reduce the formation of dissolved oxygen layer; and this oiliness titanium ingot high-temperature oxidation resistant coating can adopt the multiple coating methods such as pneumatic spraying, vacuum spraying, brushing, easy to use.But under preferable case, the weight ratio of Al powder, Zn powder, Sn powder and Cu powder is 1:0.02-0.04:0.02-0.04:0.02-0.04, can further reduce the formation of dissolved oxygen layer.Therefore, preferably, the weight ratio of Al powder, Zn powder, Sn powder and Cu powder is 1:0.02-0.04:0.02-0.04:0.02-0.04.
In the present invention, for the content of Zn powder, Sn powder and Cu powder, can be identical, also can be different, as long as content is in above-mentioned ratio range.
In the present invention, with respect to the oxidation protection agent of 1 weight part, in solid, the consumption of oiliness membrane-forming agent is preferably 0.025-0.1 weight part.Under this preferable case, can make the pH value of oiliness titanium ingot high-temperature oxidation resistant coating of the present invention is 7.5-9.5, and solid content is 85-90 % by weight, is directly coated in online titanium ingot surface, can solidify rapidly, form self-drying type coating, and because solid content is high, there will not be rete trickling phenomenon, coating tack is very good, no matter, when wet film or dry film, coating tack can meet the needs of titanium ingot roller-way bobbing machine friction, there will not be coating scaling or dry linting phenomenon.
In the present invention, for oiliness membrane-forming agent, without particular requirement, can adopt the conventional various oiliness membrane-forming agents in this area, for example, oiliness membrane-forming agent can be selected from least one in oiliness epoxy resin, polyurethane paint, acrylic latex coating and alkyd paint.But the present inventor finds under study for action, when oiliness membrane-forming agent is preferably oiliness epoxy resin, can further reduce the formation of dissolved oxygen layer.Therefore, oiliness membrane-forming agent is preferably oiliness epoxy resin, for the solid content of oiliness epoxy resin, without particular requirement, can adopt the conventional oiliness epoxy resin in this area, and the solid content of oiliness epoxy resin is preferably 40-60 % by weight.
In order further to improve oiliness titanium ingot high-temperature oxidation resistant coating of the present invention in the tack of titanium ingot surface; raw mixture of the present invention preferably also contains one or more in solidifying agent, dispersion agent and thinner; more preferably contain solidifying agent, dispersion agent and thinner; oxidation protection agent with respect to 1 weight part; the consumption of solidifying agent is preferably 0.001-0.003 weight part; the consumption of dispersion agent is preferably 0.0005-0.001 weight part, and the consumption of thinner is preferably 0.003-0.008 weight part.
In the present invention, for solidifying agent, dispersion agent, thinner concrete material separately, without particular requirement, can adopt this area conventional various solidifying agent, dispersion agent, thinner.For example, solidifying agent can be SiO 2, dispersion agent can be polyvinyl alcohol, Polyvinylpyrolidone (PVP), polyoxyethylene etc., and thinner can be selected applicable thinner according to oiliness membrane-forming agent used, and this is conventionally known to one of skill in the art, does not repeat them here.
For the preparation method of oiliness titanium ingot high-temperature oxidation resistant coating of the present invention, without particular requirement, can adopt the conventional the whole bag of tricks in this area, as long as each component is mixed.But the present inventor finds under study for action, adopts and prepares with the following method oiliness titanium ingot high-temperature oxidation resistant coating, can make each component be mixed to get more even.Concrete grammar is: first oiliness membrane-forming agent and mixing diluents are diluted, then under agitation, slowly add oxidation protection agent, and then add solidifying agent, stir, then add dispersion agent, be stirred to and be mutually uniform and stable.
Second aspect, the invention provides the application of oiliness titanium ingot high-temperature oxidation resistant coating as above in titanium ingot is produced.
The third aspect, the invention provides a kind of production method of titanium ingot, the method is included in titanium ingot carries out before anneal, and at the surface-coated oiliness titanium ingot high-temperature oxidation resistant coating of titanium ingot, oiliness titanium ingot high-temperature oxidation resistant coating is oiliness titanium ingot high-temperature oxidation resistant coating as above.
In the present invention, for anneal, without particular requirement, can adopt the annealing treating process of this area routine, for example, annealing temperature is 800-1000 ℃, and annealing time is 4-8h.
In the present invention, for the mode applying without particular determination, such as comprising pneumatic spraying, vacuum spraying, brushing etc.
In the present invention, the thickness of the photopolymer layer that the amount that oiliness titanium ingot high-temperature oxidation resistant coating applies forms after preferably making oiliness titanium ingot high-temperature oxidation resistant coating solidify is 0.2-0.4mm.When the thickness of photopolymer layer is less than 0.2mm, titanium ingot can not get sufficient high temperature protection, and when the thickness of photopolymer layer surpasses 0.4mm, cost raises.
What those skilled in the art should understand that is, titanium ingot carries out will being rolled processing after anneal, the condition of processing for rolling is without particular requirement, can adopt the normal condition of this area, for example, the condition of rolling comprises: after annealing, carry out the rolling of 10 passages, each percentage pass reduction is approximately 20mm.
Embodiment
The present invention is further illustrated for following embodiment, but therefore do not limit the present invention.
In the following Examples and Comparative Examples:
Titanium ingot: thickness 0.28m, length 7.5m, width 1.25m.
Oiliness epoxy resin: be purchased from Beijing Zhen Chuan construction work company limited.
Determination of solid content method: GB-T2793-1995.
PH values determination method: adopt pH meter (being purchased from Shanghai INESA Scientific Instrument Co., Ltd., thunder magnetic PHSJ-5 type) to measure.
Titanium ingot surface measurement of hardness method: GB/T14235.5-1993.
Rolling is the rolling of carrying out 10 passages after annealing, and each percentage pass reduction is 20mm.
Embodiment 1
The present embodiment is for illustrating the production method of oiliness titanium ingot high-temperature oxidation resistant coating of the present invention and titanium ingot.
(1) normal temperature and pressure (25 ℃, 0.1MPa) under, take 100g oiliness epoxy resin (solid content 50 % by weight) and be placed in container;
(2) add 5g polypropylene glycol diglycidyl ether (to be purchased from Changzhou Ming Tai Chemical Industry Science Co., Ltd, model: 207), stir;
(3) take 800g Al powder, 30g Zn powder, 20g Sn powder and 25g Cu powder, under agitation, slowly add in container;
(4) take 1g SiO 2, add in container, and stir;
(5) taking 0.5g polyvinyl alcohol (is purchased from Qingdao An Mao International Trading Company Ltd, Z-200) adds in container, stir, treat that liquid is uniform and stable phase, obtain oiliness titanium ingot high-temperature oxidation resistant coating A1.
The solid content of measuring oiliness titanium ingot high-temperature oxidation resistant coating A1 is that 89%, pH value is 8.3.
By oiliness titanium ingot high-temperature oxidation resistant coating for A1 automatization spray gun (be purchased from Tianjin Tuo Bao Science and Technology Ltd., model: 006_1589, following examples and comparative example with) be sprayed at titanium ingot surface, the thickness of the photopolymer layer that the amount of spraying forms after oiliness titanium ingot high-temperature oxidation resistant coating is solidified is 0.3mm, place at normal temperatures and pressures spontaneous curing after 5min, then titanium ingot is sent into annealing furnace, thermostatically heating 8h at 1000 ℃, then be rolled, after rolling, Fig. 1 is shown in by the photo of titanium ingot surface, and the Hardness Distribution of titanium ingot surface is shown in Fig. 4.
Embodiment 2
The present embodiment is for illustrating the production method of oiliness titanium ingot high-temperature oxidation resistant coating of the present invention and titanium ingot.
(1) normal temperature and pressure (25 ℃, 0.1MPa) under, take 54g oiliness epoxy resin (solid content 40 % by weight) and be placed in container;
(2) add 2.6g epoxy propane butyl ether (to be purchased from Changzhou Ming Tai Chemical Industry Science Co., Ltd, model: 501), stir;
(3) take 800g Al powder, 16g Zn powder, 16g Sn powder and 16g Cu powder, under agitation, slowly add in container;
(4) take 1.7g SiO 2, add in container, and stir;
(5) taking 0.68g Polyvinylpyrolidone (PVP) (is purchased from Guangzhou Ba Tai Chemical Co., Ltd., PVPK90) adds in container, stir, treat that liquid is uniform and stable phase, obtain oiliness titanium ingot high-temperature oxidation resistant coating A2.
The solid content of measuring oiliness titanium ingot high-temperature oxidation resistant coating A2 is that 87%, pH value is 7.7.
Use automatization spray gun spraying in titanium ingot surface oiliness titanium ingot high-temperature oxidation resistant coating A2, the thickness of the photopolymer layer that the amount of spraying forms after oiliness titanium ingot high-temperature oxidation resistant coating is solidified is 0.2mm, place at normal temperatures and pressures spontaneous curing after 5min, then titanium ingot is sent into annealing furnace, thermostatically heating 4h at 900 ℃, then be rolled, same Fig. 1 of the photo of titanium ingot surface after rolling, the Hardness Distribution of titanium ingot surface is shown in Fig. 4.
Embodiment 3
The present embodiment is for illustrating the production method of oiliness titanium ingot high-temperature oxidation resistant coating of the present invention and titanium ingot.
(1) normal temperature and pressure (25 ℃, 0.1MPa) under, take 141g oiliness epoxy resin (solid content 60 % by weight) and be placed in container;
(2) add 6.8g ethylene glycol diglycidylether (to be purchased from Changzhou Ming Tai Chemical Industry Science Co., Ltd, model: 669), stir;
(3) take 767g Al powder, 30g Zn powder, 30g Sn powder and 23g Cu powder, under agitation, slowly add in container;
(4) take 2.55g SiO 2, add in container, and stir;
(5) taking 0.85g polyoxyethylene (is purchased from and attacks green gram of novel material science and technology (Shanghai) Co., Ltd., PEO-5) add in container, stir, treat that liquid is uniform and stable phase, obtain oiliness titanium ingot high-temperature oxidation resistant coating A3.
The solid content of measuring oiliness titanium ingot high-temperature oxidation resistant coating A3 is that 85%, pH value is 9.0.
Use automatization spray gun spraying in titanium ingot surface oiliness titanium ingot high-temperature oxidation resistant coating A3, the thickness of the photopolymer layer that the amount of spraying forms after oiliness titanium ingot high-temperature oxidation resistant coating is solidified is 0.4mm, place at normal temperatures and pressures spontaneous curing after 5min, then titanium ingot is sent into annealing furnace, thermostatically heating 6h at 800 ℃, then be rolled, same Fig. 1 of the photo of titanium ingot surface after rolling, the Hardness Distribution of titanium ingot surface is shown in Fig. 4.
Embodiment 4
The present embodiment is for illustrating the production method of oiliness titanium ingot high-temperature oxidation resistant coating of the present invention and titanium ingot.
According to the method for embodiment 1, prepare oiliness titanium ingot high-temperature oxidation resistant coating and carry out the production of titanium ingot, different, the consumption of Al powder is 848g, and the consumption of Zn powder is 9g, and the consumption of Sn powder is 9g, and the consumption of Cu powder is 9g.Obtain oiliness titanium ingot high-temperature oxidation resistant coating A4, the solid content of measuring oiliness titanium ingot high-temperature oxidation resistant coating A4 is that 86%, pH value is 7.5.Same Fig. 1 of the photo of titanium ingot surface after rolling, the Hardness Distribution of titanium ingot surface is shown in Fig. 4.
Embodiment 5
The present embodiment is for illustrating the production method of oiliness titanium ingot high-temperature oxidation resistant coating of the present invention and titanium ingot.
According to the method for embodiment 1, prepare oiliness titanium ingot high-temperature oxidation resistant coating and carry out the production of titanium ingot, different, the consumption of Al powder is 674g, and the consumption of Zn powder is 67g, and the consumption of Sn powder is 67g, and the consumption of Cu powder is 67g.Obtain oiliness titanium ingot high-temperature oxidation resistant coating A5, the solid content of measuring oiliness titanium ingot high-temperature oxidation resistant coating A5 is that 90%, pH value is 9.5.Same Fig. 1 of the photo of titanium ingot surface after rolling, the Hardness Distribution of titanium ingot surface is shown in Fig. 4.
Embodiment 6
The present embodiment is for illustrating the production method of oiliness titanium ingot high-temperature oxidation resistant coating of the present invention and titanium ingot.
According to the method for embodiment 1, prepare oiliness titanium ingot high-temperature oxidation resistant coating and carry out the production of titanium ingot, different is, oiliness epoxy resin is replaced with to polyurethane paint and (be purchased from Guangzhou Di Fukale foreign trade company limited, PK-336), and by polypropylene glycol diglycidyl ether replace with urethane thinner (being purchased from Wuhan chemical).Obtain oiliness titanium ingot high-temperature oxidation resistant coating A6, the solid content of measuring oiliness titanium ingot high-temperature oxidation resistant coating A6 is that 88%, pH value is 9.1.Same Fig. 1 of the photo of titanium ingot surface after rolling, the Hardness Distribution of titanium ingot surface is shown in Fig. 4.
Comparative example 1
According to the method for embodiment 1, prepare oiliness titanium ingot high-temperature oxidation resistant coating and carry out the production of titanium ingot, different is, by the Al powder of the weight such as Zn powder, Sn powder and Cu powder replace with, obtain oiliness titanium ingot high-temperature oxidation resistant coating D1, the solid content of measuring oiliness titanium ingot high-temperature oxidation resistant coating D1 is that 89%, pH value is 8.5.After rolling, Fig. 2 is shown in by the photo of titanium ingot surface, and the Hardness Distribution of titanium ingot surface is shown in Fig. 4.
Comparative example 2
Titanium ingot surface does not spray oiliness titanium ingot high-temperature oxidation resistant coating, directly sends into annealing furnace, and at 1000 ℃, thermostatically heating 8h, is then rolled, and after rolling, Fig. 3 is shown in by the photo of titanium ingot surface, and the Hardness Distribution of titanium ingot surface is shown in Fig. 4.
Fig. 1, Fig. 2, Fig. 3 are compared and can be found out, spray oiliness titanium ingot high-temperature oxidation resistant coating of the present invention, after rolling, titanium ingot surface is smooth, flawless; The agent of spraying oxidation protection is the oiliness titanium ingot high-temperature oxidation resistant coating of Al powder, and after rolling, crackle appears in titanium ingot surface; Titanium ingot surface does not spray oiliness titanium ingot high-temperature oxidation resistant coating and directly carries out anneal, and after rolling, titanium ingot surface occurs compared with deep torn grain, and even part comes off.
The normal consistency Hv of titanium ingot is 120 left and right, if form dissolved oxygen layer in annealing process, can make the hardness of titanium ingot surface increase.As can be seen from Figure 4, apply oiliness titanium ingot high-temperature oxidation resistant coating of the present invention, can make titanium ingot after rolling at case depth during at 1mm at the most, can make hardness Hv reach 120 left and right, illustrate and adopt oiliness titanium ingot high-temperature oxidation resistant coating of the present invention, can make the thickness of the dissolved oxygen layer that titanium ingot forms in annealing process be at most 1mm; And the oxidation protection agent that adopts comparative example 1 is the oiliness titanium ingot high-temperature oxidation resistant coating of Al powder, case depth just makes hardness Hv reach 120 left and right when 2.5mm, illustrates that the thickness of the dissolved oxygen layer forming is 2.5mm; Comparative example 2, titanium ingot surface does not apply oiliness titanium ingot high-temperature oxidation resistant coating, directly carries out anneal, just makes hardness Hv reach 120 left and right when case depth is 6mm, illustrate and do not apply oiliness titanium ingot high-temperature oxidation resistant coating, titanium ingot will form the dissolved oxygen layer of about 6mm in annealing process.Visible, apply oiliness titanium ingot high-temperature oxidation resistant coating of the present invention, can greatly reduce the formation of dissolved oxygen layer.
Embodiment 1 is compared and can be found out with embodiment 4 and embodiment 5 respectively; in the oxidation protection agent used of oiliness titanium ingot high-temperature oxidation resistant coating, the weight ratio of Al powder, Zn powder, Sn powder and Cu powder is 1:0.02-0.04:0.02-0.04:0.02-0.04, can further reduce the formation of dissolved oxygen layer.Embodiment 1 and embodiment 6 are compared and can be found out, oiliness titanium ingot high-temperature oxidation resistant coating oiliness membrane-forming agent used adopts oiliness epoxy resin, can further reduce the formation of dissolved oxygen layer.
Oiliness titanium ingot high-temperature oxidation resistant coating of the present invention, can guarantee titanium ingot not oxidized cracking in constant temperature 8h surface under 1000 ℃ of high temperature, and can greatly reduce the formation of dissolved oxygen layer, can effectively reduce production costs, and improves lumber recovery and the production efficiency of titanium material; In coating, do not contain the harmful element limiting in RoHS quality, meanwhile, this oiliness titanium ingot high-temperature oxidation resistant coating does not have toxic substance volatilization in air, does not affect the environmental protection effect of construction environment etc.; Preparation technology is simple, on-the-spot preparation in the time of can using, and the preparation time is short, simple possible, also can prepare after production, at room temperature store, coating is stablized shelf-stability and can be reached more than 6 months, there will be precipitation, demixing phenomenon, still, during use, shaking up or re-start stirring can use; Can adopt the multiple coating methods such as pneumatic spraying, vacuum spraying, brushing, easy to use.The production method of titanium ingot of the present invention has good economic benefit and social benefit, in titanium plate and titanium pipe production industry, has comparatively wide popularizing application prospect.
Below describe by reference to the accompanying drawings the preferred embodiment of the present invention in detail; but; the present invention is not limited to the detail in above-mentioned embodiment; within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characterictic described in above-mentioned embodiment, in reconcilable situation, can combine by any suitable mode, for fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible array modes.
In addition, between various embodiment of the present invention, also can carry out arbitrary combination, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.

Claims (10)

1. an oiliness titanium ingot high-temperature oxidation resistant coating, is characterized in that, after described oiliness titanium ingot high-temperature oxidation resistant coating is mixed by a kind of raw mixture, obtains, and described raw mixture contains oxidation protection agent and oiliness membrane-forming agent; Described oxidation protection agent contains Al powder, Zn powder, Sn powder and Cu powder, and the weight ratio of Al powder, Zn powder, Sn powder and Cu powder is 1:0.01-0.1:0.01-0.1:0.01-0.1.
2. oiliness titanium ingot high-temperature oxidation resistant coating according to claim 1, wherein, the weight ratio of Al powder, Zn powder, Sn powder and Cu powder is 1:0.02-0.04:0.02-0.04:0.02-0.04.
3. oiliness titanium ingot high-temperature oxidation resistant coating according to claim 1 and 2, wherein, with respect to the described oxidation protection agent of 1 weight part, in solid, the consumption of described oiliness membrane-forming agent is 0.025-0.1 weight part.
4. oiliness titanium ingot high-temperature oxidation resistant coating according to claim 1 and 2, wherein, described oiliness membrane-forming agent is at least one in oiliness epoxy resin, polyurethane paint, acrylic latex coating and alkyd paint.
5. oiliness titanium ingot high-temperature oxidation resistant coating according to claim 1 and 2, wherein, described raw mixture also contains one or more in solidifying agent, dispersion agent and thinner.
6. oiliness titanium ingot high-temperature oxidation resistant coating according to claim 5; wherein; described raw mixture contains solidifying agent, dispersion agent and thinner; described oxidation protection agent with respect to 1 weight part; the consumption of described solidifying agent is 0.001-0.003 weight part; the consumption of described dispersion agent is 0.0005-0.001 weight part, and the consumption of described thinner is 0.003-0.008 weight part.
7. the application of the oiliness titanium ingot high-temperature oxidation resistant coating described in any one in titanium ingot is produced in claim 1-6.
8. the production method of a titanium ingot, it is characterized in that, described method is included in titanium ingot and carries out before anneal, surface-coated oiliness titanium ingot high-temperature oxidation resistant coating at titanium ingot, it is characterized in that, described oiliness titanium ingot high-temperature oxidation resistant coating is the oiliness titanium ingot high-temperature oxidation resistant coating described in any one in claim 1-6.
9. method according to claim 8, wherein, the mode of coating comprises pneumatic spraying, vacuum spraying, brushing.
10. method according to claim 8, wherein, the thickness of the photopolymer layer that the amount that described oiliness titanium ingot high-temperature oxidation resistant coating applies forms after described oiliness titanium ingot high-temperature oxidation resistant coating is solidified is 0.2-0.4mm.
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CN101360796A (en) * 2005-12-12 2009-02-04 纳米X有限公司 Coating material for protecting metals, especially steel, from corrosion and/or scaling, method for coating metals and metal element
JP5353105B2 (en) * 2008-07-31 2013-11-27 新日鐵住金株式会社 Surface treatment liquid for heat treatment steel and method for producing heat treatment steel
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