CN104553138A - Metal-carbon coating composite material and preparation method and application thereof - Google Patents
Metal-carbon coating composite material and preparation method and application thereof Download PDFInfo
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- CN104553138A CN104553138A CN201310499847.4A CN201310499847A CN104553138A CN 104553138 A CN104553138 A CN 104553138A CN 201310499847 A CN201310499847 A CN 201310499847A CN 104553138 A CN104553138 A CN 104553138A
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- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 claims description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
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- Paints Or Removers (AREA)
Abstract
The invention discloses a metal-carbon coating composite material, a preparation method of the metal-carbon coating composite material, the obtained metal-carbon coating composite material prepared by adopting the method and the application of the metal-carbon coating composite material as a high-temperature corrosion resistant material. The composite material comprises a metallic matrix and a carbon coating adhered to at least one surface of the metallic matrix. The metal-carbon coating composite material provided by the invention can have a good high-temperature corrosion resistant property, and have a longer service life at the temperature of 600-900 DEG C under corrosive environment. A good bonding property is generated between the metallic matrix and the carbon coating in the formed composite material.
Description
Technical field
The present invention relates to a kind of metal-carbon coating composite material and its preparation method and application, particularly, relate to a kind of metal-carbon coating composite material, metal-carbon coating composite material preparation method and the metal-carbon coating composite material prepared thereof, and a kind of metal-carbon coating composite material is as the application of high-temperature corrosion resistance material.
Background technology
In petroleum chemical industry, all there is demand widely to corrosion-inhibiting coating and coating in all kinds of metallic conduit, storage tank or reactor, and anticorrosive paint occupies the ratio more than 1/4th at the whole Coating Market of China.A lot of equipment that chemical industry uses, as the wellbore tubular of petroleum industry, the heat exchanger of chemical industry and reaction vessel etc., mostly need higher serviceability temperature, and the chemical mediator of contact is of a great variety, therefore has higher requirement to the resistance to acids and bases of coating under high temperature.The chlorination breakdown stove of such as rare earth ore concentrate, needs directly to pass into chlorine under the high temperature of a few Baidu, and according to the difference generating different chloride boiling point, the chloride of obtained rare earth metal, conventional equipment due to seriously corroded, often needs to change under chlorine condition.When and for example oil-field thick-oil well recovers the oil now, need to stretch out perfusion high-temperature steam to bottom, therefore gas injecting pipe needs good high temperature salt tolerant, sulfur tolerance.
The kind of current corrosion-inhibiting coating is very various, and raw material relates to all multiple types such as polyolefin, polyurethane, epoxy, phenolic aldehyde, pitch, Fu Xin, organosilicon, but these coating materials exist respective defect mostly.Most of organic coating duty temperature is all lower, and maximum operating temperature is generally lower than 200 DEG C.And although the coating of mineral-type such as rich zinc class coating has good weather-proof antiseptic power, poor at the antiseptic property corroded contact.The coating of minority high-temperature anticorrosion or metal material, as enamel coating, ceramic coating, nickel-base alloy etc., complex process, cost is high, causes cost to remain high.
CN1058606A discloses a kind of high-temp epoxy carbobitumen priming, finish paint and method for making thereof.This invention bituminous epoxy paint is divided into priming paint and finish paint with the use of, remove coal tar pitch in primers, add zinc oxide and prevent high-temperature-coked, and add wollastonite in powder, the coating obtained is continuing to come off without hollowing, nothing in the high temperature of 400 DEG C.The method needs to add zinc oxide in primers and prevents high-temperature-coked, and is difficult to apply at higher temperatures.
JP60195014A discloses on a kind of base material and applies specific phenyl ring base polymer, by by heat resolve coating under the condition of coating under vacuo and more than 700 DEG C, carbonization coating is covered on base material.Have electric conductivity and very high hardness under this coating high-temp, base material wherein used can be silicon, carbon, aluminium and carborundum etc.
JP56163054A discloses a kind of emulsion (epoxy or phenolic aldehyde) of thermosetting resin and heat proof material as zirconium or cobalt mixing, or add the water-soluble binder of other kind as silica gel, silicate etc., carry out the coating of burning and carbonization obtains for casting model again, under the erosion of metal melt, have the service life of long period.
JP3249173A discloses a kind of by Ti or Zr and phenolic aldehyde, furans or pitch mixing carbonization, is used as the crucible of evaporation Al, at high temperature effectively can extends the service life of crucible.
CN87106528A discloses the manufacture method of a kind of metal and glass-sealed mould and mould, is characterised in that the uniformly painting layer protective layer of mould, then through overcuring and carbonization treatment.The method applies one deck asphaltic resin in silicon nitride surface, then through overcuring and carbonization treatment, the mould obtained can be at high temperature not bonding with glass, can be used in the sealing-in of metal and glass in electronics industry.
As can be seen here, also lack at present and make metal material matrix under the high temperature conditions, as more than 450 DEG C can the method for acid resistance or alkaline corrosion.
Summary of the invention
The object of the invention is the defect in order to overcome prior art, a kind of metal-carbon coating composite material and its preparation method and application is provided.
To achieve these goals, the invention provides a kind of metal-carbon coating composite material, it is characterized in that, described composite contains metallic matrix and is attached to the carbon coating at least one surface of this metallic matrix.
Present invention also offers a kind of preparation method of metal-carbon coating composite material, the method comprises: (1) softening bituminous composition is coated on metallic matrix at least one on the surface, and be cooled to 20-40 DEG C; (2) cure treatment, solidification process and carbonization treatment are carried out successively to the bituminous composition on metal base surface; Wherein, described bituminous composition contains pitch and optional additive.
Present invention also offers the application of metal-carbon coating composite material provided by the invention as high-temperature corrosion resistance material.
Metal-carbon coating composite material provided by the invention can have the performance of good high-temperature corrosion resistance, can have longer service life under 600-900 DEG C of high temperature and corrosive atmosphere.And there is good binding ability between metallic matrix and carbon coating in the composite formed.Such as, in embodiment 1, through cure treatment, solidification process and carbonization treatment, the stainless steel substrates F1 of the band carbon coating of acquisition can have good antistrip performance and high-temperature corrosion resistance performance.Do not have cure treatment in comparative example 1, antistrip performance and the high-temperature corrosion resistance performance of the D1 obtained are poor.
Other features and advantages of the present invention are described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for description, is used from explanation the present invention, but is not construed as limiting the invention with detailed description of the invention one below.In the accompanying drawings:
Fig. 1 is the photo of the preparation process of metal-carbon coating composite material, and wherein, (a) is the outward appearance photo of the bituminous coating of coating in embodiment 1; (b) on the obtained D1 of comparative example 1 the outward appearance photo of carbon coating in test case 1 after high-temperature corrosion resistance test; C () is the outward appearance photo of carbon coating in test case 1 after high-temperature corrosion resistance test on the obtained F1 of embodiment 1;
Fig. 2 is the FT-IR comparison diagram before and after carburization, and after showing carbonization in figure, the original C-H of pitch is flexible disappears with flexural vibrations absworption peak, and after proving carbonization, coating main component is carbon;
Fig. 3 is SEM-EDS (ESEM-X-ray energy spectrometer) photo of the coating on the stainless steel substrates F1 of band carbon coating;
Fig. 4 is the carbon content SEM-EDS analysis of spectra at a point place of the coating be with on the stainless steel substrates F1 of carbon coating;
Fig. 5 is the carbon content SEM-EDS analysis of spectra at the b point place of the coating be with on the stainless steel substrates F1 of carbon coating.
Detailed description of the invention
Below the specific embodiment of the present invention is described in detail.Should be understood that, detailed description of the invention described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of metal-carbon coating composite material, it is characterized in that, described composite contains metallic matrix and is attached to the carbon coating at least one surface of this metallic matrix.
According to the present invention, the described composite that general measure means analysis can be adopted to obtain is attached to composition and the content of the coating on the surface of described metallic matrix.Such as analyze with SEM-EDS, the carbon content of the carbon coating of described composite is more than 85 % by weight; In the infrared spectrum spectrogram of the carbon coating of described composite, be 2750-3000cm in wave number
-1there is not the peak of C-H stretching vibration in place and wave number is 1300-1475cm
-1there is not the peak of C-H flexural vibrations.Can prove that the coating formed is carbon coating thus, the composite obtained is metal-carbon coating composite material.
According to the present invention, formed in metal surface carbon coating method can there is no particular limitation, under preferable case, described carbon coating can for by pitch successively through cure treatment, solidification process and carbonization treatment and obtained material.
According to the present invention, the material of described metallic matrix can be various known metal and/or alloy, and under preferable case, the material of described metallic matrix is at least one in stainless steel, carbon steel, titanium steel and cast iron.
Present invention also offers a kind of preparation method of metal-carbon coating composite material, the method comprises: (1) softening bituminous composition is coated on metallic matrix at least one on the surface, and be cooled to 20-40 DEG C; (2) cure treatment, solidification process and carbonization treatment are carried out successively to the bituminous composition on metal base surface; Wherein, described bituminous composition contains pitch and optional additive.
According to the present invention, under preferable case, in described bituminous composition, with the gross weight of described bituminous composition for benchmark, the content of described pitch is 50-100 % by weight, and the content of described additive is 0-50 % by weight.
According to the present invention, described pitch can specifically not limit, and under preferable case, the softening point of described pitch is 60-200 DEG C, and phosphorus content is more than 80%; Preferably, described pitch is at least one in asphalt, coal tar asphalt, petroleum residual oil pitch, PVC baking pitch processed and mesophase spherule modulation pitch.
According to the present invention, described additive can be the additive that this area routine uses, and may be used for the mechanical property to material, corrosion resistance and cohesive and carries out reinforcement.Under preferable case, described additive is at least one in phenolic resins, epoxy resin, short carbon fiber, carbon powder, diatomite and white carbon.Preferably, in described bituminous composition, with the gross weight of described bituminous composition for benchmark, the content of described pitch is 70-90 % by weight, and the content of described additive is 10-30 % by weight.
In the present invention, step is coated on the surface of metallic matrix by after bituminous composition thermoplastic in (1), naturally cools afterwards.
According to the present invention, step (2) processes the bituminous composition be coated on metal base surface, forms carbon coating to make bituminous composition at metal base surface.Cure treatment, solidification process and carbonization treatment can be carried out successively.
According to the present invention, described cure treatment can be that bituminous composition is become thermosetting from thermoplasticity, and the problem peeled off occurs with metallic matrix because of thawing at temperature-rise period medium pitch composition when can prevent from carrying out high temperature cabonization.Under preferable case, described cure treatment comprises vapor phase method and liquid phase method, and described vapor phase method carries out under oxygen-enriched atmosphere, and operating condition comprises: temperature is 20-200 DEG C, and the time is 10 minutes-5 hours; Described liquid phase method carries out in Strong oxdiative solution, operating condition comprises: temperature is 10-80 DEG C, time is 1 minute-5 hours, and described Strong oxdiative solution is preferably at least one in hydrogen peroxide, hypochlorite, bichromate, permanganate, benzoyl peroxide and hydrogen phosphide cumene.Wherein, described oxygen rich gas can be air, NO
2, SO
3with at least one in ozone gas; The concentration of described Strong oxdiative solution is 1-50 % by weight.
According to the present invention, described solidification process can be the physics and chemistry character changing bituminous composition further, increases the adhesive force with metallic matrix.Under preferable case, described solidification process comprises drying and solidification; The condition of described drying comprises: temperature is 60-120 DEG C, and the time is 4-24 hour; The condition of described solidification comprises: temperature is 120-300 DEG C, and the time is 4-24 hour.
According to the present invention, described carbonization treatment can be changed by the bituminous composition of coating to form carbon coating.Under preferable case, the condition of described carbonization treatment comprises: temperature is 600-1100 DEG C, and the time is 3-24 hour.
Present invention also offers the application of metal-carbon coating composite material provided by the invention as high-temperature corrosion resistance material.Such as, in Rare Earth Concentrate Decomposition chlorination furnace as the application of high-temperature corrosion resistance material.
Below will be described the present invention by embodiment.In following examples, coating antistrip performance reference standard GB/T/T 9286, the adhesive force rank of testing coating.Coating elevated temperature corrosion resistant records by placing in 700 DEG C of chlorine gas environments for 10 hours.SEM-EDS elementary analysis adopts home position testing method, uses Philips company XL30 ESEM SEM to measure.FT-IR analyzes and adopts powder pressing potassium bromide troche method, uses Nicolet company iN10 Fourier trasfonn infrared microscope spectrophotometer.
Embodiment 1
The present embodiment is for illustration of the preparation method of metal-carbon coating composite material of the present invention.
(1) applying coating: by 1g asphalt solids particle (Qilu Petrochemical 2# solid asphalt, softening point is 150 DEG C, phosphorus content is 82%), mix with 0.2g epoxy resin (Monmentive company EPIKOTE Resin 816), the bituminous composition be mixed to get is heated to 270 DEG C, with coating roll even application in 304 stainless steel sheet surface, naturally cools to room temperature 25 DEG C, obtain untreated bituminous coating, take a picture and observe outward appearance as shown in Fig. 1 (a).
(2) carbon coating processed: the stainless steel substrates sample of band coating is placed in baking oven, cure treatment 4 hours at 80 DEG C in air atmosphere.Take out sample postpositive in baking oven, drying 4 hours at 120 DEG C, then solidify 8 hours at 200 DEG C.The stainless steel substrates sample of the band coating be cured is placed in tube furnace, and in a nitrogen atmosphere, 800 DEG C of carbonizations 5 hours, obtain the stainless steel substrates F1 being with carbon coating.
The coating of carrying out obtaining before and after (2) carbon coating step processed is carried out FT-IR analysis, FT-IR spectrogram as shown in Figure 2, after showing carbonization in figure, the original C-H of pitch is flexible disappears with flexural vibrations absworption peak, and after proving carbonization, coating main component is carbon.Coating on F1 selected arbitrarily a, b to carry out SEM-EDS analysis at 2, as shown in Figures 4 and 5, the constituent content result that a, b 2 locates SEM-EDS analysis acquisition is as shown in table 1, and Fig. 3 is the SEM-EDS photo of the coating on F1 for spectrogram.
Table 1
In table 1, the C element content carrying out 2 places analyzed, more than 87 % by weight, illustrates that the coating formation on F1 is carbon coating.
Embodiment 2
The present embodiment is for illustration of the preparation method of metal-carbon coating composite material of the present invention.
(1) applying coating: 1g asphalt solids particle (Qilu Petrochemical 10# solid asphalt, softening point is 115 DEG C, and phosphorus content is 80%) is heated to 230 DEG C, with coating roll even application in 304 stainless steel sheet surface, naturally cools to room temperature 30 DEG C.
(2) carbon coating processed: the stainless steel substrates sample of band coating is immersed in the hydrogen peroxide solution of concentration 30 % by weight, cure treatment 4 hours at 45 DEG C.Taking-up is placed in baking oven, drying 4 hours at 110 DEG C, then solidifies 4 hours at 160 DEG C.The band coating stainless steel substrates sample be cured is placed in tube furnace, and in a nitrogen atmosphere, 700 DEG C of carbonizations 4 hours, obtain the stainless steel substrates F2 being with carbon coating.
The coating formation confirmed on F2 as embodiment 1 is carbon coating.
Embodiment 3
The present embodiment is for illustration of the preparation method of metal-carbon coating composite material of the present invention.
(1) applying coating: by 1g asphalt solids particle (Qilu Petrochemical 2# solid asphalt, softening point is 150 DEG C, phosphorus content is 82%) and the mixing of 0.3g diatomite, the bituminous composition be mixed to get is heated to 270 DEG C, with coating roll even application in carbon steel sheet surface, naturally cool to room temperature 30 DEG C.
(2) carbon coating processed: the carbon steel sample of band coating is immersed in the hydrogen peroxide solution of concentration 30 % by weight, cure treatment 4 hours at 45 DEG C.Taking-up is placed in baking oven, drying 6 hours at 90 DEG C, then solidifies 10 hours at 230 DEG C.The band coating stainless steel substrates sample be cured is placed in tube furnace, and in a nitrogen atmosphere, 700 DEG C of carbonizations 8 hours, obtain the stainless steel substrates F3 being with carbon coating.
The coating formation confirmed on F2 as embodiment 1 is carbon coating.
Comparative example 1
According to the method for embodiment 1, unlike, step does not have cure treatment in (2).
Obtain the stainless steel substrates D1 being with carbon coating.
Test case 1
Sample F 1-F3 and D1 is carried out antistrip performance test and high-temperature corrosion resistance test.The results are shown in Table 2.
Antistrip performance test adopts standard GB/T/T9286 method of testing.
High-temperature corrosion resistance test is by placing sample 10 hours in 700 DEG C of chlorine gas environments, and effects on surface corrosion condition is observed.
Table 2
| Numbering | Anti-strip | High-temperature corrosion resistance |
| F1 | 0 grade (none lattice comes off) | Intact |
| F2 | 1 grade (area that comes off is less than 2%) | Intact |
| F3 | 0 grade (none lattice comes off) | Intact |
| D1 | 4 grades (come off area about 50%) | Coating cracking, part is peeled off |
Untreated bituminous coating (bituminous coating that embodiment 1 step (1) obtains after completing) after applying, without coating cracking situation after high-temperature corrosion resistance test of the bituminous coating (coating on the D1 that comparative example 1 is obtained) of cure treatment and pitch coating (coating on the F1 that embodiment 1 the is obtained) situation after high-temperature corrosion resistance test after non-fusible, solidification and carbonization treatment, carry out photograph respectively to observe, as shown in Figure 1.
As can be seen from Fig. 1 photo, the bituminous coating after (2) carbon coating processed step process can have better resistance to elevated temperatures.As can be seen from the data result of table 2, method provided by the invention can obtain the metal-carbon coating composite material with fine high-temperature corrosion resistance performance, and has good binding ability between metallic matrix and carbon coating in the composite formed.
Claims (11)
1. a metal-carbon coating composite material, is characterized in that, described composite contains metallic matrix and is attached to the carbon coating at least one surface of this metallic matrix.
2. composite according to claim 1, wherein, analyze with SEM-EDS, the carbon content of the carbon coating of described composite is more than 85 % by weight; In the infrared spectrum spectrogram of the carbon coating of described composite, be 2750-3000cm in wave number
-1there is not the peak of C-H stretching vibration in place and wave number is 1300-1475cm
-1there is not the peak of C-H flexural vibrations in place.
3. composite according to claim 1, wherein, described carbon coating is by the pitch successively obtained material through cure treatment, solidification process and carbonization treatment.
4. composite according to claim 1, wherein, the material of described metallic matrix is at least one in stainless steel, carbon steel, titanium steel and cast iron.
5. a preparation method for metal-carbon coating composite material, the method comprises:
(1) softening bituminous composition is coated on metallic matrix at least one on the surface, and be cooled to 20-40 DEG C;
(2) cure treatment, solidification process and carbonization treatment are carried out successively to the bituminous composition on metal base surface;
Wherein, described bituminous composition contains pitch and optional additive.
6. preparation method according to claim 5, wherein, in described bituminous composition, with the gross weight of described bituminous composition for benchmark, the content of described pitch is 50-100 % by weight, and the content of described additive is 0-50 % by weight.
7. the preparation method according to claim 5 or 6, wherein, the softening point of described pitch is 60-200 DEG C, and phosphorus content is more than 80%; Preferably, described pitch is at least one in asphalt, coal tar asphalt, petroleum residual oil pitch, PVC baking pitch processed and mesophase spherule modulation pitch.
8. preparation method according to claim 5, wherein, described additive is at least one in phenolic resins, epoxy resin, short carbon fiber, carbon powder, diatomite and white carbon.
9. preparation method according to claim 5, wherein, described cure treatment comprises vapor phase method and liquid phase method, and described vapor phase method carries out under oxygen-enriched atmosphere, and operating condition comprises: temperature is 20-200 DEG C, and the time is 10 minutes-5 hours; Described liquid phase method carries out in Strong oxdiative solution, operating condition comprises: temperature is 10-80 DEG C, time is 1 minute-5 hours, and described Strong oxdiative solution is preferably at least one in hydrogen peroxide, hypochlorite, bichromate, permanganate, benzoyl peroxide and hydrogen phosphide cumene.
10. preparation method according to claim 5, wherein, described solidification process comprises drying and solidification; The condition of described drying comprises: temperature is 60-120 DEG C, and the time is 4-24 hour; The condition of described solidification comprises: temperature is 120-300 DEG C, and the time is 4-24 hour; The condition of described carbonization treatment comprises: temperature is 600-1100 DEG C, and the time is 3-24 hour.
Metal-carbon coating composite material in 11. claim 1-5 described in any one is as the application of high-temperature corrosion resistance material.
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