CN1209484C - Hard ceramic coating of polynary oxide and its prepn and application - Google Patents
Hard ceramic coating of polynary oxide and its prepn and application Download PDFInfo
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- CN1209484C CN1209484C CNB031359388A CN03135938A CN1209484C CN 1209484 C CN1209484 C CN 1209484C CN B031359388 A CNB031359388 A CN B031359388A CN 03135938 A CN03135938 A CN 03135938A CN 1209484 C CN1209484 C CN 1209484C
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- 238000005524 ceramic coating Methods 0.000 title claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 68
- 238000000576 coating method Methods 0.000 claims abstract description 68
- 239000000843 powder Substances 0.000 claims abstract description 31
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000005260 corrosion Methods 0.000 claims abstract description 18
- 230000007797 corrosion Effects 0.000 claims abstract description 17
- 238000007749 high velocity oxygen fuel spraying Methods 0.000 claims abstract description 15
- 238000005299 abrasion Methods 0.000 claims abstract description 12
- 239000011521 glass Substances 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- 230000007704 transition Effects 0.000 claims abstract description 8
- LNSPFAOULBTYBI-UHFFFAOYSA-N [O].C#C Chemical group [O].C#C LNSPFAOULBTYBI-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011247 coating layer Substances 0.000 claims description 22
- 238000002844 melting Methods 0.000 claims description 18
- 230000008018 melting Effects 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 12
- 239000010410 layer Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 6
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 5
- 230000005496 eutectics Effects 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 238000005204 segregation Methods 0.000 claims description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 2
- 239000011253 protective coating Substances 0.000 claims description 2
- 238000005476 soldering Methods 0.000 claims description 2
- 238000004381 surface treatment Methods 0.000 claims 1
- 239000007921 spray Substances 0.000 abstract description 16
- 238000003466 welding Methods 0.000 abstract description 8
- 229910000831 Steel Inorganic materials 0.000 abstract description 5
- 239000010959 steel Substances 0.000 abstract description 5
- 230000009471 action Effects 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 4
- 238000003889 chemical engineering Methods 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 4
- 229910052593 corundum Inorganic materials 0.000 abstract 3
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 3
- 229910011255 B2O3 Inorganic materials 0.000 abstract 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 230000004927 fusion Effects 0.000 abstract 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 description 26
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 239000010935 stainless steel Substances 0.000 description 12
- 229910001220 stainless steel Inorganic materials 0.000 description 12
- 238000007789 sealing Methods 0.000 description 10
- 229910000975 Carbon steel Inorganic materials 0.000 description 9
- 239000010962 carbon steel Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 239000002367 phosphate rock Substances 0.000 description 7
- 239000000523 sample Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 5
- 239000010953 base metal Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 230000003628 erosive effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000008676 import Effects 0.000 description 4
- 238000007750 plasma spraying Methods 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000009183 running Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 241000408529 Libra Species 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000006399 behavior Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910000989 Alclad Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000008485 antagonism Effects 0.000 description 1
- 230000002929 anti-fatigue Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- QFXZANXYUCUTQH-UHFFFAOYSA-N ethynol Chemical group OC#C QFXZANXYUCUTQH-UHFFFAOYSA-N 0.000 description 1
- -1 ferrous metals Chemical class 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000011499 joint compound Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- MPNNOLHYOHFJKL-UHFFFAOYSA-N peroxyphosphoric acid Chemical compound OOP(O)(O)=O MPNNOLHYOHFJKL-UHFFFAOYSA-N 0.000 description 1
- 239000002686 phosphate fertilizer Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Images
Abstract
The present invention relates to a multi-element oxide hard surface ceramic coating and a preparing method and applications thereof, which belongs to the technical field of composite materials. The multi-element oxide hard surface ceramic coating comprises Al2O3, TiO2, B2O3, MgO and glass powder, the ratio of the Al2O3 to the TiO2 to the B2O3 to the MgO is =50 to 60: 10 to 20: 5 to 8: 3 to 5, and the glass powder occupies by the balance. The preparing method comprises processing steps of spray welding formation of a bottom coating, a transition coating and a final coating and plasma or HVOF fire scanning fusion; after parent steel is ground by a coarse wheel, a nickel aluminium-coated bottom coating which is 0.10 mu m in thickness is spray-welded by oxygen acetylene flames; a nickel Al2O3 coated transition layer which is 0.15mm in thickness is spray-welded by plasma flames or HVOF; finally, the final coating which is composed of seven oxides is spray-welded by plasma or the HVOF, and the thickness of the final coating is 0.35 nm to 0.45mm. The hard surface ceramic coating has strong combined action of corrosion resistance and abrasion resistance. After the hard surface ceramic coating is applied to chemical engineering or acid and alkali chemical engineering equipment, the properties of corrosion resistance and abrasion resistance of the equipment can be enhanced by three to ten times, and the service life of the equipment can be extended by three to ten times.
Description
Technical field:
The present invention relates to a kind of multivariant oxide hard ceramic coating and preparation method thereof and application, belong to technical field of composite materials,
Background technology:
In modern industry and technology, the antagonism burn into resistance to wears urgent day by day with the equal excellent material demand of high temperature resistant property.For example in phosphorus chemistry industry, mix the blade that changes into stirring rake, carry the impeller of chemical centrifugal pump of phosphorous chemical industry intermediates and the pipe of convey materials to lead, all suffering the corrosion of the vitriol oil and the wearing and tearing of ground phosphate rock simultaneously.Corrosion and wearing and tearing promote mutually, have quickened the failure procedure of member, add higher working medium temperature, make the corrosion and the further aggravation of wearing and tearing of material.Though used the high-quality stainless steel at present (as 316L, 317L) or the carbon steel line with rubber, or carbon steel is coated with the anti-rotten wear-resistant material of anti-corrosive paints as above-mentioned chemical process, but effect is still undesirable, because line with rubber is under 80 ℃ medium temperature, non-stop run just can local unsticking be flaked about two months, even if import line with rubber equipment, non-stop run 4～5 months is just badly damaged, needs to change.The wear-resistant coating of anti-corruption commonly used is diabase flour, and this type coating is not firm because of combining with base material, and self is without sintering, so 25～30 days just badly damaged need of non-stop run renew part.In production processes such as system sulfuric acid, chemical fertilizer, petrochemical complex, also there is similar corrosive wear combined action problem.
In metal material field, it is lower to be difficult to develop cost, the anti-equal desirable material of rotten abrasion resistance.The metal or alloy that erosion resistance is more excellent, usually abrasion resistance poor (as titanium material and 316L or 317L stainless steel etc.); And the metal or alloy that hardness is higher, resistance to abrasion is more excellent, usually anticorrosive attribute energy relatively poor (as Wimet or Steel Bond Hard Alloy etc.).The bulk ceramics material of most oxide compounds or nitrogen carbide is anticorrosive and resistance to wears the excellent material of all holding concurrently, but the fragility and the anti-fatigue performance of bulk ceramics material are poor, counter stress is concentrated and strong grade of susceptibility of crackle is its fatal weakness, makes pottery still can not be widely used as the physical construction material so far.Yet by pottery and the multiple material of metal synthetic metal matrix stiff dough pottery, it but is the anti-rotten wear-resistant novel material of a class ideal high-performance, it has kept the obdurability of metallic substance and advantage such as the processing that easily is shaped, the anti-rotten resistance to abrasion that has also the kept pottery excellent characteristics of holding concurrently, this class material and goods thereof develop into an important branch of matrix material just gradually.Particularly aluminum oxide stiff dough pottery is answered material, and not only cost is lower for it, and has the anti-rotten abrasion resistance of ideal.
Produce the aluminum oxide hard-surface coating and can use the PCVD method, sol-gel processing and plasma spraying method.But PCVD method and sol-gel processing synthetic Al
2O
3Hardstanding is thin thickness (the former thick about 3～6 μ m, the latter only is 0.5～1.0 μ m) not only, and with the bonding force of base material a little less than, the author's test shows, at the running of ore pulp formula solid-liquid medium high speed, the Al of PVD system
2O
3Coating, only about 10 hours coating just major part come off.Therefore, for the member that in the blending agent of strong acid and high density ore in sand form, turns round, adopt plasma spraying (weldering) method more reasonable.Produce Al with plasma spraying method
2O
3Hard-surface coating, existing more both at home and abroad research report
[1-5], but these researchs all have a common ground, promptly only just produce Al with spraying method
2O
3Hard-surface coating
[7], and the resistance to abrasion of research coating, and the 30% realization metallurgical binding of only having an appointment between plasma spraying coating and the steel of base metal, and also have 12～15% porositys in the coating
[6,7]Therefore such coating is firm inadequately with combining of steel of base metal, if be applied in the phosphorous chemical industry production machinery, this type coating not only can not the withstand long term exposure rock phosphate sand the high speed wearing and tearing, and with rock phosphate sand blended strong acid (80% vitriol oil), also can pass coating porosity corrosion removal mother metal, coating is separated with mother metal.
Reference
[1] Yang Yuanzheng, Liu Zhengyi, Zhuan Yuzhi. " plasma spraying Al
2O
3+ 13%TiO
2The tissue of ceramic coating and wear resistance thereof " [J]. functional materials, 2000,31 (4); 390～392
[2]Yang?Yuanzheng，Liu?zhengyi，Zhuang?Yuzhi.“Influences?of?different?coating?designs?on?joint?strengthin?plasma?sprayed?Al
2O
3-TiO
2?coating”[J].Surf.and?Coat.Technol，1997，(89)：97～101
[3] Ren Jingri, metal and stone three. " Al
2O
3-40%TiO
2And Cr
2O
3The friction and wear characteristic of plasma sprayed coating " [J], tribology journal, 2000,20 (1)
[4]Yan?Dianran，He?Jining，Li?XiangZhi，et?al.“An?investigation?iof?the?corrosion?behavior?of?Al
2O
3ceramic?coating?in?dilute?HCl?solution”[J].Surf.and?Coat?Technol，2001，(141)：1～6
[5]Tanaka?Y，Fukumoto?M.：“Investigation?of?dominating?factors?on?flattening?behavior?of?plasma?sprayedceramic?particles”[J].Surf?and?Coat?Techol，1999，(120，121)：124～130
[6] Li Xiuyan, Pan Junde: " preparation of metal matrix ceramic composite coating and application " [J]. external metal heat treatmet, 2000,21 (5)
[7] Li Changjiu, big gloomy bright, awns Tian Jiming: " plasma spraying Al
2O
3Bonded research between particle in the coating " [J].XI AN JIAOTONG UNIVERSITY Subject Index, 1994,28 (1): 5
[8]Leivo.E.M.et?al：“wear?and?corrosion?properties?of?plasma?sprayed?Al
2O
3?and?Cr
2O
3?coatings?sealedby?Al(PO
4)”“Journal?of?Thermal?spray?Technology”，1997.6(2)
Summary of the invention:
The objective of the invention is to overcome the deficiency of prior art, can make the coating more than 95% all realize metallurgical binding and provide a kind of, and the porosity that makes coating is from 12～15% multivariant oxide hard ceramic coating and production method and the application that drop to below 3% with steel of base metal.
For realizing purpose of the present invention, specifically adopt following scheme:
1, multivariant oxide hard ceramic coating.Its component is: Al
2O
3, TiO
2, B
2O
3:, MgO and mainly by SiO
2, Na
2The glass powder that O and CaO form; The weight percent of each component is: Al
2O
3: TiO
2: B
2O
3: MgO: glass powder=50-60: 10-20: 5～8: 3-5: surplus.
2, the preparation method of multivariant oxide hard ceramic coating is made of surfacing prime coat, transition layer, final coating, plasma or HVOF flame scanning melting step.Wherein:
Prime coat is: elder generation thoroughly polishes with coarse wheel with mother metal, makes mother metal expose unsalted surface, and uneven on the surface microscopic, has been covered with " groove " or " pit hole " of microcosmic.Make prime coat with the thick Al contained Ni end of 0.1mm～0.15mm on the oxygen acetylene flame jet soldering then;
Transition layer is: make transition layer with plasma flame or the thick nickel-coated alumina powder of HVOF surfacing 0.15～0.20mm on prime coat;
Above-mentioned nickel-coated alumina powder is a commodity purchased, Al wherein
2O
3Content (weight) is: 20-40%.
Final coating is: with plasma flame or the thick described multinary oxide coating layer of claim 1 of HVOF surfacing 0.35～0.45mm; The batching of multinary oxide coating layer is mixed mutually with form of powder, and through the ball mill grinding batch mixing, to eliminate the component segregation between each powder, the batch mixing granularity after the grinding is between 150 to 230 negative orders.
And then the multivariant oxide powder spraying of final coating carries out plasma or HVOF flame scanning melting to coating after finishing, every line width 15mm of scanning melting, and the top temperature of coating reaches 1150-1200 ℃ during scanning melting.Under said temperature, the eutectic composition in the coating fully melts, and makes coating finish liquid phase sintering.
Multivariant oxide hard ceramic coating of the present invention is as the protective coating of accepting corrosion and abrasion member in phosphorous chemical industry or the soda acid chemical industry equipment simultaneously.
3, the microstructure and property of coating
(1) microhardness of coating: microhardness of coating fluctuates between Hv519～604, and its mean value is Hv554.
(2) porosity of coating: use buoyancy method to measure the porosity of coating, its result is a non-scanned fused spray-on coating, and its porosity is 13.21～14.62%, and the process scanning melting is finished the coating of liquid phase sintering, and its porosity is 3.98～4.60.The coating that the plasma flame scanning melting is crossed is handled through aluminum phosphate slurry dipping sealing of hole again, and then porosity can drop to below 0.5%, carries out the data that sealing of hole is handled about aluminum phosphate slurry Dipping, can consult document
[8]
(3) erosion resistance of coating: the mobile corrosion test of the material of participating in the experiment is at the H of 80% concentration
2SO
4Carry out in the solution, 80 ℃ of solution temperatures, four kinds of materials of participating in the experiment are installed on the stirring rake simultaneously, rotating speed rotation with 36 rev/mins, after 168 hours mobile corrosion, test out the unit time and the unit surface weightlessness of each sample with the analysis Libra, the gained result is as shown in Figure 1.From Fig. 1 result can, after the multinary oxide coating layer process plasma flame scanning melting, the corrodibility of its anti-strong acid is stronger 3.62 times than 18-8 stainless steel, stronger 1.51 times than the 316L stainless steel of German import, if above-mentioned multinary oxide coating layer is handled through aluminum phosphate slurry dipping sealing of hole again, then erosion resistance improves 1.58 times again.
(4) anti-corrosion anti-abrasion of coating decreases performance: four kinds of materials same as described above are put in and turn round in the blending agent of being made up of the sulfuric acid of 80% concentration and (60) order ground phosphate rock that (liquid-solid ratio is 6: 4; Temperature is 80 ℃ of runnings), rotating speed is 120 rev/mins, continuous operation was weighed on the analysis Libra after 96 hours, measured the unit time unit surface weightlessness of each sample, gained result such as Fig. 2.As can be seen from Figure 2, through the multinary oxide coating layer of plasma scanning melting, its anticorrosive polishing machine is stainless 7.46 times of 18-8, for Germany produces stainless 4.08 times of 316L.Under the such corrosion and the symphyogenetic operating mode of wearing and tearing, through the multinary oxide coating layer that peroxophosphoric acid slurry sealing of hole is handled, its anti-rotten abrasion resistance is little without the sample difference that sealing of hole is handled with a process scanning melting.
(5) tissue of coating and micro-area composition analysis:
Fig. 3 has provided at the 50 times amplification displaing micro pictures of steel surface with the multinary oxide coating layer of plasma spray method acquisition.A, B, each section of C are respectively base material, coating and atmospheric layer among the figure.From figure as can be known, the thickness of multinary oxide coating layer is about 0.5mm.Fig. 4 has provided the electronic probe micro-area composition distribution plan of multinary oxide coating layer section, and (a) is the micro-enlarged image of secondary electron of coating section among the figure.The micro-area composition that figure (b), (c), (d), (e) are respectively oxygen, aluminium, titanium, silicon distributes, and elements such as magnesium, boron, sodium, calcium are then more weak and unlisted because of analytical signal.As can be seen from Figure 4, Al
2O
3In whole coating, all have more uniformly to distribute, and TiO
2And SiO
2Then mainly be distributed in the outermost top layer, this shows in scanning melting liquid phase sintering process, the TiO in the powder
2May form the multiple joint compound of new more complicated eutectic with the silicate in the glass powder.
The present invention compared with prior art, has coating and the mother metal bonding force is strong, surfacing, the coating porosity degree is low, anticorrosive strong with wearing and tearing combined action ability, after using on some key equipment of phosphorous chemical industry machinery and chemical engineering industries such as relieving haperacidity and chemical fertilizer, the wear-resistant non-stop run life-span of the anti-corruption of equipment is all generally improved 3 to 10 times.
Description of drawings:
Fig. 1 is that four kinds of materials are in 80% concentration sulfuric acid and 80 ℃ of temperature current downflow corrosive experimental results.
Ordinate is the corrosion weight loss of unit time and unit surface among the figure, and abscissa is represented material category, and wherein 1 is the 18-8 stainless steel; 2 is the 316L stainless steel of German import; 3 is the multinary oxide coating layer of straight carbon steel mother metal plasma spray this patent; 4 is straight carbon steel mother metal plasma spray this patent coating, and through aluminum phosphate slurry sealing of hole.
Fig. 2 is four kinds of materials continuous operation experimental results after 96 hours in 80 ℃ of temperature and 80% concentration sulfuric acid and ground phosphate rock blending agent (liquid-solid ratio is 6: 4).
Ordinate is the weightlessness of unit time and unit surface sample among the figure, and abscissa is a material category, and 1 is the 18-8 stainless steel among the figure; 2 is German import 316L stainless steel; 3 is that the straight carbon steel mother metal is through plasma spray this patent multinary oxide coating layer; 4 be the straight carbon steel mother metal through the plasma spray multinary oxide coating layer again through aluminum phosphate slurry sealing of hole.
Fig. 3 is the 50 times enlarged section photos of base metal of carbon steel through plasma spray this patent multinary oxide coating layer.
A, B, C are respectively mother metal, coating and atmospheric layer for three sections among the figure.
Fig. 4 is the electronic probe element microdistribution figure of base metal of carbon steel through plasma spray this patent multinary oxide coating layer.
(a) is the SEM secondary electron image of coating among the figure; (b) be the distribution of oxygen element in coating; (c) be the distribution of aluminium element in coating; (d) be the distribution of titanium elements in coating; (e) be the distribution of element silicon (glass powder is brought into) in coating.
Embodiment:
1, is applied on the mixedization stirring rake of phosphorous chemical industry production unit
When not using the technology of the present invention:
The blade of this stirring rake running and extruding in 80 ℃ the vitriol oil and the composite oar material of ground phosphate rock mix the slaking raw material, therefore blade is accepted the strong acid corrosion and the ore in sand form strong wear of higher temperatures, serve as a contrast rubber on the present domestic employing carbon steel blade or be coated with brightness record rock dust dual mode and make anti-rotten erosion resistant coating, line with rubber generally can only just lose efficacy with about 3 months and need renew part, and the surface is coated with brightness record rock dust and can only uses 25-30 days.
After using the technology of the present invention:
Mixedization stirrer paddle (be of a size of on 400 * 120 * 12mm) base materials, this patent multinary oxide coating layer with thick 0.7mm on the plasma flame surfacing uses under same operating mode, but more than the non-stop run to 10 month (minimum also reaches 10 months).The inter coat that uses in this practical example is for containing Al
2O
320% nickel package alumina composite powder, final coated component is Al
2O
3: TiO
2: B
2O
3: MgO: glass powder=50: 20: 8: 5: 17, use the nickel alclad (purchase of powder market) about the thick 0.1mm of spray welding of oxyacetylene flame in the surfacing process, use the thick nickel-coated alumina powder of plasma flame surfacing 0.15mm (purchase of powder market) then, the last final multinary oxide coating layer of using plasma flame surfacing mentioned component again, the about 0.45mm of thickness, coating is not handled just can be welded in blade in the stirring rake rotating shaft through sealing of hole and is used.Welding is coated with magic glue protective layer with the excellent boron stainless steel of erosion resistance on the welding bead, the axle of stirring rake is that level is installed, so less corrosion and the wearing and tearing of accepting material on the welding bead, and an end opposite with welding bead then is the most serious preferential damaged location of corrosive wear.
2, the multiple spray tower that is used for the roasting sulphide ores workshop of non-ferrous metals smelting works
When not using the technology of the present invention:
The chi that sprays tower again is about 1000 * φ 600 (cylindrical), is made by the 316L stainless steel, spray again tower accept 200 ℃ ± SO
2Dusty gas washes away, effect when accepting the wearing and tearing of high temperature corrosion and grit.The 316L stainless steel just damaged about one month, added lead lining in the 316L stainless steel again, then can use just leakage about 60 days (accept ash-laden gas wash away the position preferentially damage leakage).
After using the technology of the present invention:
After using the multinary oxide coating layer of plasma flame surfacing this patent instead, non-stop run after 1 year still in use.The multinary oxide coating layer that surfacing sprays the tower inner face again is Al
2O
3: TiO
2: B
2O
3: MgO: glass powder=60: 15: 5: 3: 17, thickness was 0.35.The same example of the composition of prime coat, thickness and preparation method, middle layer are the thick nickel-coated alumina powder coating of 0.15mm, nickel bag Al
2O
3The Al of powder
2O
3Content (weight) is 30% (powder is bought back by market), and the method for spray-welding in middle layer is the flame passes spray fuse method.The thickness of whole hardstanding is about 0.60mm.After the surfacing preparation was finished, coating does not add the sealing of hole processing just can enter use.
3, the ore deposit oar transport pipe (internal diameter φ about 600) that is used for production of phosphate fertilizer
When not using the technology of the present invention:
Ore deposit oar transport pipe is because of the corrosion of accepting strong acid and ground phosphate rock blending agent and wearing and tearing combined action, can only non-stop run 40-50 days just leakage need repair or renew part.
After using the technology of the present invention:
Ore deposit oar transport pipe non-stop run not leakage as yet (also in use) in a year.Prime coat composition, thickness and the method for spray-welding thereof taked in the present embodiment are with embodiment 1.The thickness of inter coat is about 0.15mm, and the composition of inter coat is for containing 40%Al
2O
3Nickel bag Al
2O
3Powder (market purchase), the preparation method of inter coat is HVOF spray fuse method (High Velocity Oxygen fuel), final multinary oxide coating layer powder composition is: Al
2O
3: TiO
2: B
2O
3: MgO: glass powder=55: 18: 7: 4: 16.The preparation method of final coating is the HVOF spray fuse method, and its thickness is 0.4mm, and the thickness of whole hardstanding is about 0.65mm, and after surfacing was finished, coating did not add sealing of hole and just can come into operation.
More than among three embodiment, the batching of multinary oxide coating layer is mixed mutually with form of powder, and through the ball mill grinding batch mixing, to eliminate the component segregation between each powder, the batch mixing granularity after the grinding is between 150 to 230 negative orders.
More than plasma or the HVOF flame scanning melting step of three embodiment be, when plasma or HVOF flame scanning melting, every line width 15mm of scanning melting, the top temperature of coating reaches 1150-1200 ℃ during scanning melting, under said temperature, eutectic composition in the coating fully melts, and makes coating finish liquid phase sintering.
Claims (3)
1, multivariant oxide hard ceramic coating is characterized in that the component of hard ceramic coating is: Al
2O
3, TiO
2, B
2O
3, MgO and mainly by SiO
2, Na
2The glass powder that O and CaO form; The weight percent of each component is: Al
2O
3: TiO
2: B
2O
3: MgO: glass powder=50-60: 10-20: 5～8: 3-5: surplus.
2, the workpiece preparation method who contains the multivariant oxide hard ceramic coating of claim 1 is characterized in that present method is made of surfacing prime coat, transition layer, final coating and plasma or HVOF flame scanning melting step; Wherein:
2.1 prime coat is to use the thick Al contained Ni end of oxygen acetylene flame jet soldering 0.1～0.15mm on the workpiece after the surface treatment;
2.2 transition layer is for to make transition layer with plasma flame or the thick nickel-coated alumina powder of HVOF surfacing 0.15～0.20mm on prime coat;
2.3 final coating is with plasma flame or the thick described multinary oxide coating layer of claim 1 of HVOF surfacing 0.35～0.45mm; The batching of multinary oxide coating layer is mixed mutually with form of powder, and through the ball mill grinding batch mixing, to eliminate the component segregation between each powder, the batch mixing granularity after the grinding is between 150 to 230 orders;
2.4 when plasma or HVOF flame scanning melting, every line width 15mm of scanning melting, the top temperature of coating reaches 1150-1200 ℃ during scanning melting, and under said temperature, the eutectic composition in the coating fully melts, and makes coating finish liquid phase sintering.
3, the described multivariant oxide hard ceramic coating of claim 1 is as the protective coating of accepting corrosion and abrasion member in phosphorous chemical industry or the soda acid chemical industry equipment simultaneously.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031359388A CN1209484C (en) | 2003-09-25 | 2003-09-25 | Hard ceramic coating of polynary oxide and its prepn and application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031359388A CN1209484C (en) | 2003-09-25 | 2003-09-25 | Hard ceramic coating of polynary oxide and its prepn and application |
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|---|---|
| CN1526846A CN1526846A (en) | 2004-09-08 |
| CN1209484C true CN1209484C (en) | 2005-07-06 |
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|---|---|---|---|
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| CN1313635C (en) * | 2004-11-02 | 2007-05-02 | 江苏大学 | Flame spray welding process for titanium alloy surface wearable coating |
| CN100351420C (en) * | 2005-11-17 | 2007-11-28 | 广州有色金属研究院 | Method for supersonic flame spraying crystallizer brass plate |
| CN103484811B (en) * | 2013-10-09 | 2015-09-02 | 河北工业大学 | The preparation method of metal oxide based inorganic composite materials coating |
| CN111424228A (en) * | 2020-04-01 | 2020-07-17 | 合肥科德电力表面技术有限公司 | Flame spraying construction method for micro-melting ceramic coating |
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