CN103938185A - Preparation method for inner hole coating of tubular part - Google Patents
Preparation method for inner hole coating of tubular part Download PDFInfo
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- CN103938185A CN103938185A CN201310020151.9A CN201310020151A CN103938185A CN 103938185 A CN103938185 A CN 103938185A CN 201310020151 A CN201310020151 A CN 201310020151A CN 103938185 A CN103938185 A CN 103938185A
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- tubular member
- preparation
- vacuum
- power supply
- bias power
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- 238000000576 coating method Methods 0.000 title claims abstract description 70
- 239000011248 coating agent Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 37
- 229910003074 TiCl4 Inorganic materials 0.000 claims abstract description 31
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007789 gas Substances 0.000 claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 230000008021 deposition Effects 0.000 claims abstract description 17
- 229910052786 argon Inorganic materials 0.000 claims abstract description 15
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims abstract description 4
- 238000005086 pumping Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 23
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000010935 stainless steel Substances 0.000 claims description 16
- 229910001220 stainless steel Inorganic materials 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 229910015844 BCl3 Inorganic materials 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 5
- 230000006698 induction Effects 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- KRQUFUKTQHISJB-YYADALCUSA-N 2-[(E)-N-[2-(4-chlorophenoxy)propoxy]-C-propylcarbonimidoyl]-3-hydroxy-5-(thian-3-yl)cyclohex-2-en-1-one Chemical compound CCC\C(=N/OCC(C)OC1=CC=C(Cl)C=C1)C1=C(O)CC(CC1=O)C1CCCSC1 KRQUFUKTQHISJB-YYADALCUSA-N 0.000 claims description 3
- 239000003599 detergent Substances 0.000 claims description 3
- 238000010422 painting Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims description 2
- 239000012495 reaction gas Substances 0.000 claims 5
- 238000009413 insulation Methods 0.000 claims 1
- 238000000151 deposition Methods 0.000 abstract description 19
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 abstract description 10
- 229910033181 TiB2 Inorganic materials 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 238000009792 diffusion process Methods 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000005229 chemical vapour deposition Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 210000000038 chest Anatomy 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000004372 laser cladding Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000005036 potential barrier Methods 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Landscapes
- Chemical Vapour Deposition (AREA)
Abstract
The invention relates to a preparation method for an inner hole coating of a tubular part. The tubular part is arranged in a coating deposition device comprising an auxiliary electrode having air conduction function, a TiCl4 liquid storage tank and a tubular part clamping jig, and then placed in a vacuum chamber for vacuum pumping, argon (Ar) is introduced, a bias power supply is turned on for glow cleaning of the tubular part, reaction gases of H2, TiCl4, N2 and BCl13 are introduced, and the introduction of N2 and BCl13 is alternately switched so as to achieve the deposition of TiN and TiB2. By means of the tubular part coating deposition device, the problems of sheath layer overlapping, low ion energy and poor coating bonding force caused by limited space are solved, the problems of rapid depletion, low density and axial non-uniformity of plasma entered due to external diffusion are solved, the density and the uniformity of the plasma in a tube are improved, and high-efficiency and axial uniform deposition are achieved.
Description
Technical field
The present invention relates to a kind of preparation method of tubular member internal coating, particularly a kind of preparation method of the wear-resisting compound coating of dark bore surface of elongated tubular product part.
Background technology
The abrasion-resistant coating material and the coating technology thereof that under the hot conditions of various countries' primary study, use in recent years, comprise Ta, Mo, W, Re, Nb, the refractory metals such as Hf and alloy thereof and TiB2, the ceramic body coatings such as ZrO2, coating structure is to multi-layer multi future development, its technology of preparing comprises coating produced by laser cladding, plasma flame applies, the spraying of high speed oxygen-fuel heat, wire explosion spraying and plasma strengthen vapour deposition etc., wherein vapour deposition is owing to realizing infusibility, fire-retardant, the reliable deposition of anti-ablator, and used in a large number, vapour deposition is a kind of by physical processes such as chemical reaction or thermal evaporations, produce the gas atom of deposition material, molecule, ion or aggregate form the method for solid rete at matrix, be divided into physical vapor deposition (PVD) and chemical vapour deposition (CVD), CVD technology has around plurality of advantages such as plating property are good, but depositing temperature is higher, greatly limit its range of application.
The plasma reinforced chemical vapour deposition technology (PECVD) of plasma body being introduced to the formation of CVD technology has greatly activated reaction system, can make pyroreaction realize low temperature synthetic, reach object prepared by coating low temperature, this is because plasma temperature and energy density are high, can make reactant gas molecules generation ionization or activation, can reduce the potential barrier of compound decomposition or chemical combination, temperature of reaction improves speed of reaction when reduction, and plasma body can improve the bonding strength of coating and matrix to the activation of matrix surface in addition.
But, elongated tubular product part is prepared in TiB2/TiN coating procedure at PECVD, because limited space causes sheath ply, ion energy is low, and the outside plasma body diffusing into exhausts fast, energy density is low, and axially inhomogeneous, causes plasma application difficulty in the dark endoporus of slender member.
The existing preparation technology of TiB2/TiN compound coating is as higher in the preparation temperature of the methods such as coating produced by laser cladding, plasma flame coating, the spraying of high speed oxygen-fuel heat, wire explosion spraying, very easily cause matrix oxidation, the high temperature in coating preparation process also can affect the mechanical property of thin-walled tubular member etc. simultaneously.And plasma reinforced chemical vapour deposition technology can make reactant gas molecules generation ionization or activation, can reduce the potential barrier of compound decomposition or chemical combination, realize low temperature depositing, but elongated tubular product part is prepared in TiB2/TiN coating procedure at PECVD, striking difficulty, is difficult to the homogeneity that ensures prepared by coating.
Summary of the invention
The object of the present invention is to provide a kind of method of preparing the wear-resistant coating using under hot conditions at elongated tubular product inner bore of part surface uniform.Propose the preparation method of the wear-resisting compound coating of elongated tubular product part of the present invention, solved an inwall striking difficult problem in the elongated tubular product part PECVD process of big L/D ratio, realized the even preparation of the wear-resisting compound coating using under elongated tubular product part inwall hot conditions.
The object of the invention is to realize by such technical scheme, a kind of preparation method of tubular member internal coating, is characterized in that: make vacuum tightness reach 1.0 × 10
-2pa～2.5 × 10
-2pa, keeps vacuum to maintain, and passes into argon Ar, and vacuum tightness is down to 6 × 10
-2pa ~ 8 × 10
-2pa, maintains this vacuum tightness, opens grid bias power supply aura cleaning workpiece 5 ~ 10min, and heating, vacuum chambers temp to 300～450 DEG C, close argon gas and grid bias power supply simultaneously; Logical nitrogen N 2, hydrogen H2, titanium tetrachloride TiCl4 reactant gases, vacuum tightness is down to after 1000 ~ 1600Pa, maintain this vacuum tightness, open grid bias power supply, deposited coatings TiN 30min～120min, close grid bias power supply, stop passing into nitrogen N 2, hydrogen H2, titanium tetrachloride TiCl4 reactant gases, pass into argon Ar detergent line 5min～10min; Pass into again boron trichloride BCl3, hydrogen H2, titanium tetrachloride TiCl4 reactant gases, open grid bias power supply, deposited coatings TiB
23h～5h.
The gas flow of described argon Ar, hydrogen H2, boron trichloride BCl3, nitrogen N 2 is respectively Ar:80～100 sccm, H2:1400～1600 sccm, BCl3:450～520 sccm, N2:200～300 sccm.
Described direct current pulse power source bias voltage: 700～1000V, electric current: 1～1.2A, dutycycle: 40% ~ 60%, frequency: 40KHz.
Carrying out needing to do following preparation work before deposited coatings: the tubular member of coating to be prepared is carried out to pre-treatment, make tubular member endoporus roughness reach Ra0.8 ~ Ra1.6 by grinding, adopt successively organic solvent to clean as alcohol and acetone, and cleaning 10min～15min at organic solvent in as acetone by ultrasonic wave, tubular member takes out latter 60 DEG C dries 1h.
Tubular member is installed and in vacuum chamber, is vacuumized, first described vacuum chamber vacuumizes uses mechanical pump forvacuum, opens diffusion pump to vacuum chamber pumping high vacuum when vacuum tightness is better than 5 ~ 10Pa, and vacuum tightness is better than 6 × 10
-2pa ~ 8 × 10
-2when Pa, heat tubular members and be incubated 20min by 300～450 DEG C of described vacuum chamber temperature, continuing to be evacuated to vacuum tightness and reach 1 × 10
-2pa ~ 2 × 10
-2pa.
The present invention is by closing diffusion pump, and reservation mechanical pump carries out vacuum and maintains.
After deposited coatings finishes, stop passing into TiCl
4, BCl
3and H
2, close more than grid bias power supply Ar cleans air delivering pipeline 15min～20min, degree for the treatment of be down to 140 DEG C～below 150 DEG C, stop mechanical pump, take out tubular member.
The painting of tubular member of the present invention is deposited upon in deposited coatings device and completes, described deposited coatings device includes supporting electrode, TiCl4 container for storing liquid and the clamping fixture of gas port, described clamping fixture is fixed on the base central position of vacuum chamber, described container for storing liquid is connected with vacuum chamber by stainless steel tube, described supporting electrode be arranged on the axial line of described clamping fixture and with described DC pulse grid bias power supply anodic bonding;
Wherein said clamping fixture comprise held up by three support bars, tube wall has the tubular bracket of four fixed orificess, between described support bar and described tubular bracket, by the ceramic body connection of insulating, described tubular bracket is connected with the negative electrode of DC pulse grid bias power supply.
For reactant gases being delivered directly to tubular member inside, make it have air delivery function concurrently, described supporting electrode is tubulose, comprise that termination is the transition conduit of flat cone mouth shape and the upper induction pipe being fixedly connected with it, described gas port arranges in the tube wall end of upper induction pipe, and this gas port is more than at least two.
For TiCl4 gas is provided, described TiCl4 container for storing liquid comprises stainless steel tank body, sealing-ring, upper cover, thermopair, heating zone, pressure vacuum meter and hand stop valve, on the worktable that has powerful gas barrier, TiCl4 is poured in stainless steel tank body, stainless steel tank body oral area cover sealing-ring, on sealing-ring, put lid, upper cover and stainless steel tank body are fastenedly connected, ensure that TiCl4 can not overflow, the pipe connecting of upper cover welded top is connected with hand stop valve, after hand stop valve, connect pressure vacuum meter, two pressure vacuum meter the other ends connect respectively N2 output terminal and vacuum chamber input terminus by pipe connecting, heating zone evenly twines in stainless steel tank body and gas transmission connecting pipe surface, the end of thermocouple temperature sensitive is put between heating zone and stainless steel tank body, measure in real time the Heating temperature of heating zone to tank body, the other end of heating zone and thermopair is all connected on temperature control system, ensure TiCl4 tank body to carry out thermostatically heating, described pipe connecting adopts stainless steel tube effect all good.
Open described heating zone temperature to 70 DEG C～85 DEG C, gaseous tension 1300 Pa～8000 Pa in stainless steel tank body in described vacuum chamber temperature in heating.
In order to ensure that TiCl4 can not overflow, upper cover and stainless steel tank body screw fastening.
In order to assist TiCl4 building-up reactions under safe and reliable Working environment to form settled layer, described TiCl4 container for storing liquid is also connected with hydrogen H2 container for storing liquid, boron trichloride BCl3 container for storing liquid and nitrogen N 2 container for storing liquids, described TiCl4 container for storing liquid and hydrogen H2 container for storing liquid, nitrogen N 2 container for storing liquids connect into gas channels, and described TiCl4 container for storing liquid and hydrogen H2 container for storing liquid also connect into another gas channels with boron trichloride BCl3 container for storing liquid.
For guaranteeing that TiCl4 does not block air delivering pipeline, on described TiCl4 container for storing liquid, be also parallel with argon Ar container for storing liquid, described argon Ar container for storing liquid one end is connected between hydrogen H2 container for storing liquid and nitrogen N 2 container for storing liquid air delivering pipelines, the other end is connected between described TiCl4 container for storing liquid and boron trichloride BCl3 container for storing liquid air delivering pipeline, so that starting stage and ending phase in coating deposition are rinsed air delivering pipeline, prevent that TiCl4 is residual in air delivering pipeline.
Described tubular member clamping fixture is the tubular bracket that three support bars hold up, tube wall has four fixed orificess; between support bar and tubular bracket, insulate by ceramic body; tubular bracket is connected with the negative electrode of grid bias power supply; tubular member is fastening by four fixed orificess on tubular bracket; realizing DC pulse grid bias power supply negative electrode is connected with tubular member; guarantee the realization of glow discharge; and tubular member is neither contacted with center supporting electrode; prevent short circuit; also do not contact with vacuum-chamber wall, prevent from that vacuum chamber is charged to hurt sb.'s feelings.Support bar is contained on described vacuum chamber base, and base is supported by foot pad, central opening of the seal mounting kit, and center supporting electrode is fixedly connected with DC pulse grid bias power supply anode by external member.
After checking that tubular member and center supporting electrode are contactless, close bell.
Owing to having adopted technique scheme, the present invention has advantages of as follows:
1, the present invention prepares the wear-resisting compound coating of the TiB2/TiN rhythmo structure using under a kind of hot conditions at the bore surface of tubular member, taking TiN the end of as, prepare in the above TiB2 wear-resisting functions coating, utilize the characteristics such as TiB2 high-melting-point, high rigidity to ensure workpiece long-time reliability using under hot environment.
2, the present invention is by being connected on tubular center's supporting electrode and electric potential floating by the anode of grid bias power supply, thereby glow discharge is tied to tubular member endoporus, solve limited space and cause sheath ply, ion energy is low, coating binding force is bad problem, make potential difference clamper added negative bias values on tube wall of tubular axis line and tube wall, guarantee ion fully to accelerate and arrive surface, in realizing deposition, improving bonding force; By perforate on tubular center's supporting electrode, make it have air delivery function concurrently, reactant gases is delivered directly to tubular member inside, solving the outside plasma body diffusing into exhausts fast, density is low, axially inhomogeneous problem, improves density and the homogeneity of managing interior plasma body, realizes efficient and axial uniform deposition.
3, heat by heating zone and temperature control system is realized TiCl
4gasification under assigned temperature, is monitored tank internal pressure and is regulated required TiCl by pressure vacuum meter
4flow, ensures TiCl
4do not contact the TiO that prevents forming poisonous HCl and easily stop up air delivering pipeline with atmosphere
2powder; Hand stop valve is opened in the situation that gas circuit vacuumizes or fill Ar, controls respectively and carries H
2input and gaseous state TiCl
4output, prevent TiCl
4contact with air residual in gas circuit.For guaranteeing TiCl
4do not block air delivering pipeline, the TiCl to container for storing liquid to vacuum chamber
4air delivering pipeline, not only all adopts heating zone to heat, and has manufactured specially Ar flushing pipeline, in starting stage and the ending phase of deposition, it is rinsed, and prevents TiCl
4residual in air delivering pipeline.By above measure, realize TiCl
4vacuum storage, controlled gasification and transport smoothly.
4, the inventive method can be 35 mm at inner thorax diameter, length-to-diameter ratio is 4.4 bushing pipe inside, adopt plasma reinforced chemical vapour deposition technology to realize uniform deposition, ununiformity is controlled at ± 5% in, with respect to the naked pipe that does not do coating, improved more than 2.3 times the work-ing life that cycling hot is impacted more than 2000 DEG C.
Brief description of the drawings
Fig. 1 is the microstructural SEM photo in embodiment of the present invention 1TiB2/TiN compound coating cross section;
Fig. 2 is the microstructural SEM photo of coatingsurface prepared by the embodiment of the present invention 1 to embodiment 4;
Fig. 3 is the XRD figure spectrum of the coating prepared of the embodiment of the present invention 1 to embodiment 4;
Fig. 4 is embodiment of the present invention tubular member clamping schematic diagram;
Fig. 5 is the vertical view of Fig. 4;
Fig. 6 is the structural representation of embodiment of the present invention supporting electrode;
Fig. 7 is each composition connection diagram of deposited coatings device of the present invention;
Fig. 8 is that TiCl4 container for storing liquid of the present invention respectively forms connection diagram.
Embodiment
Mode below by embodiment further illustrates the present invention, within therefore not limiting the present invention to described scope of embodiments.
Embodiment 1: a kind of preparation method of tubular member internal coating, comprises the following steps:
A. the preparation work before deposited coatings
Pre-treatment before tubular member coating: grinding, polishing tubular member endoporus to roughness reach Ra0.8 ~ Ra1.6, clean 2～3 times with alcohol and acetone successively, in acetone, clean 10min～15min by ultrasonic wave, tubular member takes out latter 60 DEG C dries 1h again.
Tubular member (referring to Fig. 4,5,6,7,8) is installed:
Be that unsettled being placed on of 35 mm, the length-to-diameter ratio tubular member 6 that is 4.4 has on the tubular bracket 12 of four screw holes with the tube wall that three support bars 11 hold up by inner thorax diameter, between support bar 11 and tubular bracket 12, connect by insulating ceramic body 14, support bar 11 is contained on the base 41 of described vacuum chamber 4, base 41 is supported by foot pad 42, base 41 center drilling mounting kits 43, center supporting electrode 2 is fixedly connected with DC pulse grid bias power supply 5 anodes by external member 43, and described tubular bracket 12 is connected with the negative electrode of DC pulse grid bias power supply 5.
After checking that tubular member 6 and center supporting electrode 2 are contactless, close bell.
Vacuumize: first use mechanical pump 7 forvacuum, open diffusion pump 8 to vacuum chamber pumping high vacuum when vacuum tightness is 5Pa, vacuum tightness is 8 × 10
-2when Pa, heating tubular member to 450 DEG C is also incubated 20min, and the heating zone of simultaneously opening TiCl4 container for storing liquid is heated to 85 DEG C, continues that vacuum chamber is evacuated to vacuum tightness and reaches 2 × 10
-2pa.
B. depositing Ti B2/TiN coating (referring to Fig. 6,7):
Keep vacuum to maintain, pass into argon Ar, open DC pulse grid bias power supply simultaneously, make bias voltage: 1000V, electric current: 1.2A, dutycycle: 60%, frequency: 40KHz; Aura cleans tubular member 5min～10min; Then pass into reactant gases hydrogen H2, TiCl4, N
2, deposited coatings TiN 0.5h,, stop passing into reactant gases hydrogen H2, TiCl4, N
2,, close grid bias power supply, pass into argon Ar detergent line 5min～10min; Pass into again boron trichloride BCl3, hydrogen H2, titanium tetrachloride TiCl4 reactant gases, open grid bias power supply, deposited coatings TiB
23h; When deposition, make vacuum keep at 1000Pa.
Described argon Ar, hydrogen H2, BCl3,, the gas flow of N2 is respectively Ar:100 sccm, H2:1600 sccm, BCl3:520 sccm, N2:300 sccm.
C. deposited coatings finishes
Stop passing into TiCl4, BCl3 and H2, close grid bias power supply Ar and clean air delivering pipeline and be greater than 15min～20min, treat that temperature is down to 140 DEG C～150 DEG C, stop mechanical pump, take out tubular member.
Embodiment 2～4 is except the listed parameter of table 1, and other parameter and step are with embodiment 1.
Table 1
Table 2 is 35 mm for what obtain through embodiment 1～4 preparation method at inner thorax diameter, the coat-thickness shock-resistance of the tubular member inside deposition TiB2/TiN coating that length-to-diameter ratio is 4.4 and the test result of hardness.Carry out coating sample preparation and measure according to the regulation of national standard, the over-all properties of measured coating is as shown in table 2.
Table 2
| Test item | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Detection method |
| Coat-thickness um | 15.3 | 14.5 | 14.7 | 15.5 | Eddy current thickness measuring |
| Resistance to sudden heating | (1500～1600) DEG C instantaneous flame impingement does not ftracture for 810 times | (1500～1600) DEG C instantaneous flame impingement does not ftracture for 750 times | (1500～1600) DEG C instantaneous flame impingement does not ftracture for 790 times | (1500～1600) DEG C instantaneous flame impingement does not ftracture for 800 times | ? |
| Hardness HV 0.1 | 3102 | 3062 | 3050 | 3045 | GB/T6739 |
From table 2 data analysis, the TiB2/TiN coating obtaining by embodiment 1～4, its coat-thickness is even, shock-resistance is strong, hardness is high.
Fig. 1 is the TiB obtaining by embodiment 1 preparation method
2/ TiN is coated with the microstructural SEM photo of layer cross section; Find out TiB from photo
2clear and legible with TiN coating, coating and coating intersection interpenetrate; Fig. 2 is the microstructural SEM photo of coatingsurface prepared by embodiment 1 to embodiment 4, Fig. 3 is the X-ray diffraction analysis XRD figure spectrum of the coating prepared of embodiment 1 to embodiment 4, finds out that from Fig. 2 and Fig. 3 coatingsurface density and the homogeneity prepared through embodiment 1 to embodiment 4 are better.
Claims (9)
1. a preparation method for tubular member internal coating, is characterized in that: vacuumize and keep vacuum tightness 1.0 × 10
-2pa～2.0 × 10
-2pa, passes into argon Ar, adjusts vacuum tightness and maintains 6 × 10
-2pa ~ 8 × 10
-2pa, opens grid bias power supply aura cleaning workpiece 5 min ~ 10min, and heating, vacuum chambers temp to 300～450 DEG C, close argon gas and grid bias power supply simultaneously; Pass into a group reaction gas, adjust vacuum tightness and maintain 1000 ~ 1600Pa, open grid bias power supply, deposited coatings TiN 30min～120min, closes grid bias power supply, stops passing into a described group reaction gas, passes into argon Ar detergent line 5min～10min; Pass into again another group reaction gas, open grid bias power supply, deposited coatings TiB
2150 min～300 min;
A wherein said group reaction gas is nitrogen N 2, hydrogen H2, titanium tetrachloride TiCl4, and another group reaction gas is boron trichloride BCl3, hydrogen H2, titanium tetrachloride TiCl4;
The gas flow of described argon Ar, hydrogen H2, boron trichloride BCl3, nitrogen N 2 is respectively Ar:80～100 sccm, H2:1400～1600 sccm, BCl3:450～520 sccm, N2:200～300 sccm;
Described direct current pulse power source bias voltage: 700～1000V, electric current: 1～1.2A, dutycycle: 40% ~ 60%, frequency: 40KHz.
2. the preparation method of tubular member internal coating as claimed in claim 1, is characterized in that: described in vacuumize first by forvacuum, while making vacuum tightness reach 5 ~ 10Pa, then pumping high vacuum, making vacuum tightness is 6 × 10
-2pa ~ 8 × 10
-2pa, heats tubular member by temperature described in vacuum chamber and is incubated 20min, continues to be evacuated to vacuum tightness and reaches 1 × 10
-2pa ~ 2 × 10
-2pa.
3. the preparation method of tubular member internal coating as claimed in claim 1 or 2, it is characterized in that: the painting of described tubular member is deposited upon in deposited coatings device and completes, described deposited coatings device includes clamping fixture (1), supporting electrode (2) and the TiCl4 container for storing liquid (3) of band gas port (23), described clamping fixture (1) is fixed on base (41) central position of vacuum chamber (4), described TiCl4 container for storing liquid (3) is connected with vacuum chamber (4) by pipe connecting, described supporting electrode (2) be arranged on the axial line of described clamping fixture (1) and with described DC pulse grid bias power supply (5) anodic bonding,
Wherein said clamping fixture (1) comprise held up by three support bars (11), tube wall has the tubular bracket (12) of four fixed orificess (13), between described support bar (11) and described tubular bracket (12), connect by ceramic body (14) insulation, described tubular bracket (12) is connected with the negative electrode of DC pulse grid bias power supply (5).
4. the preparation method of tubular member internal coating as claimed in claim 3, it is characterized in that: described supporting electrode (2) is tubulose, comprise that termination is the transition conduit (21) of flat cone mouth shape and the upper induction pipe (22) being fixedly connected with it, described gas port (23) at least arranges more than two the tube wall end of induction pipe (22) on described.
5. the preparation method of tubular member internal coating as claimed in claim 3, is characterized in that: described TiCl4 container for storing liquid (3) is made up of stainless steel tank body (31), sealing-ring, upper cover (32), thermopair, heating zone, pressure vacuum meter (33) and hand stop valve (34), described upper cover (32) is fastened on the stainless steel tank body (31) that oral area is equipped with sealing-ring, described hand stop valve (34) is connected with upper cover (32), described hand stop valve (34) is Bonding pressure vacuum meter (33) below, pressure vacuum meter described in this (33) the other end accesses described vacuum chamber (4), described heating zone evenly twines in stainless steel tank body (31) with outside the stainless steel tube being connected with vacuum chamber (4), the end of described thermocouple temperature sensitive is placed between heating zone and stainless steel tank body (31), the output terminal of described heating zone and thermopair is connected on thermostatically heating instrument.
6. the preparation method of tubular member internal coating as claimed in claim 5, is characterized in that: open described heating zone temperature to 70 DEG C～85 DEG C, gaseous tension 1300 Pa～8000 Pa in stainless steel tank body in described vacuum chamber temperature in heating.
7. the preparation method of tubular member internal coating as claimed in claim 1 or 2, is characterized in that: before deposited coatings, the endoporus roughness of tubular member is Ra0.8 ~ Ra1.6.
8. the preparation method of tubular member internal coating as claimed in claim 7, is characterized in that: after adopting organic solvent to clean, then in organic solvent, clean 10min～15min by ultrasonic wave, tubular member takes out latter 60 DEG C dries 1h.
9. the preparation method of tubular member internal coating as claimed in claim 1 or 2, is characterized in that: after deposition finishes, stop passing into TiCl
4, BCl
3and H
2, after regulating impulse voltage and dutycycle are 0, close grid bias power supply, pass into argon Ar and clean air delivering pipeline 15min～20min, treat temperature be down to 120 DEG C～below 150 DEG C, stop vacuum and maintain.
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| CN104264126A (en) * | 2014-09-17 | 2015-01-07 | 四川大学 | Long-range micro-channel inner wall TiO2 coating chemical vapor deposition device and coating method |
| CN105668998A (en) * | 2016-01-11 | 2016-06-15 | 苏州工业园区纳米产业技术研究院有限公司 | Equipment improvement for P5000 machine BPSG process |
| CN113136562A (en) * | 2021-04-19 | 2021-07-20 | 东北大学 | High-hardness TiN protective coating capable of being coated on deep-hole part and preparation method thereof |
| CN113681939A (en) * | 2021-07-30 | 2021-11-23 | 江西昌河航空工业有限公司 | Equivalent substitution method for composite material thermocouple |
| CN114059040A (en) * | 2021-11-24 | 2022-02-18 | 四川大学 | Deposition method and device for TiN coating on inner surface of pipe network |
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| CN102154672A (en) * | 2008-04-09 | 2011-08-17 | 北京航空航天大学 | Non-metallic film with high heat conduction efficiency and anti-fouling capability and preparation method thereof |
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| CN104264126A (en) * | 2014-09-17 | 2015-01-07 | 四川大学 | Long-range micro-channel inner wall TiO2 coating chemical vapor deposition device and coating method |
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| CN113136562A (en) * | 2021-04-19 | 2021-07-20 | 东北大学 | High-hardness TiN protective coating capable of being coated on deep-hole part and preparation method thereof |
| CN113681939A (en) * | 2021-07-30 | 2021-11-23 | 江西昌河航空工业有限公司 | Equivalent substitution method for composite material thermocouple |
| CN114059040A (en) * | 2021-11-24 | 2022-02-18 | 四川大学 | Deposition method and device for TiN coating on inner surface of pipe network |
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|---|---|
| CN103938185B (en) | 2016-09-14 |
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