CN102912305A - Preparation method for amorphous Al2O3 and superfine nanocrystalline-coated ZrO2 compound coating material - Google Patents
Preparation method for amorphous Al2O3 and superfine nanocrystalline-coated ZrO2 compound coating material Download PDFInfo
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Abstract
The invention discloses a preparation method for an amorphous Al2O3 and superfine nanocrystalline-coated ZrO2 compound coating material, and relates to amorphous superfine nanocrystalline-coated compound coating materials. The purpose of the invention is to provide the preparation method for the amorphous Al2O3 and superfine nanocrystalline-coated ZrO2 compound coating material; and the method has the characteristics that reactive magnetron sputtering deposition is combined with annealing treatment and the prepared material is controllable in coating degree and thickness. The preparation method comprises the steps as follows: preprocessing a substrate; conducting the reactive sputtering deposition on a thermodynamic unsteady-state ZrAlN precursor film material; and conducting the annealing treatment on the ZrAlN precursor film material. The amorphous Al2O3 and superfine nanocrystalline-coated ZrO2 compound coating material with controllable coating degree and thickness is prepared by controlling various process parameters.
Description
Technical field
The present invention relates to the nanocrystalline composite coating material of a kind of amorphous Coated, especially relate to a kind of metastable state ZrAlN precursor mould material that utilizes on the carbide matrix material surface and prepare the amorphous Al that the coating degree is controlled, thickness is controlled
2O
3The nanocrystalline ZrO of Coated
2The method of composite coating material.
Background technology
ZrO
2A kind of important structured material and functional materials ([1] S.Somiya, N.Yamamoto, H.Yanagina. ' Science and Technology of Zirconia III ', in Advances in Ceramics, American Ceramic Society, Westerville, OH, 1988, vols.24A and24B.).ZrO
2Have excellent physics, chemical property.Hardness is large; high temperature resistant; dielectric coefficient is large; the acid-alkali-corrosive-resisting performance is strong; abrasion resistance properties is excellent, usually as the cutting tool protecting materials, particularly under the hot operation condition; but also exist the large problem of fragility ([2] Journal American Ceramic Society, 70 (1987) 689).The research discovery, the most advanced and sophisticated energy absorbing mechanism of stress-induced phase transformation mechanism and tiny crack can become ZrO
2The important method that stupalith is toughness reinforcing, metastable Tetragonal ZrO
2Become important ceramic toughening material ([3] Nature, 258 (1975) 703), when tetragonal phase zirconium oxide when the monoclinic phase zirconium white occur to change in opposite directions, phase transformation can absorb the growth energy of crackle.Simultaneously phase transformation meeting produces tiny crack, be different from larger-size, because of the fracture crack that fault in material produces, these tiny cracks can absorb the energy at fracture crack tip, effectively discharge the stress concentration state of crack tip.In conjunction with above two kinds of mechanism of action, body material has been protected in growth that can the establishment fracture crack.In addition, Tetragonal Emission in Cubic ZrO
2Can be used as simultaneously the second-phase strongthener, thereby reach enhancing, toughness reinforcing purpose.Nano level ZrO
2Than block ZrO
2, its mechanics, optics, electric property all are greatly improved, and can be used as fine structure parts, optics and electricity device.In addition, nano level ZrO
2Also be the important catalyzer of a class ([4] T.Yamaguchi.Catal.Today, 20 (1994) 199).
Al
2O
3/ ZrO
2Matrix material has excellent mechanical property, resistance toheat and biological fitness, the fields ([5] JournalAmerican Ceramic Society, 92 (2009) 2751) such as fine structure parts, thermal barrier coating, biomedical material have been applied at present.At ZrO
2Introduce the second-phase Al of the non-phase of dissolving each other on the matrix
2O
3, can refinement ZrO
2Grain-size increases ZrO
2The suffered stress of crystal grain reaches and stablizes Tetragonal or Emission in Cubic ZrO under the low temperature
2Effect.Under the applied at elevated temperature condition, can stablize ZrO
2Grain-size, keep the excellent mechanical property state ([6] Acta Mater.45 (1997) 3843, [7] Acta Mater.51 (2003) 3571) of material.No matter be Tetragonal or Emission in Cubic ZrO
2, its high-temperature creep resistance is poor, but is introducing second-phase Al
2O
3After, Al
2O
3/ ZrO
2Material possesses excellent high-temperature creep resistance ([8] Acta Materialia, 48 (2000) 4691), two Al that mutually deposit
2O
3With ZrO
2Between have lower interfacial energy, work as ZrO
2Matrix is by Al
2O
3After big area coated, atom at high temperature moved and is obstructed, and so just is conducive at high temperature keep Al
2O
3/ ZrO
2The constitutional features of material, grain-size are subject to stable the time, and the improvement in creep resistance ability is also strengthened, and has greatly improved Al
2O
3/ ZrO
2The use properties of material under hot conditions, this development to industries such as aerospace engine, motor car engine, cutting tool supercoat, Metal smeltings has and important meaning.
Prepare at present Al
2O
3/ ZrO
2The method of material has mechanical milling[9] (Journal American CeramicSociety, 89 (2006) 1280), combustion technique[10] (Journal of Materials Research, 13 (1998) 156), precipitation process[11] (Ceramics International, 34 (2008) 1797), sol – gel[12] (JournalAmerican Ceramic Society, 90 (2007) 298), post doping[13] (Acta Materialia, 50 (2002) 1125).
Summary of the invention
The object of the present invention is to provide reactive magnetron sputtering to combine with anneal, the material of preparing coats a kind of amorphous Al that degree is controlled, thickness is controlled
2O
3The nanocrystalline ZrO of Coated
2The preparation method of composite coating material.
The present invention includes following steps:
1) substrate pretreated;
2) reactive sputter-deposition thermodynamics unsteady state ZrAlN precursor mould material;
3) ZrAlN precursor mould material is carried out anneal.
In step 1), described substrate pretreated can be carried out mechanical mill polished finish, ultrasonic cleaning, the processing of ion source Bombardment and cleaning successively; Described mechanical mill polished finish, can first Wimet be used 600 order diamond disks to grind 3～5min, speed of grinding plate is 300r/min, then use 1200 order diamond disks to grind 3～5min, speed of grinding plate is 300r/min, be that the diamond polishing cream of 0.5 or 1.0 μ m carries out polished finish 5～8min at polishing disk with particle diameter again, the polishing disk rotating speed is 600r/min, is polished to the surface and is the bright mirror surface state; Recycle silicon glue polishes afterwards, and the time is 8～10min; Described ion source Bombardment and cleaning is processed, and can adopt the Hall ion source that matrix is cleaned 10～15min, and environmental stress is 2.5～3.0 * 10
-2Pa, substrate temperature are 300 ℃, and the Ar airshed is 10～15sccm, bias voltage is-100～-150V, cathodic current is 25～30A, and cathode voltage is 15～20V, and anodic current is 6～8A, and anode voltage is 50～60V.
In step 2) in, described reactive sputter-deposition thermodynamics unsteady state ZrAlN precursor mould material, the cavity environment temperature can be heated to 120～150 ℃, the carbide matrix temperature is heated to 300 ℃, pass into Ar gas, flow set is regulated operating pressure to 0.8 in the cavity～1.0Pa at 40～50sccm, with ZrAl alloy target material power regulation to 100W, sputter 3～5min; Then with ZrAl alloy target material power regulation to 125W, sputter 3～5min; Again with ZrAl alloy target material power regulation to 150W, sputter 3～5min; At last with ZrAl alloy target material power regulation to 200W, sputter 3～5min.This pre-sputter process process, in order to removing the contaminating impurity such as target material surface oxide compound, activation target material surface atom is carried the highly purified while and is also improved the sputter rate of target.Pre-sputter confirms that first the cavity environment temperature is 120～150 ℃ after finishing, and the carbide matrix temperature is 300 ℃, is passing into N
2Gas, adjust flux is so that Ar gas and N
2The gas total flux is 50～60sccm, N
2The gas intrinsic standoff ratio is 20%～30%.Rotate sample table, so that Wimet is over against the ZrAl alloy target material, with the distance of target be 8～10cm, open the target plate washer, ZrAl alloy target material d.c. sputtering power is risen to 100W, rise to 150W behind 3～5min, through rising to 200W behind 3～5min, again through rising to 250W behind 3～5min, at last again through rising to 300W behind 3～5min, under this power condition, keep appropriate time, amount to sputtering sedimentation 60～90min.
In step 3), described ZrAlN precursor mould material is carried out anneal, the Wimet of plated film can be placed 700～900 ℃ of annealing furnaces, insulation 2～3h, processing atmosphere is air.Make ZrAlN precursor mould material generation oxidation, and obvious oxidation does not occur in Wimet, still can be used as body material.And in the oxidation products of ZrAlN precursor mould material, ZrO
2Be crystal form, and Al
2O
3Be non-crystalline state, obtain amorphous Al
2O
3The nanocrystalline ZrO of Coated
2Composite coating material.By processing parameter adjustment and target constituent adjustment, can prepare the amorphous Al that the coating degree is controlled, thickness is controlled
2O
3The nanocrystalline ZrO of Coated
2Composite coating material.By the composition proportion of change ZrAl alloy target material, thereby the content of Al element in the change ZrAlN precursor mould material can be realized amorphous Al
2O
3To superfine nano-crystalline ZrO
2The adjusting of coating degree; By the control anneal time, can realize amorphous Al
2O
3The nanocrystalline ZrO of Coated
2The thickness of composite coating material is regulated.
The method that the invention use reactive magnetron sputtering combines with anneal.At certain deposition pressure, temperature, N
2Under the conditions such as dividing potential drop, by changing Zr
1-xAl
xThe alloy target material composition is prepared the different Zr of composition
1-xAl
xN precursor mould material; By suitable annealing treating process, prepare the amorphous Al that the coating degree is controlled, thickness is controlled again
2O
3The nanocrystalline ZrO of Coated
2Composite coating material.When the Al of precursor mould material content during less than 25at.%, ZrO in the zone of oxidation
2Part is by amorphous Al
2O
3Coat; When the Al of precursor mould material content is higher than 25at.%, can obtain amorphous Al
2O
3The complete nanocrystalline ZrO of Coated
2Composite coating material is from the HRTEM(high resolution transmission electron microscopy) picture can find out superfine nano-crystalline ZrO
2Fully by amorphous Al
2O
3Coat.The present invention provides and prepares the amorphous Al that the coating degree is controlled, thickness is controlled by various process parameter controls
2O
3The nanocrystalline ZrO of Coated
2The novel method of composite coating material.
The present invention is different from existing method, and novelty is used the method for reactive magnetron sputtering and anneal phase structure, at first prepares ZrAlN precursor mould material, and it is being carried out anneal, finally prepares the amorphous Al that the coating degree is controlled, thickness is controlled
2O
3The nanocrystalline ZrO of Coated
2Composite coating material.
Description of drawings
Fig. 1 is the XRD(X ray diffraction before embodiment 1 anneal) spectrogram.In Fig. 1, X-coordinate be diffraction angle 2 θ/°, ordinate zou is intensity I ntensity(a.u.), 15at.% represents that the per-cent that the atomicity of Al element accounts for metallic element total atom number is 15%.
Fig. 2 is the section S EM(scanning electronic microscope after embodiment 1 anneal) figure.In Fig. 2, magnification is 15000, and scale is 1 μ m.
Fig. 3 is the XRD spectra before embodiment 2 anneal.In Fig. 3, X-coordinate be diffraction angle 2 θ/°, ordinate zou is intensity I ntensity(a.u.), 22.5at.% represents that the per-cent that the atomicity of Al element accounts for metallic element total atom number is 22.5%.
Fig. 4 is the section S EM figure after embodiment 2 anneal.In Fig. 4, magnification is 15000, and scale is 1 μ m.
Fig. 5 is the XRD spectra before embodiment 3 anneal.In Fig. 5, X-coordinate be diffraction angle 2 θ/°, ordinate zou is intensity (Intensity(a.u.)), 30at.% represents that the per-cent that the atomicity of Al element accounts for metallic element total atom number is 30%.
Fig. 6 is the section S EM figure after embodiment 3 anneal.In Fig. 6, magnification is 15000, and scale is 1 μ m.
Fig. 7 is the afterwards HRTEM figure of zone of oxidation of embodiment 1 anneal.In Fig. 7, scale is 10nm.
Fig. 8 is the afterwards HRTEM figure of zone of oxidation of embodiment 2 anneal.In Fig. 8, scale is 10nm.
Fig. 9 is the afterwards HRTEM figure of zone of oxidation of embodiment 3 anneal.In Fig. 9, scale is 10nm.
Embodiment
1, substrate pretreated
(1) mechanical mill polished finish, first Wimet is ground 3min at 600 order diamond disks, speed of grinding plate is 300r/min, then use 1200 order diamond disks to grind 3min, speed of grinding plate is 300r/min, be that the diamond polishing cream of 0.5 or 1.0 μ m carries out polished finish 5min at polishing disk with particle diameter again, the polishing disk rotating speed is 600r/min, is polished to the surface and is the bright mirror surface state; Recycle silicon glue polishes afterwards, and the time is 8min.
(2) ultrasonic cleaning is processed, and uses acetone ultrasonic cleaning 10min, uses dehydrated alcohol ultrasonic cleaning 10min again, uses dehydrated alcohol drip washing 1min after the taking-up again.
(3) the ion source Bombardment and cleaning is processed, and adopts the Hall ion source that matrix is cleaned 10min, and environmental stress is 2.5 * 10
-2Pa, substrate temperature are 300 ℃, and the Ar airshed is 10sccm, and bias voltage is-100V, and cathodic current is 25A, and cathode voltage is 15V, and anodic current is 6A, and anode voltage is 50V.
2, reactive sputter-deposition thermodynamics unsteady state Zr
85Al
15N precursor mould material
(1) the cavity environment temperature is heated to 120 ℃, the carbide matrix temperature is heated to 300 ℃, passes into Ar gas, and flow set is regulated the interior operating pressure of cavity to 0.8Pa at 40sccm, is the Zr of 85:15 with atomic percent Zr:Al
85Al
15The alloy target material power regulation is to 100W, sputter 3min; Then with Zr
85Al
15The alloy target material power regulation is to 125W, sputter 3min; Again with Zr
85Al
15The alloy target material power regulation is to 150W, sputter 3min; At last with Zr
85Al
15The alloy target material power regulation is to 200W, sputter 3min.This pre-sputter procedure is in order to removing the contaminating impurity such as target material surface oxide compound, and activation target material surface atom is carried the highly purified while and also improved the sputter rate of target.
(2) after pre-sputter is finished, confirm that first the cavity environment temperature is 120 ℃, the carbide matrix temperature is 300 ℃, passes into N again
2Gas, adjust flux is so that Ar gas and N
2The gas total flux is 50sccm, N
2The gas intrinsic standoff ratio is 20%, and chamber pressure is 0.3Pa.Rotate sample table, so that Wimet is over against Zr
85Al
15Alloy target material, with the distance of target be 8cm, open the target plate washer, with Zr
85Al
15Alloy target material d.c. sputtering power rises to 100W, rises to 150W behind the 3min, rises to 200W through behind the 3min, rises to 250W through behind the 3min again, rises to 300W through behind the 3min more at last, keeps appropriate time under this power condition, amounts to sputtering sedimentation 60min.
3, to Zr
85Al
15N precursor mould material carries out anneal
The Wimet of plated film is placed 700 ℃ of annealing furnaces, insulation 2h, processing atmosphere is air.Make Zr
85Al
15N precursor mould material generation oxidation, and obvious oxidation does not occur in Wimet, still can be used as body material.And at Zr
85Al
15In the oxidation products of N precursor mould material, ZrO
2Be crystal form, and Al
2O
3Be non-crystalline state, obtain amorphous Al
2O
3The nanocrystalline ZrO of Coated
2Composite coating material.
4, Zr
85Al
15The chemical composition of N precursor mould material characterizes and adopts the EPMA(electron probe microanalysis (EPMA)), the atom content per-cent of coating is: Al/(Al+Zr)=15.1%.Fig. 1 is Zr
85Al
15The XRD spectra of N precursor mould material, the coating that shows preparation are the coatings with face-centred cubic structure, utilize to thank and strangle formula, and the calculating grain-size is 30nm.Fig. 2 is the section S EM figure after embodiment 1 anneal, can find Zr
85Al
15N precursor mould material all becomes columnar structure with zone of oxidation, and organizes fine and closely woven.
5, tem observation
With Zr
85Al
15After N precursor mould material carried out anneal, preparation transmission electron microscope observing sample obtained the rear discovery of HRTEM picture (referring to Fig. 7), crystal form ZrO
2Part is by non-crystalline state Al
2O
3Coat ZrO
2Grain-size inhomogeneous, between 10～100nm.
Embodiment 2
1, substrate pretreated
(1) mechanical mill polished finish, first Wimet is ground 5min at 600 order diamond disks, speed of grinding plate is 300r/min, then use 1200 order diamond disks to grind 5min, speed of grinding plate is 300r/min, be that the diamond polishing cream of 0.5 or 1.0 μ m carries out polished finish 8min at polishing disk with particle diameter again, the polishing disk rotating speed is 600r/min, is polished to the surface and is the bright mirror surface state; Recycle silicon glue polishes afterwards, and the time is 10min.
(2) ultrasonic cleaning is processed, and uses acetone ultrasonic cleaning 15min, uses dehydrated alcohol ultrasonic cleaning 15min again, uses dehydrated alcohol drip washing 2min after the taking-up again.
(3) the ion source Bombardment and cleaning is processed, and adopts the Hall ion source that matrix is cleaned 15min, and environmental stress is 3.0 * 10
-2Pa, substrate temperature are 300 ℃, and the Ar airshed is 15sccm, and bias voltage is-150V, and cathodic current is 30A, and cathode voltage is 20V, and anodic current is 8A, and anode voltage is 60V.
2, reactive sputter-deposition thermodynamics unsteady state Zr
77.5Al
22.5N precursor mould material
(1) the cavity environment temperature is heated to 150 ℃, the carbide matrix temperature is heated to 300 ℃, passes into Ar gas, and flow set is regulated the interior operating pressure of cavity to 1.0Pa at 50sccm, is the Zr of 77.5:22.5 with atomic percent Zr:Al
77.5Al
22.5The alloy target material power regulation is to 100W, sputter 5min; Then with Zr
77.5Al
22.5The alloy target material power regulation is to 125W, sputter 5min; Again with Zr
77.5Al
22.5The alloy target material power regulation is to 150W, sputter 5min; At last with Zr
77.5Al
22.5The alloy target material power regulation is to 200W, sputter 5min.This pre-sputter procedure is in order to removing the contaminating impurity such as target material surface oxide compound, and activation target material surface atom is carried the highly purified while and also improved the sputter rate of target.
(2) after pre-sputter is finished, confirm that first the cavity environment temperature is 150 ℃, the carbide matrix temperature is 300 ℃, passes into N again
2Gas, adjust flux is so that Ar gas and N
2The gas total flux is 60sccm, N
2The gas intrinsic standoff ratio is 30%, and chamber pressure is 0.5Pa.Rotate sample table, so that Wimet is over against Zr
77.5Al
22.5Alloy target material, with the distance of target be 10cm, open the target plate washer, with Zr
77.5Al
22.5Alloy target material d.c. sputtering power rises to 100W, rises to 150W behind the 5min, rises to 200W through behind the 5min, rises to 250W through behind the 5min again, rises to 300W through behind the 5min more at last, keeps appropriate time under this power condition, amounts to sputtering sedimentation 90min.
3, to Zr
77.5Al
22.5N precursor mould material carries out anneal
The Wimet of plated film is placed 900 ℃ of annealing furnaces, insulation 3h, processing atmosphere is air.Make Zr
85Al
15N precursor mould material generation oxidation, and obvious oxidation does not occur in Wimet, still can be used as body material.And at Zr
77.5Al
22.5In the oxidation products of N precursor mould material, ZrO
2Be crystal form, and Al
2O
3Be non-crystalline state, obtain amorphous Al
2O
3The nanocrystalline ZrO of Coated
2Composite coating material.
4, Zr
77.5Al
22.5The chemical composition of N precursor mould material characterizes and adopts EPMA, and the atom content ratio of coating is: Al/(Al+Zr)=22.5%.Fig. 3 is Zr
77.5Al
22.5The XRD spectra of N precursor mould material, the coating that shows preparation are the coatings with face-centred cubic structure, utilize to thank and strangle formula, and the calculating grain-size is 22nm.Fig. 4 is the section S EM figure after embodiment 2 anneal, can find Zr
77.5Al
22.5N precursor mould material all becomes columnar structure with zone of oxidation, and organizes fine and closely woven.
5, tem observation
With Zr
77.5Al
22.5After N precursor mould material carried out anneal, preparation transmission electron microscope observing sample obtained the rear discovery of HRTEM picture (referring to Fig. 8), crystal form ZrO
2Part is by non-crystalline state Al
2O
3Coat ZrO
2Grain-size inhomogeneous, between 5～80nm.
Embodiment 3
1, substrate pretreated
(1) mechanical mill polished finish, first Wimet is ground 4min at 600 order diamond disks, speed of grinding plate is 300r/min, then use 1200 order diamond disks to grind 4min, speed of grinding plate is 300r/min, be that the diamond polishing cream of 0.5 or 1.0 μ m carries out polished finish 6min at polishing disk with particle diameter again, the polishing disk rotating speed is 600r/min, is polished to the surface and is the bright mirror surface state; Recycle silicon glue polishes afterwards, and the time is 9min.
(2) ultrasonic cleaning is processed, and uses acetone ultrasonic cleaning 12min, uses dehydrated alcohol ultrasonic cleaning 12min again, uses dehydrated alcohol drip washing 1.5min after the taking-up again.
(3) the ion source Bombardment and cleaning is processed, and adopts the Hall ion source that matrix is cleaned 12min, and environmental stress is 2.8 * 10
-2Pa, substrate temperature are 300 ℃, and the Ar airshed is 13sccm, and bias voltage is-120V, and cathodic current is 27A, and cathode voltage is 18V, and anodic current is 7A, and anode voltage is 55V.
2, reactive sputter-deposition thermodynamics unsteady state Zr
70Al
30N precursor mould material
(1) the cavity environment temperature is heated to 130 ℃, the carbide matrix temperature is heated to 300 ℃, passes into Ar gas, and flow set is regulated the interior operating pressure of cavity to 0.9Pa at 45sccm, is 70: 30 Zr with atomic percent Zr:Al
70Al
30The alloy target material power regulation is to 100W, sputter 4min; Then with Zr
70Al
30The alloy target material power regulation is to 125W, sputter 4min; Again with Zr
70Al
30The alloy target material power regulation is to 150W, sputter 4min; At last with Zr
70Al
30The alloy target material power regulation is to 200W, sputter 4min.This pre-sputter procedure is in order to removing the contaminating impurity such as target material surface oxide compound, and activation target material surface atom is carried the highly purified while and also improved the sputter rate of target.
(2) after pre-sputter is finished, confirm that first the cavity environment temperature is 130 ℃, the carbide matrix temperature is 300 ℃, passes into N again
2Gas, adjust flux is so that Ar gas and N
2The gas total flux is 55sccm, N
2The gas intrinsic standoff ratio is 25%, and chamber pressure is 0.4Pa.Rotate sample table, so that Wimet is over against Zr
70Al
30Alloy target material, with the distance of target be 9cm, open the target plate washer, with Zr
70Al
30Alloy target material d.c. sputtering power rises to 100W, rises to 150W behind the 4min, rises to 200W through behind the 4min, rises to 250W through behind the 4min again, rises to 300W through behind the 4min more at last, keeps appropriate time under this power condition, amounts to sputtering sedimentation 80min.
3, to Zr
70Al
30N precursor mould material carries out anneal
The Wimet of plated film is placed 800 ℃ of annealing furnaces, insulation 2.5h, processing atmosphere is air.Make Zr
70Al
30N precursor mould material generation oxidation, and obvious oxidation does not occur in Wimet, still can be used as body material.And at Zr
70Al
30In the oxidation products of N precursor mould material, ZrO
2Be crystal form, and Al
2O
3Be non-crystalline state, obtain amorphous Al
2O
3The nanocrystalline ZrO of Coated
2Composite coating material.
4, Zr
70Al
30The chemical composition of N precursor mould material characterizes and adopts EPMA, and the atom content ratio of coating is: Al/(Al+Zr)=29.9%.Fig. 5 is Zr
70Al
30The XRD spectra of N precursor mould material, the coating that shows preparation are the coatings with face-centred cubic structure, utilize to thank and strangle formula, and the calculating grain-size is 19nm.Fig. 6 is the section S EM figure after embodiment 3 anneal, can find Zr
70Al
30N precursor mould material is columnar structure, and organizes fine and closely wovenly, but zone of oxidation is loose, non-columnar structure, occurs than multiple cracks.
5, tem observation
With Zr
70Al
30After N precursor mould material carried out anneal, preparation transmission electron microscope observing sample obtained the rear discovery of HRTEM picture (referring to Fig. 9), crystal form ZrO
2Fully by non-crystalline state Al
2O
3Coat ZrO
2Grain-size little and be evenly distributed, between 5～20nm.
Claims (6)
1. amorphous Al
2O
3The nanocrystalline ZrO of Coated
2The preparation method of composite coating material is characterized in that may further comprise the steps:
1) substrate pretreated;
2) reactive sputter-deposition thermodynamics unsteady state ZrAlN precursor mould material;
3) ZrAlN precursor mould material is carried out anneal.
2. a kind of amorphous Al as claimed in claim 1
2O
3The nanocrystalline ZrO of Coated
2The preparation method of composite coating material is characterized in that in step 1), and described substrate pretreated is to carry out successively mechanical mill polished finish, ultrasonic cleaning, the processing of ion source Bombardment and cleaning.
3. a kind of amorphous Al as claimed in claim 2
2O
3The nanocrystalline ZrO of Coated
2The preparation method of composite coating material, it is characterized in that described mechanical mill polished finish, first Wimet to be used 600 order diamond disks to grind 3～5min, speed of grinding plate is 300r/min, then use 1200 order diamond disks to grind 3～5min, speed of grinding plate is 300r/min, is that the diamond polishing cream of 0.5 or 1.0 μ m carries out polished finish 5～8min at polishing disk with particle diameter again, the polishing disk rotating speed is 600r/min, is polished to the surface and is the bright mirror surface state; Recycle silicon glue polishes afterwards, and the time is 8～10min.
4. a kind of amorphous Al as claimed in claim 2
2O
3The nanocrystalline ZrO of Coated
2The preparation method of composite coating material is characterized in that described ion source Bombardment and cleaning processing, is to adopt the Hall ion source that matrix is cleaned 10～15min, and environmental stress is 2.5～3.0 * 10
-2Pa, substrate temperature are 300 ℃, and the Ar airshed is 10～15sccm, bias voltage is-100～-150V, cathodic current is 25～30A, and cathode voltage is 15～20V, and anodic current is 6～8A, and anode voltage is 50～60V.
5. a kind of amorphous Al as claimed in claim 1
2O
3The nanocrystalline ZrO of Coated
2The preparation method of composite coating material, it is characterized in that in step 2) in, described reactive sputter-deposition thermodynamics unsteady state ZrAlN precursor mould material, be that the cavity environment temperature is heated to 120～150 ℃, the carbide matrix temperature is heated to 300 ℃, passes into Ar gas, flow set is at 40～50sccm, regulate operating pressure to 0.8 in the cavity～1.0Pa, with ZrAl alloy target material power regulation to 100W, sputter 3～5min; Then with ZrAl alloy target material power regulation to 125W, sputter 3～5min; Again with ZrAl alloy target material power regulation to 150W, sputter 3～5min; At last with ZrAl alloy target material power regulation to 200W, sputter 3～5min.
6. a kind of amorphous Al as claimed in claim 1
2O
3The nanocrystalline ZrO of Coated
2The preparation method of composite coating material is characterized in that in step 3), described ZrAlN precursor mould material is carried out anneal, is that the Wimet with plated film places 700～900 ℃ of annealing furnaces, insulation 2～3h, and processing atmosphere is air.
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|---|---|---|---|
| CN201210385373.6A CN102912305B (en) | 2012-10-11 | 2012-10-11 | Preparation method for amorphous Al2O3 and superfine nanocrystalline-coated ZrO2 compound coating material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104669071A (en) * | 2015-01-22 | 2015-06-03 | 湖南大学 | Composite material grinding and polishing technology |
| CN106048529A (en) * | 2016-07-11 | 2016-10-26 | 中国科学院宁波材料技术与工程研究所 | Corrosion resistant coating layer with self-repair capacity and preparation method thereof |
| CN109487213A (en) * | 2018-11-20 | 2019-03-19 | 山东科技大学 | A kind of anti-corrosion antifouling film and preparation method thereof based on stainless steel |
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2012
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| 《Surface & Coatings Technology》 20041114 Y. Makino，et al. Characterization of Zr-Al-N films synthesized by a magnetron sputtering method 219-222 1-6 第193卷, * |
| Y. MAKINO，ET AL.: "Characterization of Zr–Al–N films synthesized by a magnetron sputtering method", 《SURFACE & COATINGS TECHNOLOGY》 * |
| 李德军: "具有高温稳定性的ZrAlN 薄膜的合成", 《中国科学 E辑 技术科学》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104669071A (en) * | 2015-01-22 | 2015-06-03 | 湖南大学 | Composite material grinding and polishing technology |
| CN106048529A (en) * | 2016-07-11 | 2016-10-26 | 中国科学院宁波材料技术与工程研究所 | Corrosion resistant coating layer with self-repair capacity and preparation method thereof |
| CN106048529B (en) * | 2016-07-11 | 2018-10-02 | 中国科学院宁波材料技术与工程研究所 | A kind of corrosion-resistant finishes and preparation method thereof with self-reparing capability |
| CN109487213A (en) * | 2018-11-20 | 2019-03-19 | 山东科技大学 | A kind of anti-corrosion antifouling film and preparation method thereof based on stainless steel |
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