Micro-nanometer structure TiO2 coating with high hardness and high adhesion force as well as preparation method thereof

High-hardness high adhesion of nanometre structure iO2 A coating and preparation method thereof

technical field

[0001] The invention relates to the substrate surface Tio2 coating technical field, comprising a high hardness high adhesion of the micro nanometre TIO2 structure coating and preparation method.

background technology

[0002] The titanium dioxide (TiO2) by of photochemical catalysis activity is high chemical, and non-toxic, and of light corrosiveness rod and so on high performance of the degenerate prospect application of photochemical catalysis for oxidization and floating and other aspects, the background of the current is provided with importance to the environment-friendly of a native, to an industrial prospect's the research the is composed of photochemical catalysis nanometre TiO2 film or the coating is an urgent.

[0003] The traditional preparation method of TiO2 coating is a metallic materials, the physical vapour deposition and chemical gas phase deposition, electrochemical method and so on, the following preparation method of the setting rate is low; or the process is complex, comprising, high cost is expensive to the raw material and requirement device, wherein wants can realize the large application of the TIO2 to achieve to develop a novel preparation method.

[0004] The hot spraying is a high efficiency and low-cost preparing the effective process of large-area lake-flooding coating [P.Fauchais, Μ. VardelIe, OR F. Coudert, A. VardelIe, C. Delbos, J.Fazilleau, Pure App1.Chem. , 2005, 77 (2): 475-485.], And, the following hot spraying method for using the micro powder layer, and a hot spraying method, a powder particles with said action temperature of the TiO2 crystal irreversiblily a type to the or transition phase, therefore, the following hot spraying method of hard to obtain high specific with the surface region and content of anatase coating, a display of TiO2 coating photochemical catalysis effect the is co. .

[0005] The liquid phase hot spraying preparing the coating precursor or a suspension as the spray coating raw material is added to the processing technology of hot spray coating layer preparation, a method for the method for depositing a coating that the powder and preparation and coating the preparation considerably, simplified the steps, and of the spray coating of the evaporating and coating liquid of the ratio of the amount of heating, the temperature of the spray coating a temperature is low; the liquid phase hot spraying method has of the raw material particles have a growth and power of the conversion. As follows: literature

[0006] (I)F. . Toma, L. or m. Berger, C. Stahr, T. Naumann, and S. Langner, OR. Therm. SprayTechnol. , 2010,19(1-2): 262-274,

[0007] (2) Roman Jaworski, Lech Pawlowski, Francine Roudet, Stefan Kozerski, Fabrice, Petit Surface Coating and Technology, 2008, 202: 2644-2653,

[0008] (3) Chang-Jiu Li, Guan-Jun Sheep, Ze Net Material, Letters 2003,57: . 2130-2134 Of reporting by a liquid phase hot spraying method success to a nanometre structure coating 1102, wherein the EG81345 degrees centigrade, and to result in the coating adhesion kettle is further claims a improving.

[0009] Therefore, the literature to: Lech, Pawlowski Surface Coating and Technology, 2009,203: 2807-2829. That wherein explored a novel, when for preparing, with high adhesion and anatase the content of nanometre Tio2 coating with of researching value, wherein from with social and economic efficiency.

The invention

[0010] Meshes of the invention is any one of the preceding existing technology insufficiency, providing a high hardness high adhesion the micro structure nanometre Tio2 coating and preparation method.

[0011] The invention realizes the technical solution according to weight of interest is: A high hardness of adhesion's the nanometre TIO2 structure coating, wherein the TIO2 coating on the substrate surface, is Microns to IOOym, wherein the TIO2 coating a crystalline phase of the composition and TIO2 of rutile-type of anatase type, Tio2 in the Tio2 coating the mass percentage of 3% to 35%.

[0012] Metal substrate with a, but not limit to the Of low-carbon steel, stainless steel and steel bearing.

[0013] A preferably, TIO2 anatase is in the TIO2 coating the mass percentage of 20% to 30%.

[0014] The invention also provides one of the liquid phase hot spraying and following hot spraying method; and using the hot spraying flame the liquid material and powder, wherein the obtained with high hardness and high adhesion the preparation method of superfine structure nanometre TiO2 coating, the method further - comprising the following steps:

[0015] Step 1, the preparing anatase TiO2 spray coating liquid: material

[0016] Is Inorganic to 10-30 and fine wherein the magnetic stirring mixed to be uniform of anatase TIO2 structure powder and deionized water and absolute ethyl alcohol the average granularity, the spray coating liquid material, the mass percentage content of TiO2 powder is to 9%;

[0017] Step 2, and TIO2 or spraying powder material:

[0018] Is ΙΟμπι to 40 μπκ crystal of the spraying powder material is applied to the structure of titanium dioxide powder the average granularity;

[0019] Step 3, the surface of the sprayings:

[0020] The substrate surface of the blasting, said threads, knurling or an galling of the coarsening pretreatments, wherein the clean, followed by a flame spraying method, wherein the acetylene as fuel gas, an fumes in the combustion according the spray coating liquid material in the step 1) of the compressed gas atomizing, wherein the outer spray gun the feeding way conveyed to the hot spraying flame root, and spraying the conveying direction and hot spraying flame the axis direction is spray coating liquid material 30° is 50-90 degrees of the included angle, and wherein the gun to adjust the spraying powder material in the step 2 of the powder is conveyed to the hot spraying flame root, wherein the surface of the thickness is 10 microns μ to 100 μ the TIO2 coating.

[0021] The preparation of: method

[0022] The step of step 1, the volume ratio of the de-ionized water and absolute ethyl alcohol and is preferably 1: 1 To 4: 1; The magnetic stirring rotational speed is preferably 200r/min to 400r/min, wherein the mixing time is preferably 1 to 4 hours.

[0023] The step of step 3, the spray coating liquid material with two-phase the compressed air pressure preferably 0. mpa to 0. mpa, the flow rate preferably 1. 5Nm3/h to 4. 5Nm3/h; The conveying speed of spraying powder material is preferably 5g/min to 15g/min;

[0024] The step of step 3, the fuel gas pressure preferably 0. mpa to 0. 15MPa, the flow rate preferably 1. ONmVh to 2. ONmVh; The lower flammable gas pressure preferably 0. 3MPa to 0. 0.3-0.7 mpa, the flow rate preferably 2. ONmVh to 3. 5Nm3/h;

[0025] The step of said 3, wherein the spraying distance from is 90-100 mm and.

[0026] In order to using the invention the hardness and adhesive is one of Tio2 coating, wherein the microhardness instrument and adhesion coating machine bearing device is; the hardness of the Tio2 coating through the coating microhardness detecting method, adhesive is between the Tio2 coating and substrate through the coating adhesion detecting method.

[0027] The coating microhardness detection method comprises: Wherein the cross - section of the upper Tio2 coating polishing sample, the microhardness for digital display sclerometer measuring the cross - section, wherein the weight of 25g, said to the time is 10s. The prescription formula:

ττ 2 Ρ. a

[0028] Hv according to claim r- of sm

a d2 2

[0029] The formula: P of the added weight;

[0030] a impressing the inclined pipe; and

[0031] α the square edges four corners and a cone heads is not included angle (predetermined is) 136°.

[0032] The sample test the 5 locus; the final hardness and average value.

[0033] The adhering test method comprises: The weight mechanism via adhesion coating machine bearing device of the weight of the delimiting a needle, and is the TiO2 coating sample, wherein a flow of delimit and surface coating, wherein the delimits coating or end of the anti-biological to one of the ultrasonic thereof, signal the novel the value for coating and bonding strength, namely the upper. The invention claims a parameter detecting method is: The production 12N/min, test 60N weight, bearing speed lmm/min, bearing the length. The sample to 5 of the bearing test, the final upper weight of the average value.

[0034] A surface coating TIO2 in the invention provides of of a type and oxide, and Of anatase content of high, Tio2 coating on the Tio2 coating and of the existing technology, with high hardness, high adhesion and a high type the content, wherein the important application value, wherein with social and economic efficiency hopefully. TiO2 coating the preparation method of the invention claims ingeniously the liquid phase hot spraying and following hot spraying method atom, a functional group:

[0035] (1) Are transferred to the hot spraying flame TIO2 the liquid material and powder, preferably with the coating according of the liquid phase hot spraying and following hot spraying method power; the prepared from the coating and liquid phase hot spraying method for preparing, wherein microhardness and adhesive the improving, the microhardness capable of 534. 1HV, about for 10 times; the upper of weight of 25. 5N, about for 3 times;

[0036] (2) In the conveying the ratio of the TIO2 material and powder by regulating flame spraying method, the control to result in the TIO2 the coating type and or the components, wherein a is a polymer, and TiO2 coating with high mechanical; performanceAt the same time, wherein the control conveying, and can realize the coating, in particular surface coating nanometre Tio2 comparative nanoparticles controllable dosage, protecting the photo-catalysis performance of coating.

brief description fo the drawings

[0037] Figure 1 is a high hardness high adhesion the preparation method schematic two of a structure nanometre Tio2 coating;

[0038] With 2 of the IN-SITU of honey TIO2 of coating the contrast comprising administering to a pharmaceutical composition according to claim 1, compulsive 2, compulsive threes complex, as

[0039] Figure 3 a, b, c and d contrast the SEM section shape of heating TIO2 of coating the substantially as a pharmaceutical composition according to claim 1, compulsive 2, compulsive threes of by respectively;

[0040] With 4 of the microhardness a heating of TIO2 of coating the contrast comprising administering to a pharmaceutical composition according to claim 1, compulsive 2, compulsive threes complex, as

[0041] With 5 of the adhesive is 2a of TIO2 of coating the contrast comprising administering to a pharmaceutical composition according to claim 1, compulsive 2, compulsive threes of obtain.

Wherein the mixture thereof

[0042] The manufacturing detailed further description to the invention of light of the herein described with substantially as straw, 0-50% to a point that the following wherein the substantially as a is the purpose of the synchronous the upper to the invention, and according to any of claims function.

[0043] 1 Described herein described marker is: Spray coating liquid material 1, a powder coating material, 2 of combustions gas, 3 of fuel gas 4, spraying 5 flame.

[0044] Combined is as follows:

[0045] Is one of the combined with the following compulsive, wherein the substantially as the substrate surface coating TIO2 crystal phase has structure with type TiO2, wherein the existing liquid phase hot spraying method, for preparing the method is as follows: thereof

[0046] Deionized water and absolute ethyl alcohol according to volume ratio of 1: 1 In preparing the solvent, the market average size wherein the From 10-30 degrees and crystal is of the TIO2 type powder of) in the solvent, wherein a spray coating liquid material is the magnetic stirring uniformly mixing;

[0047] The spray coating of the substrate to a mm 304 stainless steel disks thickness is. A spraying, the Al2O3 and grain is added to the blasting of the spray coating a surface, dispersion and post- two hours to conduct the liquid phase hot spraying, the has a thickness is 40 microns μ TiO2 coating.

[0048] The microhardness of the TiO2 coating using the coating microhardness detecting method is about 52. 2HV, the The upper coating using the coating adhesion detecting method is about 9. 2N.

[0049] Substantially as 1:

[0050] The substantially as; the substrate and mm 304 stainless steel disks is thickness, wherein the surface of the TIO2 coating is 40 μ m, wherein the TIO2 coating a crystalline phase of the composition and TIO2 of rutile-type of anatase, thereof according to the weight parts of anatase, Tio2 of 3 to 35%. The concrete preparation method of the Tio2 coating is as follows:

[0051] Deionized water and absolute ethyl alcohol according to volume ratio of 1: The 1 in preparing the solvent, the market average size wherein the From 10-30 degrees and crystal is of the TIO2 type powder of) in the solvent, wherein the TIO2 the solid content of the magnetic stirring uniformly mixing is Iwt% spray coating liquid is 1. The spray coating powder material 2 of market average size is ΙΟμπι to 40 μπκ crystal is of rutile-type TiO2 powder. The spray coating of the substrate to a mm 304 stainless steel disks thickness is. A spraying, the Al2O3 and grain is added to the blasting of the spray coating a surface, dispersion and post- two hours to conduct the hot processing.

[0052] As shown in Figure 1; and pressure is 0.4MPa, the flow rate of the 3Nm3/h compressed air the spray coating liquid material is 1, and use of the fire spray gun the feeding way, wherein the spraying material liquid conveying direction and spray coating flame 5 axis direction is 50-90 degrees of the included angle between the spraying flame 5 roots. At the same time, wherein the fire spray gun to adjust the powder in of TiO2 powder of the IOg/- conveying is conveyed to the spray coating flame 5 roots. The flame spraying method, wherein as fuel gas 4, wherein the fuel gas pressure is 0. Mpa, the flow rate is 1. 5Nm3/h; The oxygen a gas 3 and combustion, the control the gas pressure is 0. a, the flow rate of 3Nm3/h; The spray coating method for controlling the spraying distance is mm, the spray coating time, and to a coating thickness of about 40 microns μ.

[0053] The microhardness of the TIO2 coating using the coating microhardness detecting method is about 220. 8HV, the TIO2 of coating the upper coating for adhering test method is about 25. 3N.

[0054] Wherein the ratio of the contrast the example, wherein the substantially as and other performance according of TIO2 coating composite flame spraying method for preparing a distinct improved.

[0055] Substantially as 2:

[0056] The substantially as and pharmaceutical composition according to claim 1 as a compound, which is of the substantially as TIO2 the solid content of the spray coating liquid material is #t%, wherein when experimental conditions are the.

[0057] The microhardness of the TIO2 coating using the coating microhardness detecting method is about 173. 1HV, the TIO2 of coating the upper coating for adhering test method is about 17. 7N.

[0058] Wherein the ratio of the contrast the example, wherein the substantially as and other performance according of TIO2 coating composite flame spraying method for preparing a distinct improved.

[0059] Substantially as 3:

[0060] The substantially as and pharmaceutical composition according to claim 1 as a compound, which is of the substantially as TIO2 the solid content of the spray coating liquid material is 7wt%, wherein when experimental conditions are the.

[0061] The microhardness of the Tio2 coating using the coating microhardness detecting method is about 534. 1HV, the TIO2 of coating the upper coating for adhering test method is about 25. 5N.

[0062] Wherein the ratio of the contrast the example, wherein the substantially as and other performance according of TIO2 coating composite flame spraying method for preparing a distinct improved.

[0063] With 2 of the IN-SITU of honey TIO2 of coating the contrast comprising administering to a pharmaceutical composition according to claim 1, compulsive 2, compulsive threes of obtain. The result shows of using the liquid material and a micro powder and spray coating raw material; the air flame spraying preparing the Tio2 coating comprises anatases and or the seed crystal, and along with of the solution is composed of the nanometre TiO2 solid content, and obtaining the coating type the content of the considerably the.

[0064] Figure 3) is contrasts the substantially as and b is implemented claim 1, wherein is claim 2, wherein the cross - section shape SEM heating of TIO2 on as threes of obtain. The result shows of using the liquid material and a micro powder and spray coating raw material, after using the clean flame spraying preparing the TIO2 a coating of a cobalt, wherein the flat particles of formed by coating framework structure with the substrate surface collision, wherein the liquid material after evaporating the other nano particle is arranged on the inner hole and a binding site flat particles. The along with of the solution is composed of the nanometre TiO2 solid content, and obtaining the coating the nano particle further content considerably the. The TIO2 the coating according and pharmaceutical composition according to claim 3 by the nano particle has been found of the whole coating area, wherein the continuous nanometre structure coating.

[0065] With 4 of the microhardness a heating method of TiO2 coating to contrast comprising administering to a pharmaceutical composition according to claim 1, compulsive 2, compulsive threes of obtain. The result shows of using the liquid material and a micro powder and spray coating raw material; and a coating of the air flame spraying preparing the TiO2 coating and liquid phase flame spraying method prepared, wherein microhardness with an evolutionarily significant, reinforced, wherein the 3 microhardness of TIO2 coating to 534. 1HV, about contrast to the Tio2 coating is substantially as more than 10 times.

[0066] With 5 of the adhesive is 2a of the TiO2 coating to contrast comprising administering to a pharmaceutical composition according to claim 1, compulsive 2, compulsive threes of obtain. The result shows of using the liquid material and a micro powder and spray coating raw material; and a coating of the air flame spraying preparing the TiO2 coating and liquid phase flame spraying method prepared, wherein the adhesive is an evolutionarily significant, reinforced, wherein the TiO2 film adhesive according to claim threes to obtain is 25. 5N, about to contrast TIO2 the coating is substantially as about 3 times.

[0067] Substantially as 4:

[0068] The substantially as and pharmaceutical composition according to claim 1 as a compound, which is of the substantially as the conveying speed of micro powder to 5g/min, wherein when experimental conditions are the.

[0069] The microhardness of the TIO2 coating using the coating microhardness detecting method is about 320. 8HV, the The upper coating using the coating adhesion detecting method is about 18. 3N.

[0070] Wherein the ratio of the contrast the example, wherein the substantially as and other performance according of TIO2 coating composite flame spraying method for preparing a distinct improved.

[0071] Substantially as 5:

[0072] The substantially as and pharmaceutical composition according to claim 1 as a compound, which is of the substantially as the conveying speed of micro powder to 15g/min, wherein when experimental conditions are the.

[0073] The microhardness of the TIO2 coating using the coating microhardness detecting method is about 480. 5HV, the TIO2 of coating the upper coating for adhering test method is about 24. 7N.

[0074] Wherein the ratio of the contrast the example, wherein the substantially as and other performance according of TIO2 coating composite flame spraying method for preparing a distinct improved.

[0075] Substantially as 6:

[0076] The substantially as and pharmaceutical composition according to claim 1 as a compound, which is of the substantially as the fuel gas flow rate is 1.0Nm3/h, wherein the air flow amount is 2. 5Nm3/h, wherein when experimental conditions are the.

[0077] The microhardness of the TIO2 coating using the coating microhardness detecting method is about 387. 5HV, the The upper coating using the coating adhesion detecting method is about 19. 2N.

[0078] Wherein the ratio of the contrast the example, wherein the substantially as and other performance according of TIO2 coating composite flame spraying method for preparing a distinct improved.

[0079] Substantially as 7:

[0080] The substantially as and pharmaceutical composition according to claim 1 as a compound, which is of the substantially as the fuel gas flow rate is 2. 0Nm3/h, wherein the air flow amount is 3. 5Nm3/h, wherein when experimental conditions are the.

[0081] The microhardness of the Tio2 coating using the coating microhardness detecting method is about 390. 4HV, the The upper coating using the coating adhesion detecting method is about 21. 5N.

[0082] Wherein the ratio of the contrast the example, wherein the substantially as and other performance according of TIO2 coating composite flame spraying method for preparing a distinct improved.

[0083] Substantially as 8:

[0084] The substantially as and pharmaceutical composition according to claim 1 as a compound, which is of the substantially as the spraying distance mm; the experimental conditions of the.

[0085] The microhardness of the TIO2 coating using the coating microhardness detecting method is about 505. 8HV, the TIO2 of coating the upper coating for adhering test method is about 24. 6N.

[0086] Wherein the ratio of the contrast the example, wherein the substantially as and other performance according of TIO2 coating composite flame spraying method for preparing a distinct improved.

[0087] Substantially as 9:

[0088] The substantially as and pharmaceutical composition according to claim 1 as a compound, which is of the substantially as the spraying distance is 1-10, wherein when experimental conditions are the.

[0089] The microhardness of the TIO2 coating using the coating microhardness detecting method is about 397. 6HV, the The upper coating using the coating adhesion detecting method is about 20. 2N.

[0090] Wherein the ratio of the contrast the example, wherein the substantially as and other performance according of TIO2 coating composite flame spraying method for preparing a distinct improved.

[0091] The substantially as of said and qi-tonifying and to this invention claims a technical solution in the detail, wherein the compound is the mixture of the mixture of the concrete compulsive of the invention, wherein for limiting the invention, each of any according and improved in this invention claims a range of ABR+OBR process, which comprises the invention extent of protection.