A rare earth doped yttrium zirconium oxide spray material, a coating preparation method and application thereof

Abstract

The application discloses a rare earth doped yttrium zirconium oxide spraying material and a coating preparation method and application, and belongs to the field of rare earth material preparation. The rare earth doped yttrium zirconium oxide spraying material comprises lanthanum cerium carbonate, yttrium carbonate, aluminum oxide, hydroxyethyl cellulose, dodecyl benzyl ammonium chloride, n-heptane, deionized water, peach gum powder and zirconium oxide; the mixed slurry is obtained by mixing and ball milling the components in the spraying material, then the mixed slurry is mixed and stirred with the peach gum powder, and then the rare earth doped yttrium zirconium oxide spraying material coating is obtained through spray granulation and plasma spraying. Compared with the original yttrium zirconium oxide spraying powder, the yttrium zirconium oxide is modified by using the lanthanum cerium carbonate and the aluminum oxide, the wear resistance of the spraying powder is improved, the original white coating can be changed into black, and the application prospect is achieved in the fields of electronic ceramics, cutters and gas nozzles.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of rare earth material preparation, and more particularly to a rare earth doped yttrium zirconium oxide spraying material and a coating preparation method. BACKGROUND

[0002] Spraying material is a material used in thermal spraying technology to obtain a desired coating on the surface of a workpiece. Spraying materials can be divided into four categories according to their composition and structure: single-component spraying materials, alloy spraying materials, composite spraying materials, and hybrid spraying materials.

[0003] The patent document with the application number 201310384218.7, "Titanium-nitrogen-carbon-aluminum-oxygen nanoceramic coating on the surface of low-carbon steel and a preparation method", discloses a nanoceramic coating, which is composed as follows: from the surface of the steel substrate outward, there are, in order, a titanium nitride layer, a titanium carbide layer, a titanium oxide layer, and an aluminum oxide layer; the total thickness of the nanoceramic coating is 8-12 microns, and each single layer meets the following characteristics: the thickness of the titanium nitride layer is 1-3 microns, the thickness of the titanium carbide layer is 2.5-3 microns, the thickness of the titanium oxide layer is 0.5-1 micron, and the thickness of the aluminum oxide layer is 4-5 microns. As can be seen, the nanoceramic coating is a multi-layer structure, each layer is composed of different nanomaterials, and therefore, the protection of the substrate is relatively ideal, and it has certain corrosion resistance and wear resistance, but it still has some shortcomings.

[0004] The patent document with the application number 201210476363.3, "A nanocomposite coating", discloses a nanocomposite coating, which includes a metal substrate and a nanoceramic coating, and a nanometal primer layer is provided between the metal substrate and the nanoceramic coating; the composition of the nanoceramic coating is an aluminum oxide and chromium oxide compound; the metal primer layer is nickel-chromium; the weight proportion of the aluminum oxide component in the nanoceramic coating is 85%-95%, and the weight proportion of the chromium oxide component is 5%-15%. As can be seen, the nanocomposite coating is a nanoceramic layer, which is a ceramic material with aluminum oxide as the main component, and the performance is mainly based on the performance of aluminum oxide and chromium oxide, which is a traditional ceramic material. The difference is that the coating uses nanotechnology, and a nanometal primer layer is added between the two layers to increase the connection between the metal substrate and the nanoceramic layer. However, the performance has not been improved, and it still lacks sufficient toughness.

[0005] The spraying materials provided in the above prior art have poor flowability and low sphericity, and the coating hardness and wear resistance are poor due to uneven composition of the spraying powder. Therefore, it is urgent to provide a new thermal spraying powder to improve the wear resistance of the thermal spraying layer formed by the thermal spraying powder. SUMMARY

[0006] Therefore, the present application provides a rare earth doped yttrium zirconium oxide spraying material and a coating preparation method and application.

[0007] To achieve the above object, the present application adopts the following technical solutions:

[0008] A rare earth doped yttrium zirconium spraying material comprises lanthanum cerium carbonate, yttrium carbonate, aluminum oxide, hydroxyethyl cellulose, dodecyl benzyl ammonium chloride, n-heptane, deionized water, peach gum powder and zirconium oxide.

[0009] Preferably, the mass ratio of the lanthanum cerium carbonate, yttrium carbonate, aluminum oxide, hydroxyethyl cellulose, dodecyl benzyl ammonium chloride, n-heptane, deionized water, peach gum powder and zirconium oxide is (0.01-5):(8-20):(0.1-5):(0.1-3):(0.01-0.5):(1-3):(150-250):(0.05-3):100.

[0010] The rare earth doped yttrium stabilized zirconium oxide spraying material prepared by the present application has high sphericity and good fluidity. The application of rare earth elements in the coating material refines the coating grain, purifies the grain boundary structure and produces solid solution strengthening. The hydroxyethyl cellulose has good dispersion effect and can reduce powder agglomeration and shorten the grinding time during sand mill fine grinding. The peach gum powder acts as a binder in the spray granulation process and helps uniform agglomeration between particles. The hydroxyethyl cellulose added during the grinding process has a film-forming effect, which can improve the sphericity of the powder during the spray granulation process. During the grinding process, many bubbles will appear due to the increased viscosity of the fine powder, which affects the grinding process. The addition of n-heptane can play a defoaming role. The present application has low preparation cost, controllable particle size, good fluidity, high hardness of the obtained coating and good wear resistance.

[0011] Another object of the present application is to provide a preparation method of a rare earth doped yttrium zirconium spraying material coating, comprising the following steps:

[0012] (1) Each component is weighed according to the above-mentioned proportion in the rare earth doped yttrium zirconium spraying material, and the lanthanum cerium carbonate, yttrium carbonate, zirconium oxide, aluminum oxide, hydroxyethyl cellulose, dodecyl dimethyl benzyl ammonium chloride, n-heptane and part of the deionized water are prepared into a slurry, which is fine ground in a sand mill at room temperature to obtain a mixed slurry;

[0013] (2) The peach gum powder is added to the remaining deionized water, and a peach gum powder sol is obtained after mixing, heating and keeping warm. The mixed slurry is added to the peach gum powder sol and stirred at room temperature to perform spray granulation to obtain a precursor powder. The precursor powder is calcined at high temperature to obtain a spherical spraying powder, i.e. the rare earth doped yttrium zirconium spraying material;

[0014] (3) the plasma spraying process is adopted, the spraying power is 15-32KW, the voltage is 40-55V, the current is 360-560A, the argon gas flow is 25-45L / min, the powder feeding rate is 40-60g / min, the spraying distance is 10-25cm, and the coating thickness is 80-150mu.

[0015] Preferably, the circulating fine grinding process in step (1) is divided into two steps, first, the zirconium beads with a particle size of 0.3mm are used for fine grinding for 30-40min, the speed of the sand mill is 1500-2000r / min, then the zirconium beads with a particle size of 0.1mm are used for fine grinding for 60-90min, the speed of the sand mill is 2000-2500r / min.

[0016] Preferably, the speed of the sand mill is 2000-2500r / min, and the mass ratio of the zirconium beads in the sand mill to the zirconia in the mixed slurry is (1-3):1.

[0017] The present application fully grinds the raw materials before spray granulation, which can make the solid phase reaction of each material occur fully in the subsequent sintering and spraying process, produce dispersion strengthening effect on the coating, and improve the hardness and wear resistance of the coating.

[0018] Preferably, in step (2), the mass ratio of peach gum powder to the remaining deionized water is 1:(3.5-5); and the heating and keeping warm is kept at 90℃ for 3-6h.

[0019] The appropriate amount of peach gum powder plays a crucial role in the agglomeration of micro-nano oxide particles, which is beneficial to the bonding between the particles and makes it easier to obtain spherical particles during spray granulation.

[0020] Preferably, the parameters of the spray granulation are as follows: the inlet air temperature is 120-200℃, the outlet air temperature is 60-130℃, the feeding speed is 30-45ml / min, and the speed is 9000r / min-18000r / min.

[0021] The above parameters can accurately control the particle size range of the granulated powder.

[0022] Preferably, the calcination is carried out at 1300℃ for 3h, which can fully decompose and volatilize the organic matter in the granulated powder, and at the same time, make the lanthanum cerium, yttrium and zirconium in the granulated powder occur solid solution reaction.

[0023] Preferably, the median particle size D50 of the rare earth doped yttrium zirconium oxide spraying material is 35-75mu, which can make the spraying powder flow smoothly and uniformly through the plasma spraying powder feeder, and ensure the uniformity of the coating quality.

[0024] The present application also aims to provide the preparation method of the rare earth doped yttrium zirconium oxide spraying material coating and the application of the rare earth doped yttrium zirconium oxide spraying material coating in electronic ceramics, cutters and gas nozzles.

[0025] Compared with the prior art, the present application has the following beneficial effects:

[0026] Compared with the original yttrium zirconium oxide spraying powder, the present application modifies the yttrium zirconium oxide by using lanthanum cerium carbonate and aluminum oxide, improves the wear resistance of the spraying powder, and changes the original white coating. BRIEF DESCRIPTION OF DRAWINGS

[0027] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiments or the prior art description. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor on the basis of the provided drawings.

[0028] Figure 1 SEM image of the spraying material prepared for the present application embodiment 1;

[0029] Figure 2 Comparison photo of the coating prepared for the present application embodiment 1 and the coating of comparative example 1, wherein a is embodiment 1 and b is comparative example 1;

[0030] Figure 3 SEM image of the spraying material prepared for comparative example 3;

[0031] Figure 4 SEM image of the spraying material prepared for comparative example 4. DETAILED DESCRIPTION

[0032] The technical solutions in the embodiments of the present application will be described clearly and completely below in combination with the drawings in the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the protection scope of the present application.

[0033] Embodiment 1

[0034] The present embodiment provides a preparation method of a rare earth doped yttrium zirconium oxide spraying material coating, comprising the following steps:

[0035] (1) The mass ratio of lanthanum cerium carbonate, yttrium carbonate, alumina, hydroxyethyl cellulose, dodecylbenzyl ammonium chloride, n-heptane, deionized water, peach gum powder and zirconium oxide is 0.05:12:1:0.5:0.03:3:200:2:100, each component is weighed and prepared;

[0036] (2) The lanthanum cerium carbonate, yttrium carbonate, zirconium oxide, alumina, part of the deionized water, hydroxyethyl cellulose, dodecyl dimethyl benzyl ammonium chloride and n-heptane are prepared into slurry, and are circulated and finely ground at room temperature in a nano sand mill. Firstly, the zirconium beads with a particle size of 0.3 mm are used for fine grinding for 30 min, the rotation speed of the sand mill is 1900 r / min, the material is finely ground to a median particle size D50 of 1.75 μm, then the zirconium beads with a particle size of 0.1 mm are selected for fine grinding for 90 min, the rotation speed of the sand mill is 2500 r / min, the particle size of the material is finely ground to 160 nm, the mass ratio of the zirconium beads to the alumina in the sand mill is 2.3:1, and the mixed slurry is obtained,

[0037] (3) The peach gum powder is mixed with the remaining deionized water (mass ratio of 1:3.5) and is kept at 90°C for 5 h, and is cooled to room temperature to obtain a peach gum powder sol. The finely ground mixed slurry is added with the peach gum powder sol, the mass ratio of the solute in the peach gum powder sol to the zirconium oxide is 0.02:1, and is stirred at room temperature for 30 min (rotation speed of 600 r / min). Spray granulation is carried out, the inlet air temperature of the spray granulator is 130°C, the outlet air temperature is controlled at 75°C, the feeding speed is controlled at 40 ml / min, and the rotation speed is controlled at 12000 r / min. The precursor powder is obtained, the precursor powder is calcined at 1300°C for 3 h, and the yttrium zirconium oxide spherical spray powder with a median particle size D50 of 45 μm and very good flowability is obtained;

[0038] (4) The plasma spraying process is adopted, the spraying power is controlled at 29.23 KW, the voltage is 53.1 V, the current is 550.5 A, the argon gas flow is 30 L / min, the powder feeding rate is 50 g / min, the spraying distance is controlled at 20 cm, and the black wear-resistant coating with a hardness HV0.1 of 1051, a volume wear rate of 2.1×10 -4 mm 3 / N·min (load of 100 N, frequency of 5 Hz, and test time of 120 min) is obtained.

[0039] Example 2

[0040] The embodiment provides a preparation method of a rare earth doped yttrium zirconium oxide spraying material coating, comprising the following steps:

[0041] (1) The mass ratio of lanthanum cerium carbonate, yttrium carbonate, alumina, hydroxyethyl cellulose, dodecylbenzyl ammonium chloride, n-heptane, deionized water, peach gum powder and zirconium oxide is 2:9:0.5:2:0.2:1:250:2:100, each component is weighed and prepared;

[0042] (2) The lanthanum cerium carbonate, yttrium carbonate, zirconium oxide, aluminum oxide, part of the deionized water, hydroxyethyl cellulose, dodecyl dimethyl benzyl ammonium chloride, n-heptane are prepared into slurry, and are recycled and finely ground in the nano sand mill at room temperature. Firstly, the zirconium beads with a particle size of 0.3 mm are used for fine grinding for 35 min, the rotation speed of the sand mill is 1500 r / min, the material is finely ground to a median particle size D50 of 1.69 μm, then the zirconium beads with a particle size of 0.1 mm are used for fine grinding for 75 min, the rotation speed of the sand mill is 2000 r / min, the particle size of the material is finely ground to 173 nm, the mass ratio of the zirconium beads to the aluminum oxide in the sand mill is 2.3:1, and the mixed slurry is obtained;

[0043] (3) The peach gum powder is mixed with the remaining ionized water (the mass ratio is 1:5) and is kept at 90℃ for 4 h, and is cooled to room temperature to obtain a peach gum powder sol. The finely ground mixed slurry is added with the peach gum powder sol, the mass ratio of the solute in the peach gum powder sol to the zirconium oxide is 0.02:1, and is stirred at room temperature for 30 min (the rotation speed is 600 r / min). Spray granulation is carried out, the inlet air temperature of the spray granulation is 200℃, the outlet air temperature is controlled to 120℃, the feeding speed is controlled to 35 ml / min, and the rotation speed is controlled to 18000 r / min. The precursor powder is obtained. The precursor powder is calcined at 1300℃ for 3 h to obtain the yttrium zirconium oxide spherical spray powder with a median particle size D50 of 41.3 μm and very good flowability;

[0044] (4) The plasma spraying process is adopted, the spraying power is controlled to 26.4 KW, the voltage is 48.6 V, the current is 543.2 A, the argon gas flow is 35 L / min, the powder feeding rate is 55 g / min, the spraying distance is controlled to 20 cm, and the black wear-resistant coating with a hardness HV0.1 of 937, a volume wear rate of 2.6×10 -4 mm 3 / N·min (the load is 100 N, the frequency is 5 Hz, and the test time is 120 min) is obtained.

[0045] Example 3

[0046] The embodiment provides a preparation method of a rare earth doped yttrium zirconium oxide spray coating, which comprises the following steps:

[0047] (1) The mass ratio of the lanthanum cerium carbonate, yttrium carbonate, aluminum oxide, hydroxyethyl cellulose, dodecyl benzyl ammonium chloride, n-heptane, deionized water, peach gum powder and zirconium oxide is 0.1:9:2.5:0.5:0.1:3:150:0.5:100, and each component is weighed and prepared;

[0048] (2) The lanthanum cerium carbonate, yttrium carbonate, zirconium oxide, aluminum oxide, part of deionized water, hydroxyethyl cellulose, dodecyl dimethyl benzyl ammonium chloride, n-heptane are prepared into slurry, and are recycled and finely ground in a nano sand mill at room temperature. Firstly, the material is finely ground for 40 min by using zirconium beads with a particle size of 0.3 mm at a sand mill speed of 1500 r / min, and the material is finely ground to a median particle size D50 of 2.13 μm. Then, the material is finely ground for 90 min by using zirconium beads with a particle size of 0.1 mm at a sand mill speed of 2300 r / min, so that the particle size of the material is finely ground to 154 nm. The mass ratio of the zirconium beads to the aluminum oxide in the sand mill is 2.0:1, and a mixed slurry is obtained,

[0049] (3) The peach gum powder is mixed with the remaining ionized water (mass ratio of 1:3) and is kept at 90℃ for 6 h, and is cooled to room temperature to obtain a peach gum powder sol. The finely ground mixed slurry is added with the peach gum powder sol, and the mass ratio of the solute in the peach gum powder sol to the zirconium oxide is 0.005:1. The mixture is stirred at room temperature for 30 min (at a speed of 600 r / min), is subjected to spray granulation, the inlet air temperature of the spray granulation is 120℃, the outlet air temperature is controlled to be 65℃, the feeding speed is controlled to be 32 ml / min, and the rotation speed is controlled to be 10000 r / min, so that a precursor powder is obtained. The precursor powder is calcined at 1300℃ for 3 h, and a spherical yttrium zirconium oxide spray powder with a median particle size D50 of 47.3 μm and very good flowability is obtained.

[0050] (4) The plasma spraying process is adopted, the spraying power is controlled to be 26.26 KW, the voltage is controlled to be 53.3 V, the current is controlled to be 492.7 A, the argon gas flow is controlled to be 27 L / min, and the spraying distance is controlled to be 20 cm, so that a black wear-resistant coating with a hardness HV0.1 of 850, a volume wear rate of 3.8×10 -4 mm 3 / N·min (load of 100 N, frequency of 5 Hz, and test time of 120 min) is obtained.

[0051] Comparative Example 1

[0052] The preparation method is the same as that in Example 1, and other conditions are unchanged. The lanthanum cerium carbonate is not added in the preparation of the slurry, and the yttrium carbonate is replaced by yttrium oxide. The obtained coating is white, and the volume wear rate is 2.5×10 -4 mm 3 / N·min.

[0053] Comparative Example 2

[0054] The preparation method is the same as that in Example 1, and other conditions are unchanged. The spray granulation rotation speed is controlled to be 15000 r / min, and the median particle size D50 of the powder is 41.4 μm. Comparative Example 3

[0055] The preparation method is the same as that of Example 1, and other conditions are unchanged. The slurry is circulated and finely ground in a sand mill for 10 min. The median particle size D50 of the obtained powder is 48 μm, but the powder micro-morphology is rougher. The volume wear rate of the obtained coating is 3.4 x 10 -4 mm 3 / N·min. Comparative Example 4

[0056] The preparation method is the same as that of Example 1, and other conditions are unchanged. No hydroxyethyl cellulose is added in the spray granulation process. The particle size of the obtained spray powder is uneven, the sphericity is not good, and the powder flowability is not good.

[0057] The various embodiments in the specification are described in a progressive manner, and each embodiment focuses on the difference from other embodiments. The same or similar parts between the various embodiments can be referred to each other. For the device disclosed in the embodiments, since it corresponds to the method disclosed in the embodiments, the description is relatively simple, and the related parts can be referred to the method part.

[0058] The above description of the disclosed embodiments enables a person skilled in the art to implement or use the present application. Various modifications to the embodiments will be apparent to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present application. Therefore, the present application will not be limited to the embodiments shown herein, but will conform to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method of producing a rare earth doped yttria zirconia spray material coating, characterized by, It comprises the following steps: (1) prepare a slurry of cerium lanthanum carbonate, yttrium carbonate, zirconium oxide, aluminum oxide, hydroxyethyl cellulose, dodecyl dimethyl benzyl ammonium chloride, n-heptane and part of deionized water, and then recycle and fine grind in a sand mill at room temperature to obtain a mixed slurry; (2) add peach gum powder to the remaining deionized water, heat and keep warm after mixing to obtain a peach gum powder sol, then stir the obtained mixed slurry at room temperature and spray granulate to obtain a precursor powder; the obtained precursor powder is calcined at a high temperature to obtain a spherical spray powder, i.e. the rare earth doped yttrium zirconium oxide spray material; the calcination is carried out at 1300℃ for 3h; (3) use a plasma spraying process with a spraying power of 15-32KW, a voltage of 40-55V, a current of 360-560A, an argon gas flow rate of 25-45L / min, a powder feeding rate of 40-60g / min, a spraying distance of 10-25cm, and a coating thickness of 80-150μm; wherein the mass ratio of the cerium lanthanum carbonate, yttrium carbonate, aluminum oxide, hydroxyethyl cellulose, dodecyl benzyl ammonium chloride, n-heptane, deionized water, peach gum powder and zirconium oxide is (0.01-5):(8-20):(0.1-5):(0.1-3):(0.01-0.5):(1-3):(150-250):(0.05-3):100; the recycle and fine grinding process in step (1) is divided into two steps: first, use zirconium beads with a particle size of 0.3mm to fine grind for 30-40min at a sand mill speed of 1500-2000r / min, and then use zirconium beads with a particle size of 0.1mm to fine grind for 60-90min at a sand mill speed of 2000-2500r / min; in step (2), the mass ratio of peach gum powder to the remaining deionized water is 1:(3.5-5); the heating and keeping warm is carried out at 90℃ for 3-6h.

2. The method of claim 1, wherein the method further comprises: the mass ratio of zirconium beads to zirconium oxide in the mixed slurry in the sand mill is (1-3):

1.

3. The method of claim 1, wherein the method further comprises: the parameters for the spray granulation are: an air inlet temperature of 120-200℃, an air outlet temperature of 60-130℃, a feeding speed of 30-45ml / min, and a rotation speed of 9000r / min-18000r / min.

4. The method of claim 1, wherein the method further comprises: The median particle size D50 of the rare earth doped yttrium zirconium oxide spray material is 35-75μm.

5. The application of the rare earth doped yttrium zirconium oxide spray material coating prepared by the method of any one of claims 1-4 in electronic ceramics, cutting tools, gas nozzles, and scenarios where automobile large shafts and mechanical transmission shafts are in contact with lubricating oil.

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