A core-shell structure pigment Zn2SiO4@SiO2 powder, a preparation method and application thereof

Abstract

The application relates to a core-shell structure pigment Zn2SiO4@SiO2 powder and a preparation method and application thereof. The core-shell structure pigment Zn2SiO4@SiO2 powder comprises Zn2SiO4 particles and a SiO2 layer distributed on the surface of the Zn2SiO4 particles; preferably, the particle size of the Zn2SiO4 particles is 50 nm-2 mu m; preferably, the thickness of the SiO2 layer is 16-37 nm; and preferably, the SiO2 layer is amorphous SiO2.

Description

TECHNICAL FIELD

[0001] The application relates to a low-ratio, ultraviolet radiation resistant core-shell structure pigment Zn2SiO4@SiO2 powder and a preparation method and application thereof, and belongs to the field of thermal control coatings for spacecrafts. BACKGROUND

[0002] A spacecraft experiences a special thermal environment in space, and the temperature difference of up to hundreds of degrees between the sun-facing surface and the shaded surface makes the spacecraft have to be subjected to thermal design and control. In addition to factors such as the intensity of the space radiation source and the orbit parameters, the surface temperature of the spacecraft is proportional to the 1 / 4 power of the solar absorption / radiation ratio of the surface material thereof. With the integration of electronic chips, the reliability of the spacecraft will decrease by 5% for each 1℃ increase in the device temperature at the level of 70-80℃, which puts forward more stringent requirements for the thermal design of the spacecraft in the space environment. Therefore, a thermal control coating with as low a solar absorption / radiation ratio as possible can more effectively ensure that the spacecraft is in a normal working temperature range.

[0003] In addition to the above low-ratio requirement, the space stability of the thermal control coating is another key performance index, which determines the reliability and service life of the spacecraft in orbit, and the change amount of the solar absorption is usually used as a parameter for describing the stability. Assuming that the solar absorption of the coating increases from the initial value 0.21 to 0.48, it is calculated (front vertical irradiation, back heat insulation, and the radiation rate is unchanged, 0.92) that the surface temperature of the spacecraft is from 271.7K to 334K, and the temperature difference is as high as 62.3K. Therefore, the degradation of the performance of the coating seriously restricts the service life and thermal control of the spacecraft. SUMMARY

[0004] In view of the above problems, the application provides a low-ratio, ultraviolet radiation resistant core-shell structure pigment Zn2SiO4@SiO2 powder and a preparation method and application thereof.

[0005] In a first aspect, the application provides a core-shell structure pigment Zn2SiO4@SiO2 powder, which comprises Zn2SiO4 particles and a SiO2 layer distributed on the surface of the Zn2SiO4 particles; preferably, the SiO2 layer is amorphous SiO2.

[0006] Preferably, the particle size of the Zn2SiO4 particles is 50nm-2um.

[0007] Preferably, the thickness of the SiO2 layer is 16-37nm.

[0008] In a second aspect, the application provides a preparation method of the core-shell structure pigment Zn2SiO4@SiO2 powder, which comprises the following steps: (1) adding Zn2SiO4 powder into a mixed solution of anhydrous ethanol and water, adding ammonia water and ball milling beads for ball milling treatment, and then adding TEOS for secondary ball milling treatment to obtain a suspension solution;

[0009] (2) centrifuging, drying and heat-treating the obtained suspension solution to obtain core-shell structure pigment Zn2SiO4@SiO2 powder.

[0010] Preferably, the average particle size of the Zn2SiO4 powder is 50 nm to 2 μm; the volume ratio of anhydrous ethanol in the mixed solution of anhydrous ethanol and water is 60 to 95%, preferably 90%; the purity of the anhydrous ethanol, TEOS and ammonia water is all superior grade.

[0011] Preferably, the rotation speed of the ball milling treatment is 20 to 50 r / min, and the total time of the ball milling treatment is 2 to 5 hours; the ratio of the volume of TEOS to the mass of Zn2SiO4 powder is 1 to 4 mL / g.

[0012] Preferably, the centrifugation rate is 3000 to 7000 r / min, and the centrifugation time is 3 to 10 minutes.

[0013] Preferably, the drying temperature is 40 to 120 ℃, and the time is 2 to 12 hours.

[0014] Preferably, the heat treatment temperature is 900 to 1100 ℃, preferably 1000 ℃, and the sintering time is 1 to 3 hours; preferably, the heating rate of the heat treatment is 3 to 10 ℃ / min.

[0015] In a third aspect, the present application provides a core-shell structure pigment Zn2SiO4@SiO2-based thermal control coating, comprising: the core-shell structure pigment Zn2SiO4@SiO2 powder and an inorganic binder; the content of the core-shell structure pigment Zn2SiO4@SiO2 powder in the core-shell structure pigment Zn2SiO4@SiO2-based thermal control coating is 30 to 60 wt%; preferably, the inorganic binder is at least one selected from potassium silicate or sodium silicate.

[0016] Preferably, the total thickness of the core-shell structure pigment Zn2SiO4@SiO2-based thermal control coating is 120 to 200 μm.

[0017] Preferably, the core-shell structure pigment Zn2SiO4@SiO2-based thermal control coating is formed on the surface of a base material, and the base material comprises one of Al alloy, Cu alloy, titanium alloy, stainless steel and SiC-based composite material.

[0018] In a fourth aspect, the present application provides a preparation method of a core-shell structure pigment Zn2SiO4@SiO2-based thermal control coating, comprising:

[0019] (1) uniformly mixing the core-shell structure pigment Zn2SiO4@SiO2 powder, the inorganic binder and water to form a coating slurry;

[0020] (2) Spraying the obtained coating slurry on the surface of the substrate material after polishing treatment, and then drying to obtain the core-shell structure pigment Zn2SiO4@SiO2-based thermal control coating.

[0021] Preferably, the mass percentage of the core-shell structure pigment Zn2SiO4@SiO2 in the coating slurry is 30-60%, the mass percentage of the inorganic binder is 30-60%, and the balance is water.

[0022] Beneficial effects:

[0023] (1) In the present application, the core-shell structure pigment Zn2SiO4@SiO2 has low solar absorption (0.04-0.09) and high emissivity (0.93), and has stronger heat dissipation capacity. Compared with Zn2SiO4 pigment, the shell SiO2 structure can act as a buffer layer to reduce the interaction between the space radiation source and the core pigment, and the ultraviolet radiation stability is significantly improved.

[0024] (2) The preparation process of the present application is simple and easy to operate, the equipment requirement is simple, the raw materials are easily available commercial raw materials, and the prepared core-shell structure pigment can be produced in small batches. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 XRD pattern of the raw material Zn2SiO4 powder;

[0026] Figure 2 XRD pattern of the Zn2SiO4@SiO2 powder prepared in Example 1;

[0027] Figure 3 XRD pattern of the Zn2SiO4@SiO2 powder prepared in Example 2;

[0028] Figure 4 XRD pattern of the Zn2SiO4@SiO2 powder prepared in Example 3;

[0029] Figure 5 XRD pattern of the Zn2SiO4@SiO2 powder prepared in Example 4;

[0030] Figure 6 TEM image of the raw material Zn2SiO4 powder;

[0031] Figure 7 TEM image of the Zn2SiO4@SiO2 powder prepared in Example 1;

[0032] Figure 8 TEM image of the Zn2SiO4@SiO2 powder prepared in Example 2;

[0033] Figure 9 TEM image of Zn2SiO4@SiO2 powder prepared in Example 1;

[0034] Figure 10 TEM image of Zn2SiO4@SiO2 powder prepared in Example 2;

[0035] Figure 11 Diffuse reflectance spectrum of Zn2SiO4@SiO2 powder prepared in Example 1;

[0036] Figure 12 Diffuse reflectance spectrum of Zn2SiO4@SiO2 powder prepared in Example 2;

[0037] Figure 13 Diffuse reflectance spectrum of Zn2SiO4@SiO2 based coating prepared in Example 2;

[0038] Figure 14 Diffuse reflectance spectrum of Zn2SiO4@SiO2 powder prepared in Example 3;

[0039] Figure 15 Diffuse reflectance spectrum of Zn2SiO4@SiO2 powder prepared in Example 4;

[0040] Figure 16 Diffuse reflectance spectrum of Zn2SiO4 based coating prepared in Comparative Example 1. DETAILED DESCRIPTION

[0041] The present application is further illustrated by the following examples, which are not intended to limit the present application.

[0042] In the present disclosure, the raw material composition of the core-shell structured pigment based thermal control coating with low absorption-emission ratio and anti-ultraviolet radiation includes core-shell structured pigment Zn2SiO4@SiO2 powder, potassium silicate inorganic binder and deionized water.

[0043] In an optional embodiment, the core-shell structured pigment Zn2SiO4@SiO2 powder is synthesized from Zn2SiO4 powder and tetraethyl orthosilicate (TEOS) by sol-gel method. The thickness of the shell structure SiO2 can be 16-37 nm. On one hand, the shell structure acts as a buffer layer, reflecting or stopping part of the ultraviolet rays in the SiO2 shell, which is equivalent to reducing the interaction of ultraviolet rays with the inner core pigment. On the other hand, after the ultraviolet rays passing through the shell structure damage the inner core pigment, the interface effect causes the accumulation of internal defects caused by ultraviolet radiation at the core-shell interface, increasing the recombination probability of electron-hole pairs.

[0044] The Zn2SiO4 powder is added into a mixed solution of anhydrous ethanol and water, and an appropriate amount of ammonia water is added to obtain a mixture 1. An appropriate amount of ball milling beads is added into the mixture 1 for wet ball milling, and the mass ratio of the mixture 1 to the ball milling beads is 0.5-2:1. The ball milling speed is 20-50 r / min, and the ball milling time is 2-5 h. The average particle size of the Zn2SiO4 powder is 50 nm-2 μm. The volume ratio of the anhydrous ethanol to the water in the mixed solution of the anhydrous ethanol and water is 60-95%, preferably 90%. The concentration of the ammonia water is 5-30 wt%, and the volume ratio of the amount of the ammonia water to the mixed solution of the anhydrous ethanol and water is 1:10-20.

[0045] TEOS is added into the mixture 1 after ball milling, and the ball milling is continued. The ball milling speed is 20-50 r / min, and the ball milling time is 2-5 h to obtain a mixture 2. The volume ratio of the TEOS to the mass of the Zn2SiO4 powder is 1-4 mL / g.

[0046] The mixture 2 is subjected to centrifugation, and the lower precipitate is taken out and then dried and heat treated to obtain a core-shell structure pigment Zn2SiO4@SiO2 powder. The centrifuge speed of the centrifuge used is 3000-7000 r / min, and the centrifugation time is 3-10 min.

[0047] The core-shell structure pigment Zn2SiO4@SiO2, a potassium silicate inorganic binder and water are uniformly mixed to form a coating slurry. The mass percentage of the core-shell structure pigment Zn2SiO4@SiO2 powder is 30-60%, the mass percentage of the potassium silicate and other inorganic binders is 30-60%, and the mass percentage of deionized water is 10-20%.

[0048] The coating slurry is sprayed on an alloy substrate after polishing treatment, and the spraying is performed for 3-6 times so that the total thickness of the coating is 120-200 μm. The interval time of each spraying is 20-60 min, and the spraying is solidified in air at room temperature. After the last spraying, the coating is dried in a drying oven to obtain a core-shell structure pigment Zn2SiO4@SiO2-based thermal control coating with low ratio and anti-ultraviolet radiation. The drying temperature is 40-120 °C, and the drying time is 2-12 h. The substrate material includes one of Al alloy, Cu alloy, titanium alloy, stainless steel and SiC-based composite material.

[0049] In the present application, the solar absorption ratio of the core-shell structure pigment-based thermal control coating with low ratio and anti-ultraviolet radiation is as low as 0.09, and the hemispherical emissivity is as high as 0.93, and the coating has stronger heat dissipation capacity. After 1500 ESH vacuum ultraviolet radiation in a ground space simulation, the change amount of the solar absorption ratio of the core-shell structure pigment Zn2SiO4@SiO2-based coating is reduced from 0.14 to 0.12 compared with the Zn2SiO4 pigment-based coating, and the ultraviolet radiation stability is significantly improved. The coating can be used as a high-heat-dissipation and long-life thermal control coating.

[0050] The following examples are further illustrated in detail to explain the present application. It should be understood that the following examples are only used to further illustrate the present application and cannot be understood as limiting the scope of protection of the present application. Some non-essential improvements and adjustments made by those skilled in the art according to the above content of the present application are within the scope of protection of the present application. The specific process parameters and the like described in the following examples are only one example in the appropriate range, i.e. those skilled in the art can select within the appropriate range according to the description herein, and are not limited to the specific values of the following examples.

[0051] Example 1

[0052] Zn2SiO4 powder, tetraethyl orthosilicate (TEOS, analytical pure), ammonia (analytical pure), and deionized water were used as raw materials. 50 g of Zn2SiO4 powder and 25 mL of ammonia were added to 450 mL of anhydrous ethanol and 50 mL of deionized water to form a solvent mixture, and then the mixture was subjected to drum ball milling for 2 h to obtain a uniformly dispersed Zn2SiO4 mixture solution with adsorbed -OH functional groups. 50 mL of TEOS was added to 200 mL of anhydrous ethanol, and the mixture was subjected to magnetic stirring for 1 h to obtain a uniformly dispersed TEOS precursor solution. The uniformly dispersed TEOS precursor solution was added to the Zn2SiO4 mixture solution with adsorbed -OH functional groups, and drum ball milling was continued for 3 h. After ball milling, the mixture was centrifuged at a speed of 5000 r / min using a centrifuge, and the lower layer of precipitate was removed and dried. The dried precipitate was then heated to 1000 ℃ at a heating rate of 5 ℃ / min, and then maintained at 1000 ℃ for 2 h. The furnace was then cooled to room temperature, and the powder was removed after cooling. The powder was then ground to obtain a core-shell structured pigment Zn2SiO4@SiO2. The XRD pattern of the prepared core-shell structured pigment Zn2SiO4@SiO2 is shown in Figure 2 , the TEM morphology is shown in Figure 7 , the thickness of the SiO2 layer is 16-18 nm, the diffuse reflectance spectrum is shown in Figure 11 , and the solar absorption is 0.04.

[0053] Example 2

[0054] Zn2SiO4 powder, tetraethyl orthosilicate (TEOS, analytical pure), ammonia (analytical pure), deionized water as raw materials. 50 g of Zn2SiO4 powder and 25 mL of ammonia were added to 450 mL of anhydrous ethanol and 50 mL of deionized water to form a solvent mixture, and then the mixture was subjected to drum ball milling for 2 h to obtain a uniform dispersion of Zn2SiO4 mixed solution with adsorbed -OH functional groups. 100 mL of TEOS was added to 200 mL of anhydrous ethanol, and the mixture was subjected to magnetic stirring for 1 h to obtain a uniform dispersion of TEOS precursor solution. The uniform dispersion of TEOS precursor solution was added to the Zn2SiO4 mixed solution with adsorbed -OH functional groups, and drum ball milling was continued for 3 h. After ball milling, the mixture was centrifuged at a speed of 5000 r / min, and the lower layer of the precipitate was removed, dried, and then heated to 1000℃ at a heating rate of 5℃ / min, and then kept at this temperature for 2 h, and then cooled to room temperature. After the powder was cooled, it was removed and ground to obtain the core-shell structure pigment Zn2SiO4@SiO2. The XRD pattern of the prepared core-shell structure pigment Zn2SiO4@SiO2 is shown in Figure 3 , the TEM morphology is shown in Figure 8 , the SiO2 layer thickness is 24-26 nm, the diffuse reflectance spectrum is shown in Figure 12 , and the solar absorption is 0.05.

[0055] The coating preparation process includes the following: the core-shell structure pigment Zn2SiO4@SiO2, potassium silicate inorganic binder and deionized water are mixed in a mass ratio of 30 g, 30 g and 5 g respectively, and subjected to magnetic stirring for 24 h to obtain a uniformly mixed coating slurry. The coating slurry was sprayed on the polished alloy substrate at room temperature, and the spraying was repeated 4 times with an interval of 1 h for solidification, and finally dried in a drying oven at 120℃ for 12 h to obtain a core-shell structure pigment-based coating test piece with a thickness of 180 μm. The diffuse reflectance spectrum of the prepared core-shell structure pigment-based coating is shown in Figure 13 , and the solar absorption is 0.09.

[0056] Example 3

[0057] Zn2Si04 powder, tetraethyl orthosilicate (TEOS, analytical pure), ammonia (analytical pure), deionized water as raw materials. The raw material 50 g of Zn2Si04 powder and 25 mL of ammonia were added to 450 mL of anhydrous ethanol and 50 mL of deionized water to mix, and then the mixture was subjected to drum ball milling for 2 h to obtain a uniformly dispersed Zn2Si04 mixture solution with adsorbed -OH functional groups. 150 mL of TEOS was added to 200 mL of anhydrous ethanol, and the mixture was subjected to magnetic stirring for 1 h to obtain a uniformly dispersed TEOS precursor solution. The uniformly dispersed TEOS precursor solution was added to the Zn2Si04 mixture solution with adsorbed -OH functional groups, and drum ball milling was continued for 3 h. After the ball milling, the mixture was centrifuged at a speed of 5000 r / min on a centrifuge, and the lower layer of the precipitate was taken out, dried, and then heated to 1000 ℃ at a heating rate of 5 ℃ / min, kept for 2 h, and then cooled to room temperature with the furnace. After the powder was cooled, it was taken out and ground to obtain a core-shell structure pigment Zn2Si04@Si02. The XRD pattern of the prepared core-shell structure pigment Zn2Si04@Si02 is shown in Figure 4 , the TEM morphology is shown in Figure 9 , the thickness of the Si02 layer is 35-37 nm, the diffuse reflectance spectrum is shown in Figure 14 , and the solar absorption is 0.05.

[0058] Example 4

[0059] Zn2Si04 powder, tetraethyl orthosilicate (TEOS, analytical pure), ammonia (analytical pure), deionized water as raw materials. The raw material 50 g of Zn2Si04 powder and 25 mL of ammonia were added to 450 mL of anhydrous ethanol and 50 mL of deionized water to mix, and then the mixture was subjected to drum ball milling for 2 h to obtain a uniformly dispersed Zn2Si04 mixture solution with adsorbed -OH functional groups. 150 mL of TEOS was added to 200 mL of anhydrous ethanol, and the mixture was subjected to magnetic stirring for 1 h to obtain a uniformly dispersed TEOS precursor solution. The uniformly dispersed TEOS precursor solution was added to the Zn2Si04 mixture solution with adsorbed -OH functional groups, and drum ball milling was continued for 3 h. After the ball milling, the mixture was centrifuged at a speed of 5000 r / min on a centrifuge, and the lower layer of the precipitate was taken out, dried, and then heated to 1000 ℃ at a heating rate of 5 ℃ / min, kept for 2 h, and then cooled to room temperature with the furnace. After the powder was cooled, it was taken out and ground to obtain a core-shell structure pigment Zn2Si04@Si02. The XRD pattern of the prepared core-shell structure pigment Zn2Si04@Si02 is shown in Figure 5 , the TEM morphology is shown in Figure 10 , the thickness of the Si02 layer is 22-24 nm, the diffuse reflectance spectrum is shown in Figure 15 , and the solar absorption is 0.06.

[0060] Comparative Example 1

[0061] The preparation process of the Zn2Si04-based coating includes the following:

[0062] The Zn2Si04pigment, potassium silicate inorganic binder and deionized water were mixed in a mass ratio of 30 g, 30 g and 5 g respectively, and magnetically stirred for 24 h to obtain a uniformly mixed coating slurry. The coating slurry was sprayed on the polished alloy substrate at room temperature, a total of 4 times, with a solidification time of 1 h between each spraying, and finally dried in a drying oven at 120°C for 12 h to obtain a Zn2Si04-based coating specimen with a thickness of 180 pm. The diffuse reflectance spectrum of the prepared Zn2Si04-based coating is shown in Figure 16 The solar absorption is 0.13.

[0063] Table 1 is the performance parameter of the core-shell structure pigment Zn2Si04@Si02-based coating of Example 2 before / after ground space simulation 1500 ESH vacuum ultraviolet irradiation:

[0064]

Claims

1. A method for preparing an ultraviolet radiation resistant core-shell structured pigment Zn2SiO4@SiO2 powder, characterized in that, The core-shell structure pigment Zn2SiO4@SiO2 powder comprises Zn2SiO4 particles and a SiO2 layer distributed on the surface of the Zn2SiO4 particles; The preparation method of the core-shell structure pigment Zn2SiO4@SiO2 powder comprises: (1) adding Zn2SiO4 powder into a mixed solution of anhydrous ethanol and water, first adding ammonia water and ball milling beads for ball milling treatment, and then adding TEOS for secondary ball milling treatment to obtain a suspension solution; wherein the volume ratio of the TEOS to the mass of the Zn2SiO4 powder is 1-4 mL / g; (2) centrifuging, drying and heat treating the obtained suspension solution to obtain the core-shell structure pigment Zn2SiO4@SiO2 powder; wherein the centrifugation rate is 3000-7000 r / min, and the centrifugation time is 3-10 min; the heat treatment temperature is 900-1100℃, and the heat treatment time is 1-3 hours.

2. The preparation method of the core-shell structure pigment Zn2SiO4@SiO2 powder according to claim 1, characterized in that, The particle size of the Zn2SiO4 particles is 50 nm-2 μm.

3. The preparation method of the core-shell structure pigment Zn2SiO4@SiO2 powder according to claim 1, characterized in that, The thickness of the SiO2 layer is 16-37 nm.

4. The method for preparing the core-shell structure pigment Zn2SiO4@SiO2 powder according to claim 1, characterized in that, The SiO2 layer is amorphous SiO2.

5. The preparation method of the core-shell structure pigment Zn2SiO4@SiO2 powder according to claim 1, characterized in that, The average particle size of the Zn2SiO4 powder is 50 nm-2 μm.

6. The method for preparing the core-shell structure pigment Zn2SiO4@SiO2 powder according to any one of claims 1-5, characterized in that, The volume ratio of anhydrous ethanol in the mixed solution of anhydrous ethanol and water is 60-95%; the purity of the anhydrous ethanol, the tetraethyl orthosilicate and the ammonia water is all superior grade.

7. The method according to claim 6, wherein the method is characterized by, The volume ratio of anhydrous ethanol in the mixed solution of anhydrous ethanol and water is 90%.

8. The method for preparing the core-shell structure pigment Zn2Si04@Si02 powder according to any one of claims 1-5, characterized in that, The rotation speed of the ball milling treatment is 20-50 r / min, and the total ball milling treatment time is 2-5 hours.

9. The method for preparing the core-shell structure pigment Zn2SiO4@SiO2 powder according to any one of claims 1-5, characterized in that, The drying temperature is 40-120℃, and the drying time is 2-12 hours; The heat treatment temperature is 1000℃, and the sintering time is 1-3 hours.

10. The method according to claim 9, wherein the method is characterized by, The heating rate of the heat treatment is 3-10℃ / min.

11. A core-shell structured pigment Zn2Si04@Si02-based thermal control coating, characterized in that, The core-shell structure pigment Zn2SiO4@SiO2 powder prepared by the preparation method of any one of claims 1-10 and an inorganic binder; the content of the core-shell structure pigment Zn2SiO4@SiO2 powder in the core-shell structure pigment Zn2SiO4@SiO2 based thermal control coating is 30-60 wt%.

12. The core-shell structured pigment Zn2SiO4@SiO2-based thermal control coating according to claim 11, characterized in that, The inorganic binder is selected from at least one of potassium silicate or sodium silicate.

13. The core-shell structured pigment Zn2Si04@Si02-based thermal control coating according to claim 11, characterized in that, The total thickness of the core-shell structure pigment Zn2SiO4@SiO2 based thermal control coating is 120-200 μm.

14. The core-shell structured pigment Zn2Si04@Si02-based thermal control coating according to any one of claims 11-13, characterized in that, The core-shell structure pigment Zn2SiO4@SiO2 based thermal control coating is formed on the surface of a base material, and the base material comprises one of Al alloy, Cu alloy, titanium alloy, stainless steel and SiC based composite material.

15. A method for preparing the core-shell structured pigment Zn2Si04@Si02-based thermal control coating according to any one of claims 11-14, characterized in that, The method comprises: (1) uniformly mixing the core-shell structure pigment Zn2SiO4@SiO2 powder, the inorganic binder and water to form a coating slurry; (2) spraying the obtained coating slurry on the surface of the abraded base material, and then drying to obtain the core-shell structure pigment Zn2SiO4@SiO2 based thermal control coating.

16. The method of claim 15, wherein, The mass percentage of the core-shell structure pigment Zn2SiO4@SiO2 in the coating slurry is 30-60%, the mass percentage of the inorganic binder is 30-60%, and the balance is water.

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