Preparation and sintering process of black zirconia composite material

Abstract

This application discloses a preparation and sintering process for a black zirconia composite material, belonging to the technical field of ceramic product preparation processes. The key technical steps include: S1, mixing recycled zirconia, zirconia, and graphene in a weight percentage ratio of (15-20):(70-75):(5-10); S2, uniformly mixing the mixed recycled zirconia, zirconia, and graphene in a ball mill, and then spray-drying the milled mixture to obtain a primary powder; S3, uniformly mixing the primary powder, black pigment, binder, and dispersant, pre-pressing the mixture using a mold, and then performing warm isostatic pressing to obtain a green body; S4, debinding and sintering the pressed green body to obtain the black zirconia composite material; S5, cooling after sintering. This application can increase the utilization rate of recycled zirconia, improve resource utilization, and ensure the color uniformity of the black zirconia composite material.

Description

Technical Field

[0001] This application belongs to the field of ceramic product preparation technology, and particularly relates to a preparation and sintering process of a black zirconia composite material. Background Technology

[0002] In recent years, with the development of black zirconia ceramics, they have been increasingly used in electronic products, decorations, household goods, medical applications, piezoelectric ceramics, and sensor ceramics, such as mobile phone casings, watch casings, and knives. There are two main traditional processes for preparing black zirconia ceramics: one is the vacuum blackening method, which generally requires a blackening temperature of around 1500℃. This method is relatively high, and the fired product often exhibits varying degrees of red and white discoloration, resulting in poor blackness. The other method involves adding black pigments to the zirconia matrix.

[0003] A Chinese patent with publication number CN108640678B discloses a black zirconia ceramic material, a method for preparing black zirconia ceramic, and an article thereof. The black zirconia ceramic material comprises the following components by weight percentage: 80%–95% zirconia; 2.5%–5% yttrium oxide; and the balance of black pigment. The black pigment comprises the following components by weight percentage: 0–40% iron oxide, 0–30% chromium oxide, 10%–30% cobalt oxide, 0–10% manganese oxide, 0–10% nickel oxide, 5%–30% aluminum oxide, 0–6% zinc oxide, and 0–5% silicon oxide. The weight percentages of iron oxide, chromium oxide, cobalt oxide, manganese oxide, nickel oxide, aluminum oxide, zinc oxide, and silicon oxide are percentages of the total weight of the black pigment.

[0004] Although the above preparation method produces a pure color and high blackness after sintering, with increasing emphasis on the ecological environment and the need for sustainable development, research on material preparation processes has led to the addition of recycled zirconia materials to improve the utilization rate of raw materials in order to increase the recycling of zirconia. However, after sintering and grinding, the recycled zirconia materials have low purity and activity. Due to limitations in the sintering process, it is difficult to ensure the color uniformity of black zirconia composite materials by adding different proportions of recycled zirconia materials. Summary of the Invention

[0005] The purpose of this application is to address the aforementioned technical problems by providing a preparation and sintering process for black zirconia composite materials, which increases the utilization rate of recycled zirconia materials, improves resource utilization, and ensures the color uniformity of the black zirconia composite materials.

[0006] This application provides a preparation and sintering process for a black zirconia composite material, the specific steps of which include:

[0007] S1, take zirconium oxide recycled material, zirconium oxide and graphene and mix them in the following weight percentage: (15-20): (70-75): (5-10);

[0008] S2, the well-mixed zirconium oxide recycled material, zirconium oxide and graphene mixture are put into a ball mill and mixed evenly. The ball-milled mixture is then made into primary powder by spray drying technology.

[0009] S3, the primary powder, black pigment, binder and dispersant are uniformly mixed, pre-pressed with a mold and subjected to warm isostatic pressing to obtain a green body;

[0010] S4, the statically pressed green body is debonded and sintered to obtain a black zirconium oxide composite material;

[0011] S5, after sintering, is cooled down;

[0012] In step S4, the sintering temperature is controlled between 1350-1550℃, and the holding time is 2-6 hours.

[0013] Furthermore, in step S1, the zirconium oxide recycled material is obtained by thoroughly washing with hydrochloric acid and then calcining at 700°C.

[0014] Furthermore, in step S2, the primary powder particle size is below 80 nm.

[0015] Furthermore, in step S3, the black pigment is made of iron oxide, chromium oxide, cobalt oxide, manganese oxide, nickel oxide, aluminum oxide, zinc oxide, and silicon oxide.

[0016] Furthermore, in step S3, the pressing parameters for isostatic pressing are: temperature 100℃-150℃, isostatic pressure 200-300MPa, and holding time 150-180min.

[0017] Furthermore, in step S3, the dispersant is 3%-5% of the weight of the primary powder, and the dispersant is one or more of poly(amino methacrylate), ammonium polyacrylate, sodium tripolyphosphate, polyethylene glycol, and sodium hexametaphosphate.

[0018] Furthermore, in step S4, the temperature for dispensing the adhesive is 800℃-900℃, and the dispensing time is 40h-80h.

[0019] Furthermore, in step S4, the heating rate of the sintering temperature is controlled at 10-25℃ / minute, and the heating is stopped for 10 minutes after every 100℃ increase.

[0020] Furthermore, in step S4, the cooling rate is first controlled at 1-3℃ / 5 minutes to cool down to 550℃, then controlled at 2-5℃ / minute to cool down to 100℃, and finally cooled down to room temperature.

[0021] The beneficial effects of this application are:

[0022] 1. By processing recycled zirconium oxide, zirconium oxide, and graphene through sand milling, and then mixing with black pigment, the mixture is successively molded, debinded, sintered, and cooled to obtain a black zirconium oxide composite material.

[0023] 2. The mixture of zirconium oxide recycled material, zirconium oxide, and graphene is ground in a ball mill to improve grinding efficiency. At the same time, the graphene is uniformly mixed with the zirconium oxide recycled material and zirconium oxide to improve the activity of the zirconium oxide recycled material during sintering and improve the uniformity of color.

[0024] 3. Adding graphene can also prevent cracking of products and improve the excellent mechanical properties of black zirconia composite materials.

[0025] 4. By setting stable heating and cooling rates, the stable activation of the recycled zirconium oxide material is ensured, preventing product cracking. Attached Figure Description

[0026] Figure 1 This is a process flow diagram of the preparation and sintering process of the black zirconium oxide composite material of this application; Detailed Implementation

[0027] The technical solutions of the embodiments of this application will be clearly described below with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of this application. All other embodiments obtained by those skilled in the art based on the embodiments of this application are within the scope of protection of this application.

[0028] The terms "first," "second," etc., used in the specification and claims of this application are used to distinguish similar objects and not to describe a specific order or sequence. It should be understood that such use of data can be interchanged where appropriate so that embodiments of this application can be implemented in orders other than those illustrated or described herein, and the objects distinguished by "first," "second," etc., are generally of the same class and the number of objects is not limited; for example, a first object can be one or more. Furthermore, in the specification and claims, "and / or" indicates at least one of the connected objects, and the character " / " generally indicates that the preceding and following objects are in an "or" relationship.

[0029] The embodiments of this application are described in detail below with reference to the accompanying drawings, through specific examples and application scenarios.

[0030] Example 1:

[0031] A preparation and sintering process for a black zirconia composite material is provided, the specific steps of which include:

[0032] S1, take zirconium oxide recycled material, zirconium oxide and graphene and mix them in a weight percentage of 15:70:5;

[0033] S2, the well-mixed zirconium oxide recycled material, zirconium oxide and graphene mixture are put into a ball mill and mixed evenly. The ball-milled mixture is then made into primary powder by spray drying technology.

[0034] S3, the primary powder, black pigment, binder and dispersant are uniformly mixed, pre-pressed with a mold and subjected to warm isostatic pressing to obtain a green body;

[0035] S4, the statically pressed green body is debonded and sintered to obtain a black zirconium oxide composite material;

[0036] S5, after sintering, is cooled down;

[0037] In step S4, the sintering temperature is controlled at 1400℃ and the holding time is 4 hours.

[0038] Furthermore, in step S1, the zirconium oxide recycled material is obtained by thoroughly washing with hydrochloric acid and then calcining at 700°C.

[0039] Furthermore, in step S2, the primary powder particle size is below 80 nm.

[0040] Furthermore, in step S3, the black pigment is made of iron oxide, chromium oxide, cobalt oxide, manganese oxide, nickel oxide, aluminum oxide, zinc oxide, and silicon oxide.

[0041] Furthermore, in step S3, the pressing parameters for isostatic pressing are: temperature 100℃, isostatic pressure 250MPa, and holding time 160min.

[0042] Furthermore, in step S3, the dispersant is 3% of the weight of the primary powder, and the dispersant is one or more of poly(amino methacrylate), ammonium polyacrylate, sodium tripolyphosphate, polyethylene glycol, and sodium hexametaphosphate.

[0043] Furthermore, in step S4, the temperature for dispensing the adhesive is 800℃, and the dispensing time is 40 hours.

[0044] Furthermore, in step S4, the heating rate of the sintering temperature is first controlled at 10°C / minute, and the heating is stopped for 10 minutes after every 100°C increase.

[0045] Furthermore, in step S4, the cooling rate is first controlled at 1℃ / 5 minutes to cool down to 550℃, then controlled at 2℃ / minute to cool down to 100℃, and finally cooled down to room temperature.

[0046] Example 2:

[0047] A preparation and sintering process for a black zirconia composite material is provided, the specific steps of which include:

[0048] S1, take zirconium oxide recycled material, zirconium oxide and graphene and mix them in a weight percentage of 15:75:5;

[0049] S2, the well-mixed zirconium oxide recycled material, zirconium oxide and graphene mixture are put into a ball mill and mixed evenly. The ball-milled mixture is then made into primary powder by spray drying technology.

[0050] S3, the primary powder, black pigment, binder and dispersant are uniformly mixed, pre-pressed with a mold and subjected to warm isostatic pressing to obtain a green body;

[0051] S4, the statically pressed green body is debonded and sintered to obtain a black zirconium oxide composite material;

[0052] S5, after sintering, is cooled down;

[0053] In step S4, the sintering temperature is controlled at 1400℃ and the holding time is 4 hours.

[0054] Furthermore, in step S1, the zirconium oxide recycled material is obtained by thoroughly washing with hydrochloric acid and then calcining at 700°C.

[0055] Furthermore, in step S2, the primary powder particle size is below 80 nm.

[0056] Furthermore, in step S3, the black pigment is made of iron oxide, chromium oxide, cobalt oxide, manganese oxide, nickel oxide, aluminum oxide, zinc oxide, and silicon oxide.

[0057] Furthermore, in step S3, the pressing parameters for isostatic pressing are: temperature 100℃, isostatic pressure 250MPa, and holding time 160min.

[0058] Furthermore, in step S3, the dispersant is 3% of the weight of the primary powder, and the dispersant is one or more of poly(amino methacrylate), ammonium polyacrylate, sodium tripolyphosphate, polyethylene glycol, and sodium hexametaphosphate.

[0059] Furthermore, in step S4, the temperature for dispensing the adhesive is 800℃, and the dispensing time is 40 hours.

[0060] Furthermore, in step S4, the heating rate of the sintering temperature is first controlled at 10°C / minute, and the heating is stopped for 10 minutes after every 100°C increase.

[0061] Furthermore, in step S4, the cooling rate is first controlled at 2℃ / 5 minutes to cool down to 550℃, then controlled at 3℃ / minute to cool down to 100℃, and finally cooled down to room temperature.

[0062] Example 3:

[0063] A preparation and sintering process for a black zirconia composite material is provided, the specific steps of which include:

[0064] S1, take zirconium oxide recycled material, zirconium oxide and graphene and mix them in a weight percentage of 20:75:5;

[0065] S2, the well-mixed zirconium oxide recycled material, zirconium oxide and graphene mixture are put into a ball mill and mixed evenly. The ball-milled mixture is then made into primary powder by spray drying technology.

[0066] S3, the primary powder, black pigment, binder and dispersant are uniformly mixed, pre-pressed with a mold and subjected to warm isostatic pressing to obtain a green body;

[0067] S4, the statically pressed green body is debonded and sintered to obtain a black zirconium oxide composite material;

[0068] S5, after sintering, is cooled down;

[0069] In step S4, the sintering temperature is controlled at 1400℃ and the holding time is 4 hours.

[0070] Furthermore, in step S1, the zirconium oxide recycled material is obtained by thoroughly washing with hydrochloric acid and then calcining at 700°C.

[0071] Furthermore, in step S2, the primary powder particle size is below 80 nm.

[0072] Furthermore, in step S3, the black pigment is made of iron oxide, chromium oxide, cobalt oxide, manganese oxide, nickel oxide, aluminum oxide, zinc oxide, and silicon oxide.

[0073] Furthermore, in step S3, the pressing parameters for isostatic pressing are: temperature 100℃, isostatic pressure 250MPa, and holding time 160min.

[0074] Furthermore, in step S3, the dispersant is 3%-5% of the weight of the primary powder, and the dispersant is one or more of poly(amino methacrylate), ammonium polyacrylate, sodium tripolyphosphate, polyethylene glycol, and sodium hexametaphosphate.

[0075] Furthermore, in step S4, the temperature for dispensing the adhesive is 800℃, and the dispensing time is 40 hours.

[0076] Furthermore, in step S4, the heating rate of the sintering temperature is initially controlled at 15°C / minute, and the heating is stopped for 10 minutes after every 100°C increase.

[0077] Furthermore, in step S4, the cooling rate is first controlled at 2℃ / 5 minutes to cool down to 550℃, then controlled at 3℃ / minute to cool down to 100℃, and finally cooled down to room temperature.

[0078] Example 4:

[0079] A preparation and sintering process for a black zirconia composite material is provided, the specific steps of which include:

[0080] S1, take zirconium oxide recycled material, zirconium oxide and graphene and mix them in a weight percentage of 20:70:10;

[0081] S2, the well-mixed zirconium oxide recycled material, zirconium oxide and graphene mixture are put into a ball mill and mixed evenly. The ball-milled mixture is then made into primary powder by spray drying technology.

[0082] S3, the primary powder, black pigment, binder and dispersant are uniformly mixed, pre-pressed with a mold and subjected to warm isostatic pressing to obtain a green body;

[0083] S4, the statically pressed green body is debonded and sintered to obtain a black zirconium oxide composite material;

[0084] S5, after sintering, is cooled down;

[0085] In step S4, the sintering temperature is controlled at 1500℃ and the holding time is 5 hours.

[0086] Furthermore, in step S1, the zirconium oxide recycled material is obtained by thoroughly washing with hydrochloric acid and then calcining at 700°C.

[0087] Furthermore, in step S2, the primary powder particle size is below 80 nm.

[0088] Furthermore, in step S3, the black pigment is made of iron oxide, chromium oxide, cobalt oxide, manganese oxide, nickel oxide, aluminum oxide, zinc oxide, and silicon oxide.

[0089] Furthermore, in step S3, the pressing parameters for isostatic pressing are: temperature 140℃, isostatic pressure 260MPa, and holding time 160min.

[0090] Furthermore, in step S3, the dispersant is 5% of the weight of the primary powder, and the dispersant is one or more of poly(amino methacrylate), ammonium polyacrylate, sodium tripolyphosphate, polyethylene glycol, and sodium hexametaphosphate.

[0091] Furthermore, in step S4, the temperature for dispensing the adhesive is 850℃, and the dispensing time is 70h.

[0092] Furthermore, in step S4, the heating rate of the sintering temperature is first controlled at 20°C / minute, and the heating is stopped for 10 minutes after every 100°C increase.

[0093] Furthermore, in step S4, the cooling rate is first controlled at 2℃ / 5 minutes to cool down to 550℃, then controlled at 3℃ / minute to cool down to 100℃, and finally cooled down to room temperature.

[0094] Below, we will conduct experiments to observe the appearance of the black zirconia composite materials prepared in Examples 1-4 above. The product surfaces are all smooth and intact, without cracks, warping, or other phenomena. We will also test the density, bending strength, Vickers hardness, and color uniformity. The test results are shown in Table 1.

[0095] Table 1. Performance test results of black zirconium oxide composite materials

[0096] Example 1 6.03 1575 1201 1.2 Example 2 6.04 1581 1210 1.3 Example 3 6.04 1583 1214 0.7 Example 4 6.05 1592 1013 0.8

[0097] As can be seen from Table 1, the smaller the color uniformity ΔE value, the higher the uniformity. The black zirconia composite material prepared by this invention has excellent mechanical properties. When using recycled zirconia material, it is necessary to add an appropriate amount of graphene material to improve the color uniformity of the black zirconia composite material.

[0098] It should be noted that, in this document, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitations, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes that element. Furthermore, it should be noted that the scope of the methods and apparatuses in the embodiments of this application is not limited to performing functions in the order shown or discussed, but may also include performing functions substantially simultaneously or in the reverse order, depending on the functions involved. For example, the described methods may be performed in a different order than described, and various steps may be added, omitted, or combined. Additionally, features described with reference to certain examples may be combined in other examples.

[0099] The embodiments of this application have been described above with reference to the accompanying drawings. However, this application is not limited to the specific embodiments described above. The specific embodiments described above are merely illustrative and not restrictive. Those skilled in the art can make many other forms under the guidance of this application without departing from the spirit and scope of the claims, and all of these forms are within the protection scope of this application.

Claims

1. A process for the preparation and sintering of black zirconia composites, characterized in that, The specific steps include: S1, take zirconium oxide recycled material, zirconium oxide and graphene and mix them in the following weight percentage: (15-20): (70-75): (5-10); S2, the well-mixed zirconium oxide recycled material, zirconium oxide and graphene mixture are put into a ball mill and mixed evenly. The ball-milled mixture is then made into primary powder by spray drying technology. S3, the primary powder, black pigment, binder and dispersant are uniformly mixed, pre-pressed with a mold and subjected to warm isostatic pressing to obtain a green body; S4, the green body obtained by warm isostatic pressing is debinding and sintering; S5, after sintering, is cooled to obtain a black zirconia composite material; In step S4, the sintering temperature is controlled between 1350-1550℃, and the holding time is 2-6 hours. In step S3, the pressing parameters for isostatic pressing are: temperature 100℃-150℃, isostatic pressure 200-300MPa, and holding time 150-180min. In step S4, the heating rate of the sintering temperature is first controlled at 10-25℃ / minute, and the heating is stopped for 10 minutes every 100℃ increase. In step S4, the cooling rate is first controlled at 1-3℃ / 5 minutes to cool down to 550℃, then the cooling rate is controlled at 2-5℃ / minute to cool down to 100℃, and finally the temperature is cooled down to room temperature. In step S1, the zirconium oxide recycled material is obtained by thoroughly washing with hydrochloric acid and then calcining at 700°C. In step S3, the black pigment is made of iron oxide, chromium oxide, cobalt oxide, manganese oxide, nickel oxide, aluminum oxide, zinc oxide, and silicon oxide. In step S4, the temperature for dispensing the adhesive is 800℃-900℃, and the dispensing time is 40h-80h.

2. The process for preparation and sintering of black zirconia composites as claimed in claim 1 wherein, In step S2, the primary powder particle size is below 80 nm.

3. The process for preparation and sintering of black zirconia composites as claimed in claim 1 wherein, In step S3, the dispersant is 3%-5% of the weight of the primary powder, and the dispersant is one or more of poly(amino methacrylate), ammonium polyacrylate, sodium tripolyphosphate, polyethylene glycol, and sodium hexametaphosphate.

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