A jade decorative material and its preparation method

Abstract

This invention discloses a jade decorative material and its preparation method. The jade decorative material is prepared by melting, molding, and annealing etching waste mud containing calcium fluoride and additional raw materials. By mass percentage, the raw material composition of the jade decorative material includes: 14.30%–25.03% etching waste mud, wherein the etching waste mud contains calcium fluoride; and 74.97%–85.70% additional raw materials, wherein the additional raw materials include glass-forming substances, high-refractive-index substances, and coloring substances. This invention can effectively utilize harmful etching waste mud, achieve fluoride ion solidification treatment, reduce environmental risks, and obtain good economic benefits.

Description

Technical Field

[0001] This invention belongs to the field of waste mud resource utilization technology, and relates to a jade decorative material and its preparation method. Specifically, it relates to a jade decorative material prepared using etching waste mud containing calcium fluoride and its preparation method. Background Technology

[0002] Since the advent of foldable screen phones in 2018, sales have increased year by year. One of the keys to the folding effect of foldable screen phones lies in the screen protection material. The screen protection materials of foldable screen phones are usually CPI (transparent polyimide) and UTG (ultra-thin flexible glass, with a thickness of only 30 micrometers). Compared with CPI, UTG has better light transmittance, rigidity, and toughness, with less noticeable creases and better screen flatness when unfolded, without the obvious crease phenomenon of CPI.

[0003] Currently, foldable screen phones mostly use UTG as the cover material. UTG production methods include one-step molding and two-step molding. One-step molding is difficult to implement, so chemical thinning is widely used both domestically and internationally for UTG production. Chemical thinning involves etching the glass surface with hydrofluoric acid to achieve glass thinning. As the etching process increases, the HF concentration decreases, reducing the erosion ability and generating a large amount of etching waste liquid. This etching waste liquid contains a large amount of fluoride ions (F...). - If not handled properly and allowed to enter the soil, it can cause enormous harm to plants, animals, and even humans.

[0004] Chemical precipitation is currently the most common method for treating etching waste liquid. It involves adding a specific proportion of lime powder to the etching waste liquid, where the lime powder captures fluoride ions to form calcium fluoride. This method is simple to operate, low in cost, and effective. However, it generates a large amount of fluoride-containing etching sludge. Directly landfilling this sludge is costly and poses high safety risks, and there is also the risk of a small amount of uncaptured fluoride ions (F...). - The fluorine-containing etching sludge poses a significant risk of seeping into soil and water systems, therefore, effective resource recovery methods need to be studied.

[0005] Current research on the resource utilization of fluorine-containing etching waste sludge includes:

[0006] 1. Calcium fluoride is refined from fluorine-containing etching waste sludge, which is an efficient way to recover fluorine resources;

[0007] 2. Fluorine-containing etching waste sludge is added to cement-based composite materials to replace part of the cement. To ensure the working performance of the cement-based materials, the amount of fluorine-containing etching waste sludge added should be less than 10%.

[0008] 3. In synergy with other mineral raw materials, sintering is used to prepare ceramic materials;

[0009] 4. Melt it together with domestic waste sludge and broken glass to prepare microcrystalline glass;

[0010] 5. The fluorine-containing etching waste mud is incinerated in a harmless manner, and the ash residue from the incineration is used to prepare lightweight building aggregates.

[0011] 6. A highly efficient enhanced clinker mineralizer was prepared by synergistic mineralization of fluorine-containing etching waste sludge and trace heavy metal oxides.

[0012] 7. Synergistic preparation of artificial fluorite blocks with emulsified asphalt for use in steelmaking processes;

[0013] 8. Mesoporous silica materials were prepared using fluorine-containing etching waste sludge to adsorb hexamethyldisilazane.

[0014] Most of the above-mentioned resource utilization methods for fluorine-containing etching waste sludge have not been put into actual production applications, resulting in low comprehensive utilization rates of fluorine-containing etching waste sludge. Furthermore, some methods involve the release of fluoride ions (F...). - The solidification stability is poor, and it will migrate out under certain water or acid / alkali conditions. Therefore, it is necessary to study other more efficient and stable methods for treating fluorine-containing etching sludge. Summary of the Invention

[0015] To address the shortcomings of existing technologies, this invention provides a jade-like decorative material prepared from etching waste sludge containing calcium fluoride, along with its preparation method. It utilizes CaF2, the main component of the etching waste sludge, as a resource, leveraging its opaque properties in a glass matrix. With the addition of other raw materials, it is prepared into a milky, mutton-fat-colored or light blue jade-like decorative material. This material can replace high-grade decorative marble or artificial stone building materials, while simultaneously removing harmful fluoride ions (F...). - It is effectively solidified within it.

[0016] This invention discloses a jade decorative material, wherein the raw material composition of the jade decorative material, by weight percentage, includes:

[0017] The etching waste sludge comprises 14.30% to 25.03%; wherein the etching waste sludge contains calcium fluoride.

[0018] The added raw materials are 74.97% to 85.70%; wherein the added raw materials include glass-forming substances, high refractive index substances and coloring substances.

[0019] As a further improvement of the present invention, the mass fraction of calcium fluoride in the etching waste mud is 40% to 60%, and the remainder is calcium sulfate dihydrate.

[0020] As a further improvement of the present invention

[0021] The glass-forming materials include quartz sand, potassium feldspar, soda ash, anhydrous borax, zinc oxide, calcite, and sodium nitrate;

[0022] The high refractive index material includes cerium oxide and lanthanum oxide, with a refractive index of not less than 1.8;

[0023] The coloring substances include cobalt oxide, copper oxide, and iron oxide.

[0024] As a further improvement of the present invention, the potassium feldspar can be replaced by other raw materials that can provide Al2O3, and the anhydrous borax can be replaced by other raw materials that can provide B2O3.

[0025] As a further improvement of the present invention, the raw material composition of the jade decorative material, by weight percentage, includes: 14.30%–25.03% etching waste mud, 36.37%–41.57% quartz sand, 25.81%–29.50% potassium feldspar, 2.74%–3.13% soda ash, 1.65%–1.87% anhydrous borax, 1.56%–1.79% zinc oxide, 4.69%–5.36% calcite, 1.56%–1.79% sodium nitrate, 0.16%–0.18% cerium oxide, 0.23%–0.27% lanthanum oxide, 0.08%–0.09% copper oxide, 0.040%–0.044% cobalt oxide, and 0.08%–0.09% iron oxide.

[0026] As a further improvement of the present invention, the chemical composition of the jade decorative material, by mass percentage, includes: SiO2 62.78%–68.91%, Al2O3 6.41%–6.55%, Na2O 3.98%–4.43%, K2O 2.33%–2.70%, CaO 5.41%–7.20%, MgO 0.28%–0.37%, ZnO 2.00%–2.25%, B2O3 1.15%–1.35%, CaF2 7.41%–13.01%, CeO2+La2O3 0.46%–0.51%, and CuO+CoO+Fe2O3 0.32%–0.36%.

[0027] This invention also discloses a method for preparing jade decorative materials, comprising:

[0028] The etching waste sludge is pretreated, including drying, crushing and sieving.

[0029] Weigh the pretreated etching waste mud and the required external raw materials according to the preset ratio, mix them evenly, and obtain the batch material;

[0030] The batch materials are melted to obtain a melt;

[0031] The melt is shaped to obtain a shaped sample;

[0032] The molded sample is annealed to obtain a milky, mutton fat-colored or light blue jade decorative material.

[0033] As a further improvement of the present invention, the pretreatment of etching waste sludge includes:

[0034] The etching waste mud is placed in a dryer and dried to obtain dried etching waste mud blocks;

[0035] The dried etching waste mud blocks are put into a pulverizer and made into powder;

[0036] The pulverized powder is sieved to obtain powder with a mesh size of 40 to 100 and is ready for use.

[0037] As a further improvement of the present invention, the melting process parameters are: temperature of 1500℃~1560℃, and time of 3h~5h.

[0038] As a further improvement of the present invention, the annealing process parameters are as follows: first, the furnace is kept at 630℃~655℃ for 1h~2h, and then cooled to room temperature at 5℃ / min.

[0039] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0040] The jade decorative material produced by this invention exhibits excellent flexural strength, wear resistance, and chemical corrosion resistance, and is particularly effective against fluoride ions (F). - The curing effect meets the requirements, and the preparation process is simple, with high production efficiency, and can efficiently treat etching waste mud. Attached Figure Description

[0041] Figure 1 The XRD pattern of the etching waste mud used in this invention;

[0042] Figure 2 Physical images and comparative images of jade decorative materials with different amounts of etching waste mud prepared according to the present invention;

[0043] Figure 3 This is a schematic diagram illustrating the production technology of the jade decorative material prepared according to the present invention.

[0044] Figure 4 This is a comparison diagram of some physical and chemical properties of the jade decorative material prepared in Example 5 of the present invention with those of granite and marble;

[0045] Figure 5 Comparison of fluoride (F-) leaching amounts in jade decorative material samples with different amounts of etching waste mud prepared according to the present invention. Detailed Implementation

[0046] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0047] The present invention will now be described in further detail with reference to the accompanying drawings:

[0048] This invention provides a jade decorative material prepared using calcium fluoride-containing etching waste mud and its preparation method. The jade decorative material is prepared by melting, molding and annealing a compound material composed of calcium fluoride-containing etching waste mud and added raw materials. It can effectively utilize harmful etching waste mud, achieve fluoride ion solidification treatment, reduce environmental risks and obtain good economic benefits.

[0049] The raw material composition of the jade decorative material provided by this invention, by mass percentage, includes:

[0050] The etching waste sludge contains 14.30% to 25.03% calcium fluoride, preferably with a mass fraction of 40% to 60%, and the remainder is calcium sulfate dihydrate.

[0051] The added raw materials comprise 74.97%–85.70% of the total composition; these added raw materials include glass-forming substances, high-refractive-index substances, and coloring substances; specifically: the glass-forming substances include quartz sand, potassium feldspar, soda ash, anhydrous borax, zinc oxide, calcite, and sodium nitrate; the high-refractive-index substances include cerium oxide and lanthanum oxide, with a refractive index not less than 1.8; the coloring substances include cobalt oxide, copper oxide, and iron oxide, which are beneficial for forming cyan and opalescent colors. Furthermore, potassium feldspar can be replaced by other raw materials that can provide Al₂O₃, and anhydrous borax can be replaced by other raw materials that can provide B₂O₃.

[0052] The manufacturing mechanism of the jade decorative material of this invention utilizes the opaque phase separation effect of calcium fluoride in etching waste mud to increase the "concentration" of the opaque phase in the matrix glass, leading to a decrease in the solubility of high-refractive-index oxides and promoting the precipitation of high-refractive-index oxides. This creates a visible light scattering and interference effect, resulting in a jade-like appearance with a milky sheen and opacity. Figure 3 As shown, colorants are used to control the appearance color, making it achieve a more realistic appearance color effect.

[0053] Specifically:

[0054] The raw material composition of the jade decorative material, by weight percentage, includes: 14.30%–25.03% etching waste mud, 36.37%–41.57% quartz sand, 25.81%–29.50% potassium feldspar, 2.74%–3.13% soda ash, 1.65%–1.87% anhydrous borax, 1.56%–1.79% zinc oxide, 4.69%–5.36% calcite, 1.56%–1.79% sodium nitrate, 0.16%–0.18% cerium oxide, 0.23%–0.27% lanthanum oxide, 0.08%–0.09% copper oxide, 0.040%–0.044% cobalt oxide, and 0.08%–0.09% iron oxide.

[0055] The chemical composition of the jade decorative material, by mass percentage, includes: SiO2 62.78%–68.91%, Al2O3 6.41%–6.55%, Na2O 3.98%–4.43%, K2O 2.33%–2.70%, CaO 5.41%–7.20%, MgO 0.28%–0.37%, ZnO 2.00%–2.25%, B2O3 1.15%–1.35%, CaF2 7.41%–13.01%, CeO2+La2O3 0.46%–0.51%, and CuO+CoO+Fe2O3 0.32%–0.36%.

[0056] This invention provides a method for preparing jade decorative materials, comprising:

[0057] Step 1: Pre-treat the etching waste sludge:

[0058] The etching waste mud is placed in a dryer and dried to obtain dried etching waste mud blocks; the dried etching waste mud blocks are placed in a pulverizer to make powder; the pulverized powder is sieved to obtain 40-100 mesh powder for later use.

[0059] Step 2, Ingredients:

[0060] The main raw materials for this jade-like decorative material are quartz sand, potassium feldspar, soda ash, anhydrous borax, zinc oxide, calcite, sodium nitrate, cerium oxide, lanthanum oxide, copper oxide, cobalt oxide, iron oxide, and etching waste mud. The following percentages are weighed by mass: quartz sand 36.37%–41.57%, potassium feldspar 25.81%–29.50%, soda ash 2.74%–3.13%, anhydrous borax 1.65%–1.87%, zinc oxide 1.56%–1.79%, calcite 4.69%–5.36%, sodium nitrate 1.56%–1.79%, cerium oxide 0.16%–0.18%, lanthanum oxide 0.23%–0.27%, copper oxide 0.08%–0.09%, cobalt oxide 0.040%–0.044%, iron oxide 0.08%–0.09%, and etching waste mud from step 1 14.30%–25.03%.

[0061] Step 3, Mix:

[0062] The raw materials weighed in step 2 are mixed in a mixer to form a batch.

[0063] Step 4, Melting:

[0064] The batching materials are melted in a high-temperature furnace at 1500℃~1560℃ for 3h~5h to prepare a melt.

[0065] Step 5, Shaping:

[0066] The obtained melt is quickly poured into a heat-resistant mold for casting or rolled into a plate shape on a steel plate.

[0067] Step 6, Annealing:

[0068] The molded sample was placed in an annealing furnace at 630℃~655℃ and kept at 1h~2h, and then cooled to room temperature at 5℃ / min to prepare a milky mutton fat color or light blue jade decorative material.

[0069] Preferred embodiments of the present invention are given and described in detail.

[0070] Example 1:

[0071] A method for preparing jade decorative materials using etching waste mud specifically includes the following steps:

[0072] a. Place the etching waste mud in a drying oven at 105℃ for 3 hours to obtain dried etching waste mud blocks.

[0073] b. Place the dried etching waste mud blocks into a ball mill and grind them into powder.

[0074] c. The ground waste mud particles are sieved to obtain waste mud powder of 40-100 mesh; among which, the XRD pattern of the etching waste mud is as follows. Figure 1 As shown, the etching sludge contains calcium fluoride.

[0075] d. Ingredients: The glass batch is prepared by mass percentage of 41.57% quartz sand, 3.13% soda ash, 29.50% potassium feldspar, 1.79% sodium nitrate, 1.89% anhydrous borax, 1.79% zinc oxide, 5.36% calcite, 0.18% cerium oxide, 0.27% lanthanum oxide, 0.09% copper oxide, 0.040% cobalt oxide, 0.09% iron oxide, and 14.30% etching waste mud.

[0076] e. Mixing: Place the weighed batching materials on a mixer for 10 to 15 minutes and mix thoroughly.

[0077] f. Melting: The mixed batch materials are placed in a high-temperature furnace at 1560℃ and heated to melt for 3 hours to obtain the melt.

[0078] g. Molding: The obtained melt is quickly poured into a mold to obtain a shaped sample.

[0079] h. Annealing: Place the molded sample in an annealing furnace at 630℃ and hold for 2 hours, then cool it to room temperature at 5℃ / min to obtain the product.

[0080] Examples 2 to 6

[0081] A method for preparing jade decorative materials using etching waste mud, the specific raw material ratios and corresponding melting and annealing temperatures are shown in Table 1:

[0082] Table 1

[0083]

[0084] Except for the amount of waste sludge, the amount of added raw materials, the melting temperature and the annealing temperature in the table above, the rest of the steps are the same as in Example 1.

[0085] The chemical compositions of the jade decorative materials prepared in Examples 1 to 6 are shown in Table 2:

[0086] Table 2

[0087]

[0088] The raw material proportions, melting temperatures, and annealing temperatures of Comparative Examples 1 to 3 are shown in Table 3.

[0089] Table 3

[0090]

[0091]

[0092] The chemical compositions of the samples prepared in Comparative Examples 1 to 3 are shown in Table 4:

[0093] Table 4

[0094]

[0095] Depend on Figure 2 It can be seen that Example 1 of the present invention can produce a light blue jade decorative material, and Examples 2 to 6 can produce a milky mutton fat jade decorative material; the etching waste mud in the batch of Comparative Example 1 is 12.76%, and the prepared sample has relatively transparent edges and cannot achieve a good jade appearance color effect; the etching waste mud in the batch of Comparative Example 2 is 26.18%, and the sample surface is prone to cracks, making it difficult to use in actual production; the batch of Comparative Example 3 does not use high refractive index oxides (cerium oxide and lanthanum oxide), and the milky color of the produced sample is relatively poor.

[0096] The comparison diagram of some physicochemical properties of the jade decorative material prepared in Example 5 with granite and marble is shown below. Figure 4 As shown, jade decorative materials exhibit superior flexural strength, wear resistance, and chemical corrosion resistance compared to granite and marble.

[0097] The fluoride ions (F) in the jade decorative material samples prepared in Examples 1 to 4 - Leaching amount for example Figure 5 As shown.

[0098] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A jade decorative material, characterized in that, The raw material composition of the jade decorative material, by weight percentage, includes: Etching waste sludge 14.30%~25.03%; wherein, the etching waste sludge contains calcium fluoride; The added raw materials comprise 74.97%~85.70%; wherein, the added raw materials include glass-forming substances, high-refractive-index substances, and coloring substances; the high-refractive-index substances include cerium oxide and lanthanum oxide, with a refractive index not less than 1.8; the coloring substances include cobalt oxide, copper oxide, and iron oxide; by mass percentage, the raw material composition of the jade decorative material includes: etching waste mud 14.30%~25.03%, quartz sand 36.37%~41.57%, and potassium feldspar 25.81%. %~29.50%, soda ash 2.74%~3.13%, anhydrous borax 1.65%~1.87%, zinc oxide 1.56%~1.79%, calcite 4.69%~5.36%, sodium nitrate 1.56%~1.79%, cerium oxide 0.16%~0.18%, lanthanum oxide 0.23%~0.27%, copper oxide 0.08%~0.09%, cobalt oxide 0.040%~0.044%, iron oxide 0.08%~0.09%.

2. The jade decorative material as described in claim 1, characterized in that, The mass fraction of calcium fluoride in the etching sludge is 40%~60%.

3. The jade decorative material as described in claim 1, characterized in that, The potassium feldspar is replaced by other raw materials that can provide Al2O3, and the anhydrous borax is replaced by other raw materials that can provide B2O3.

4. The jade decorative material as described in any one of claims 1 to 3, characterized in that, The chemical composition of the jade decorative material, by mass percentage, includes: SiO2 62.78%~68.91%, Al2O3 6.41%~6.55%, Na2O 3.98%~4.43%, K2O 2.33%~2.70%, CaO 5.41%~7.20%, MgO 0.28%~0.37%, ZnO 2.00%~2.25%, B2O3 1.15%~1.35%, CaF2 7.41%~13.01%, CeO2+La2O3 0.46%~0.51%, and CuO+CoO+Fe2O3 0.32%~0.36%.

5. A method for preparing a jade decorative material as described in any one of claims 1 to 4, characterized in that, include: The etching waste sludge is pretreated, including drying, crushing and sieving. Weigh the pretreated etching waste mud and the required external raw materials according to the preset ratio, mix them evenly, and obtain the batch material; The batch materials are melted to obtain a melt; The melt is shaped to obtain a shaped sample; The molded sample is annealed to obtain a milky, mutton fat-colored or light blue jade decorative material.

6. The method for preparing jade decorative material as described in claim 5, characterized in that, The pretreatment of etching waste sludge includes: The etching waste mud is placed in a dryer and dried to obtain dried etching waste mud blocks; The dried etching waste mud blocks are put into a crusher and made into powder; The pulverized powder is sieved to obtain powder with a mesh size of 40-100 and set aside for later use.

7. The method for preparing jade decorative material as described in claim 5, characterized in that, The melting process parameters are: temperature 1500℃~1560℃, time 3h~5h.

8. The method for preparing jade decorative material as described in claim 5, characterized in that, The annealing process parameters are as follows: first, hold the annealing furnace at 630℃~655℃ for 1h~2h, and then cool it to room temperature at 5℃ / min.

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