Ceramic etching solution, preparation method and application thereof, and etched ceramic

Abstract

The invention relates to the technical field of ceramic etching, and discloses a ceramic etching solution, a preparation method and application thereof, and etched ceramic. The etching solution contains H < + >, NH4 < + >, anions and polysaccharide, the molar concentration of H < + > in the etching solution is 3.0-5.1 mol / L, the molar concentration of NH4 < + > in the etching solution is 5.6-10.0 mol / L, and the mass fraction of polysaccharide in the etching solution is 3-8 wt%; h < + > is provided by inorganic acid; a main chain basic unit of the polysaccharide is a six-membered ring, and a side chain contains hydroxyl. The etching solution provided by the invention has simple and easily available components, has appropriate etching strength to ceramics, and can form an anchor bolt structure on the surface of the ceramics through one-step etching reaction, thereby being beneficial to effective combination of plastic and the ceramics.

Description

Technical Field

[0001] The invention relates to the technical field of ceramic etching, in particular to a ceramic etching liquid and a preparation method and application thereof, and etching ceramics. Background Art

[0002] Ceramics have been widely used in consumer electronics such as mobile phone structural parts and smart wearables in recent years because of their characteristics such as jade-like smooth touch, scratch and wear resistance, no signal shielding, excellent heat dissipation performance and polishability.

[0003] When applied to consumer electronics, ceramics and plastics are often combined. However, ceramics and plastics are very different, and simply physically combining the two cannot meet the application requirements.

[0004] To improve the bonding strength between plastic and ceramic, existing techniques typically involve chemically modifying the ceramic surface to create functional groups that react with the plastic, or chemically etching the ceramic surface to increase the surface area in contact with the plastic. However, due to the high hardness and strong corrosion resistance of ceramics, chemical modification is difficult to perform, making chemical etching the most common method. Current ceramic etching solutions, however, lack sufficient etching strength, requiring activation treatment before etching and surface treatment after etching, which is equivalent to multiple etching processes. Summary of the Invention

[0005] The purpose of the present invention is to overcome the problems of complicated etching process and insufficient etching strength of ceramic etching solution in the prior art.

[0006] In order to achieve the above object, the first aspect of the present invention provides a ceramic etching solution, which contains H + NH4 + , anions and polysaccharides;

[0007] The etching solution contains H + The molar concentration is 3.0-5.1 mol / L, NH4 + The molar concentration is 5.6-10.0 mol / L, and the mass fraction of polysaccharide is 3-8 wt%;

[0008] The H + Provided by inorganic acids;

[0009] The main chain basic unit of the polysaccharide is a six-membered ring, and the side chain contains a hydroxyl group.

[0010] A second aspect of the present invention provides a method for preparing the ceramic etching solution described in the first aspect, the method comprising:

[0011] In the presence of water, the inorganic acid, NH4 + The compound and the polysaccharide are subjected to a aging treatment to obtain a ceramic etching solution.

[0012] The third aspect of the present invention provides use of the ceramic etching solution described in the first aspect in etching zirconia ceramics.

[0013] The fourth aspect of the present invention provides an etched ceramic produced by the application described in the third aspect.

[0014] Compared with the prior art, the present invention has the following beneficial effects:

[0015] The components of the ceramic etching solution provided by the present invention work synergistically to remove the active phase in the ceramic. The microporous structure of appropriate depth formed on the ceramic surface effectively increases the roughness of the ceramic surface, increasing the bonding area between the ceramic and the plastic, allowing the plastic to penetrate these microporous structures and form a mechanical interlock. That is, after the plastic enters the pores on the metal oxide surface, it forms a chemical bond with the metal oxide, and combined with the mechanical force of the pores (the adsorption force brought about by the high specific surface area), it forms an anchoring effect. The ceramic etching solution provided by the present invention has high etching strength and does not require pre-etching activation treatment or post-etching surface treatment. The etching reaction is completed in a single step to form an anchoring structure on the ceramic surface.

[0016] The ceramic etching solution provided by the invention can cause uniform corrosion of ceramics.

[0017] The method for preparing a ceramic etching solution provided by the present invention has universal applicability and is convenient for large-scale production.

[0018] The etched ceramic surface provided by the present invention is honeycomb-shaped and has strong bonding force with plastic. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is a schematic diagram of the principle of etching ceramics with the ceramic etching solution provided by the present invention;

[0020] Figure 2 is the SEM image of unetched zirconia ceramic;

[0021] Figure 3 is a SEM image of the zirconia ceramic after being etched by the ceramic etching solution provided in Example 1 of the present invention;

[0022] Figure 4 This is a pore size analysis diagram of micropores produced after zirconia ceramics are etched with the ceramic etching solution provided in Example 1 of the present invention. DETAILED DESCRIPTION

[0023] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0024] As mentioned above, the first aspect of the present invention provides a ceramic etching solution containing H + NH4 + , anions and polysaccharides;

[0025] The etching solution contains H + The molar concentration is 3.0-5.1 mol / L, NH4 + The molar concentration is 5.6-10.0 mol / L, and the mass fraction of polysaccharide is 3-8 wt%;

[0026] The H + Provided by inorganic acids;

[0027] The main chain basic unit of the polysaccharide is a six-membered ring, and the side chain contains a hydroxyl group.

[0028] The components of the ceramic etching solution of the present invention work synergistically to remove the active phase from the ceramic. The resulting microporous structure of appropriate depth on the ceramic surface effectively increases the roughness of the ceramic surface, increasing the bonding area between the ceramic and the plastic. This allows the plastic to penetrate these microporous structures, creating a mechanical interlock. Specifically, after the plastic enters the pores on the metal oxide surface, it forms a chemical bond with the metal oxide, which, combined with the mechanical force of the pores (the adsorption force brought about by the high specific surface area), creates an anchoring effect. The ceramic etching solution provided by the present invention thus has high etching strength and eliminates the need for pre-etching activation treatment or post-etching surface treatment. The etching reaction is completed in a single step, forming an anchoring structure on the ceramic surface.

[0029] H in the etching solution of the present invention + Provided by inorganic acid, it provides an acidic environment and a strong ion environment for etching. Proton hydrogen will preferentially react with the active oxides in the ceramic to form a honeycomb surface with certain micropores. NH4 is added to the etching solution. + The main purpose is to adjust the pH of the etching solution to avoid excessive damage to the product surface by strong acid, and NH4 + The buffering effect reduces the drastic fluctuation of local pH, prevents the formation of passivation layers such as Zr(OH)4 on the product surface, and ensures uniform corrosion.

[0030] At the same time, polysaccharides are added to the ceramic etching solution, and the basic structural unit of the main chain is limited to a six-membered ring polysaccharide, so its main chain has a certain rigid structure, ensuring that it forms a stable network colloid in the solution, and the hydroxyl groups of the polysaccharide side chains are regularly distributed in space, enhancing the adsorption strength and coverage uniformity; the six-membered ring structure is preferentially adsorbed on the edge of the micropores generated by etching, inhibiting the further diffusion of active molecules through the steric hindrance effect, and through the specific concentration of H in the ceramic etching solution, the adsorption of the active molecules is enhanced. + NH4 + By combining with each other, the depth of micropores and the uniformity of micropore distribution can be effectively controlled.

[0031] The present invention Figure 1 The schematic diagram of the principle of ceramic etching liquid is provided as an example. The polysaccharide backbone provided by the polysaccharide in the ceramic etching liquid matches the anions and hydrogen ions, thereby achieving effective and uniform etching of the ceramic.

[0032] Preferably, the polysaccharide is selected from at least one of xanthan gum, starch, and gum arabic. The inventors of the present invention selected xanthan gum, starch, and gum arabic because xanthan gum, starch, and gum arabic are naturally occurring polysaccharides with a multi-hydroxy structure entangled with polymer chains. When dissolved in water, they form a colloid (hydroxyl groups provide hydrophilicity), which can increase the viscosity of the etching solution, allowing it to evenly adhere to the ceramic surface and ensure reaction uniformity. The entanglement and coverage of the hydroxyl polymer chains on the ceramic surface form a physical barrier (dynamic protective film), and the hydrogen bonds at the ends of the branched chains quickly guide the protons and anions in the etching solution to the exposed ceramic surface. The continuous alternation of shielding and traction causes the ceramic surface to exhibit regular erosion, forming a honeycomb surface. In addition, the raw materials are readily available and low in cost. Adding a small amount can achieve a thickening effect, effectively controlling costs. The material is non-toxic and has good biodegradability, which is in line with the development of environmentally friendly etching processes.

[0033] It should be noted that the selection of the above-mentioned polysaccharides is based only on the acquisition of raw materials and cost considerations, and several preferred substances are listed. The polysaccharides of this application only need to meet the requirements that the basic structural unit of the main chain is a six-membered ring, the side chain contains hydroxyl groups, and the etching system is stable.

[0034] Preferably, the anion comprises F - , and F in the etching solution - The molar concentration is 8.2-13.6 mol / L. The inventors of the present invention have discovered that in this preferred embodiment, fluoride ions have a strong electronegativity, causing fluoride ions to combine with protons to form hydrofluoric acid. Strong hydrogen bonding interactions exist between hydrofluoric acid molecules, which can selectively remove active phases in ceramics, increase the roughness of the ceramic inner surface, form a microporous structure, and increase the bonding area, thereby enabling the etched ceramic to have a higher specific surface area, thereby improving the bonding ability between the ceramic and the plastic.

[0035] It should be noted that the F - The molar concentration of (or F) includes both free and bound F - .

[0036] Preferably, the inorganic acid comprises HF and HCl. - and Cl - It can make the ceramic etching solution more penetrable, will preferentially adsorb on the ceramic surface, and can exclude oxygen atoms in active metal oxides (such as Fe2O3, Al2O3, etc.), accelerating the surface reaction; in addition, Cl - Can be combined with Zr 4+ Formation of soluble complex (ZrCl6 2- ), which can adjust the rate of dissolution of zirconium oxide in ceramics.

[0037] Preferably, the NH4 + The present inventors have found that, in this preferred embodiment, at least one of ammonium bifluoride, ammonium fluorosilicate, ammonium fluoride, and ammonium chloride is a uniform fine powder in the system environment, has a high specific surface area, can be quickly dispersed in the system, provides a sufficient source of soluble fluoride ions and chloride ions, stabilizes the HF or HCl concentration in the etching solution, can make the ceramic etching solution more stable, and extend the service life of the ceramic etching solution.

[0038] Preferably, the inorganic acid includes H2SO4 and H3PO4. The inventors of the present invention have discovered that, in this preferred embodiment, the phosphorus in the phosphate ions can combine with the zirconium atoms on the ceramic surface to form stable P-Zr-O covalent bonds. This bonding can destroy the original crystal structure of zirconium oxide, weaken its stability, and accelerate surface dissolution. When H2SO4 is mixed with other strong acids, it can enhance the formation of micro-nanoscale roughness, further regulating the etching rate, micropore depth, and uniformity of micropore distribution.

[0039] Preferably, the molar ratio of the HF to the HCl in the ceramic etching solution is (0.8-2.0): 1. The inventors of the present invention have found that in this preferred embodiment, the etching rate of the ceramic surface can be further adjusted.

[0040] Preferably, the molar ratio of the H2SO4 to the H3PO4 in the ceramic etching solution is 1:(1.3-3.2). The inventors of the present invention have found that in this preferred embodiment, the etching speed, micropore depth and uniformity of micropore distribution can be further adjusted.

[0041] As mentioned above, the second aspect of the present invention provides a method for preparing the ceramic etching solution described in the first aspect, the method comprising:

[0042] In the presence of water, the inorganic acid, NH4 + The compound and the polysaccharide are subjected to a aging treatment to obtain a ceramic etching solution.

[0043] Preferably, the aging treatment conditions include: a temperature of 35-45° C. and a stirring frequency of 30-50 Hz.

[0044] As mentioned above, the third aspect of the present invention provides the use of the ceramic etching solution described in the first aspect in etching ceramics.

[0045] According to a preferred embodiment, the application is carried out by a method comprising the following steps:

[0046] The ceramic etching liquid is used to etch the area to be etched in the ceramic to obtain the etched ceramic.

[0047] Preferably, the ceramic is one of zirconia ceramics, alumina ceramics and magnesia ceramics.

[0048] Preferably, the zirconia ceramic comprises: 85-95wt% ZrO2, 2-6wt% Y2O3, 1-3wt% HfO2, 1-3wt% Fe2O3, 0.5-1.5wt% Al2O3, 0.5-1.5wt% CoO, and 0.1-1wt% ZnO2.

[0049] Preferably, the etching treatment conditions include: temperature of 10-25° C. and time of 1-4 hours.

[0050] According to another preferred embodiment, before the etching process, the ceramic is first subjected to a degreasing process under ultrasonic conditions.

[0051] Preferably, the degreasing treatment is carried out using an alkaline detergent for 80-180 seconds.

[0052] According to another preferred embodiment, in order to remove alkaline detergent and impurities attached to the ceramic surface, after the degreasing treatment, the ceramic after the degreasing treatment is further washed with an acidic detergent and then water. Exemplarily, the acidic detergent washing time is 80-180 seconds.

[0053] The present invention has no special requirements for the selection of the alkaline detergent and the acidic detergent. Those skilled in the art can make their selections based on technical means known in the art. The present invention will not elaborate on them here, and those skilled in the art should not interpret them as limitations of the present invention.

[0054] Preferably, after the etching process, the etched ceramic is sequentially subjected to alkali washing, acid washing, water washing and drying.

[0055] The present invention has no particular restrictions on the conditions of the alkaline washing and the acid washing. It is only necessary to remove the impurities generated by the etching treatment and the residual ceramic etching solution on the ceramic surface after the etching treatment. Those skilled in the art can choose according to technical means known in the art, and the present invention will not elaborate on them here.

[0056] The present invention has no special requirements for the selection of the water, and those skilled in the art can select it as needed. For example, the water can be pure water or deionized water.

[0057] The present invention has no special requirements for the drying conditions, and those skilled in the art can select them as needed.

[0058] The present invention will be described in detail below through examples. In the following examples, unless otherwise specified, the raw materials are all commercially available.

[0059] HF: concentration is 40wt%, CAS: 7664-39-3.

[0060] HCl: concentration 36 wt%, CAS: 7647-01-0.

[0061] H2SO4: concentration is 40wt%, CAS: 7664-93-9.

[0062] H3PO4: concentration is 85wt%, CAS: 7664-38-2.

[0063] Ammonium bifluoride: NH4HF2, solid, CAS: 1341-49-7.

[0064] Ammonium fluorosilicate: (NH4)2SiF6, solid, CAS: 16919-19-0.

[0065] Ammonium fluoride: NH4F, solid, CAS: 12125-01-8.

[0066] Polysaccharides:

[0067] Starch: solid, CAS: 9005-25-8.

[0068] Xanthan gum: solid, CAS: 11138-66-2.

[0069] Gum Arabic: solid, CAS: 9000-01-5.

[0070] Inulin: solid, CAS: 9005-80-5.

[0071] The specific composition of the zirconia ceramic (45 mm × 18 mm × 2 mm) to be etched in the following example is: 90.15 wt% ZrO2, 3.88 wt% Y2O3, 1.85 wt% HfO2, 1.82 wt% Fe2O3, 0.98 wt% Al2O3, 0.84 wt% CoO, and 0.48 wt% ZnO2.

[0072] The calculation formulas for the contents of various ions and components in the ceramic etching solutions obtained in the following examples are as follows:

[0073] Example 1-8 Free NH4 in etching solution + The sources are ammonium bifluoride, ammonium fluorosilicate, ammonium fluoride, ammonium chloride, free H + The main source is the ionization of two strong electrolytes, sulfuric acid and hydrochloric acid, F - Mainly free F - and bound HF, HF2 - 、SiF6 2- The components in the etching solution undergo the following ionization reactions:

[0074]

[0075] HCl→H + +Cl -

[0076] (Ionization in a strong acid environment is suppressed, so it is ignored)

[0077] HF→H + +F - (Ionization in a strong acid environment is suppressed, so it is ignored)

[0078] Taking Example 1 as an example, a detailed calculation description is provided:

[0079] 1). Calculate the total volume of the solution:

[0080]

[0081] 2) Calculation Molar concentration:

[0082]

[0083] 3). Calculate free H + Molar concentration:

[0084]

[0085] 4). Calculate the molar concentration of total F:

[0086]

[0087] 5) Calculate the molar ratio of HF and HCl to be added:

[0088] 6). Calculate the molar ratio of added H2SO4 and H3PO4:

[0089] Example 1

[0090] This example is used to illustrate the preparation of a ceramic etching solution according to the following steps with reference to the formula in Table 1:

[0091] In the presence of pure water, inorganic acid, NH4 + The compound and polysaccharide were subjected to aging treatment (temperature 40°C, stirring frequency 50 Hz) to obtain a ceramic etching solution, which was named etching solution K1;

[0092] H in etching solution K1 + The molar concentration is 4.3 mol / L, NH4 + The molar concentration is 9.7 mol / L, and the mass fraction of polysaccharide is 3 wt%; F - The molar concentration is 12.2 mol / L, the molar ratio of HF and HCl is 0.8:1; the molar ratio of H2SO4 and H3PO4 is 1:1.6.

[0093] Example 2

[0094] This example was carried out using a method similar to that of Example 1, except that: the formula;

[0095] See Table 1 for details. The unlisted parts are the same as in Example 1. A ceramic etching solution is prepared and named etching solution K2.

[0096] H in etching solution K2 + The molar concentration is 3.7 mol / L, NH4 + The molar concentration is 6.9 mol / L, and the mass fraction of polysaccharide is 3 wt%; F - The molar concentration is 10.8 mol / L, the molar ratio of HF and HCl is 1.4:1; the molar ratio of H2SO4 and H3PO4 is 1:3.2.

[0097] Example 3

[0098] This example was carried out using a method similar to that of Example 1, except that: the formula;

[0099] See Table 1 for details. The unlisted parts are the same as in Example 1. A ceramic etching solution is prepared and named etching solution K3.

[0100] H in etching solution K3 + The molar concentration is 5.1 mol / L, NH4 + The molar concentration is 5.6 mol / L, and the mass fraction of polysaccharide is 4 wt%; - The molar concentration is 8.2 mol / L, the molar ratio of HF and HCl is 1:1; the molar ratio of H2SO4 and H3PO4 is 1:1.3.

[0101] Example 4

[0102] This example was carried out using a method similar to that of Example 1, except that: the formula;

[0103] See Table 1 for details. The unlisted parts are the same as in Example 1. A ceramic etching solution is prepared and named etching solution K4.

[0104] H in etching solution K4 + The molar concentration is 3.1 mol / L, NH4 + The molar concentration of F is 7.5 mol / L, and the mass fraction of polysaccharide is 8 wt%; - The molar concentration is 11.6 mol / L, the molar ratio of HF and HCl is 2:1; the molar ratio of H2SO4 and H3PO4 is 1:2.8.

[0105] Example 5

[0106] This example was carried out using a method similar to that of Example 1, except that: the formula;

[0107] See Table 1 for details. The unlisted parts are the same as in Example 1. A ceramic etching solution was prepared and named etching solution K5.

[0108] H in etching solution K5 + The molar concentration is 3.6 mol / L, NH4 + The molar concentration of F is 10.0 mol / L, and the mass fraction of polysaccharide is 5 wt%; - The molar concentration is 12.9 mol / L, the molar ratio of HF and HCl is 1:1; the molar ratio of H2SO4 and H3PO4 is 1:2.1.

[0109] Example 6

[0110] This example was carried out using a method similar to that of Example 1, except that: the formula;

[0111] See Table 1 for details. The unlisted parts are the same as in Example 1. A ceramic etching solution was prepared and named etching solution K6.

[0112] H in etching solution K6 + The molar concentration is 3.2 mol / L, NH4 + The molar concentration of F is 9.6 mol / L, and the mass fraction of polysaccharide is 5 wt%; - The molar concentration is 13.6 mol / L, the molar ratio of HF and HCl is 1.8:1; the molar ratio of H2SO4 and H3PO4 is 1:2.1.

[0113] Example 7

[0114] This example was carried out using a method similar to that of Example 1, except that: the formula;

[0115] See Table 1 for details. The unlisted parts are the same as in Example 1. A ceramic etching solution was prepared and named etching solution K7.

[0116] H in etching solution K7 + The molar concentration is 4.1 mol / L, NH4 + The molar concentration is 9.1 mol / L, and the mass fraction of polysaccharide is 5 wt%; F - The molar concentration is 12.7 mol / L, and the molar ratio of HF to HCl is 1.2:1.

[0117] Example 8

[0118] This example was carried out using a method similar to that of Example 1, except that: the formula;

[0119] See Table 1 for details. The unlisted parts are the same as in Example 1. A ceramic etching solution was prepared and named etching solution K8.

[0120] H in etching solution K8 + The molar concentration is 3.0 mol / L, NH4 + The molar concentration is 9.4 mol / L, and the mass fraction of polysaccharide is 5 wt%; - The molar concentration of HF is 13.0 mol / L, and the molar ratio of HF to HCl is 1.2:1.

[0121] Comparative Example 1

[0122] In the presence of 250 mL of pure water, 43 mL of HF was subjected to aging treatment (conditions were the same as in Example 1) to obtain a ceramic etching solution, which was named etching solution D-K1.

[0123] Comparative Example 2

[0124] In the presence of 215 mL of pure water, 43 mL of HF and 30 mL of HCl were aging treated (conditions were the same as in Example 1) to obtain a ceramic etching solution, which was named etching solution D-K2.

[0125] Comparative Example 3

[0126] In the presence of 111 mL of pure water, 39 mL of HF, 64 mL of HCl, 21 mL of H2SO4, 16 mL of H3PO4 and 15 g of starch were ripened (conditions were the same as in Example 1) to obtain a ceramic etching solution, named etching solution D-K3.

[0127] Comparative Example 4

[0128] This comparative example was carried out in a similar manner to Example 1, except that no polysaccharide was added in this comparative example;

[0129] The addition amounts of the remaining components identical to those in Example 1 were 1‰ of the corresponding components in Example 1 (i.e., 18 mL of pure water, 26.32 mL of HF, 63.56 mL of HCl, 27.69 mL of H2SO4, 15.98 mL of H3PO4, 54 g of NH4HF2, and 51 g of NH4F);

[0130] The unlisted parts are the same as in Example 1 to prepare a ceramic etching solution, which is named etching solution D-K4.

[0131] Comparative Example 5

[0132] This comparative example was carried out in a similar manner to Example 1, except that the amount of starch used in this comparative example was 30 g and the amount of xanthan gum used was 15 g;

[0133] The addition amounts of the remaining components identical to those in Example 1 were 1‰ of the corresponding components in Example 1 (i.e., 18 mL of pure water, 26.32 mL of HF, 63.56 mL of HCl, 27.69 mL of H2SO4, 15.98 mL of H3PO4, 54 g of NH4HF2, and 51 g of NH4F);

[0134] The unlisted parts are the same as in Example 1 to prepare a ceramic etching solution, named etching solution D-K5;

[0135] The mass fraction of polysaccharide in etching solution D-K5 is 15 wt %.

[0136] Comparative Example 6

[0137] This comparative example was carried out in a similar manner to Example 1, except that the amount of starch used in this comparative example was 1.5 g, and the amount of xanthan gum used was 1.5 g;

[0138] The addition amounts of the remaining components identical to those in Example 1 were 1‰ of the corresponding components in Example 1 (i.e., 18 mL of pure water, 26.32 mL of HF, 63.56 mL of HCl, 27.69 mL of H2SO4, 15.98 mL of H3PO4, 54 g of NH4HF2, and 51 g of NH4F);

[0139] The unlisted parts are the same as in Example 1, and a ceramic etching solution is prepared, which is named etching solution D-K6;

[0140] The mass fraction of polysaccharide in etching solution D-K6 is 1 wt %.

[0141] Comparative Example 7

[0142] This comparative example was carried out in a similar manner to Example 1, except that the starch and xanthan gum in Example 1 were replaced with inulin (9 g) in this comparative example.

[0143] The addition amounts of the remaining components identical to those in Example 1 were 1‰ of the corresponding components in Example 1 (i.e., 18 mL of pure water, 26.32 mL of HF, 63.56 mL of HCl, 27.69 mL of H2SO4, 15.98 mL of H3PO4, 54 g of NH4HF2, and 51 g of NH4F);

[0144] The unlisted parts are the same as in Example 1 to prepare a ceramic etching solution, which is named etching solution D-K7.

[0145] Table 1

[0146] Example 1 Example 2 Example 3 Example 4 Pure water / L 18 30 15 24 Inorganic acid HF / L 26.32 39.47 39.47 52.63 HCl / L 63.56 55.93 76.27 50.85 <![CDATA[H2SO4 / L]]> 27.69 18.46 23.08 13.85 <![CDATA[H3PO4 / L]]> 15.98 21.30 10.65 14.20 <![CDATA[Compound containing NH4 + > <![CDATA[NH4HF2 / KG]]> 54 90 36 / <![CDATA[NH4F / KG]]> 51 / / 48 <![CDATA[(NH4)2SiF6 / KG]]> / / 54 42 polysaccharides Starch / KG 6 6 / 15 Xanthan gum / KG 3 / 6 6 Gum Arabic / KG / 3 6 3

[0147] Table 1

[0148]

[0149]

[0150] Test Example 1

[0151] The ceramic etching solutions obtained in the above examples were applied to the etching of zirconia ceramics (each set of ceramic etching solutions was used to etch three pieces of zirconia ceramics in parallel). The specific method is as follows:

[0152] S1: Protect the non-etched area of ​​the zirconia ceramic with acid-resistant ink to expose the etched area;

[0153] S2: Under ultrasonic conditions, the zirconia ceramic is degreased (washed with an alkaline detergent for 120 seconds), and then the degreased zirconia ceramic is washed with an acidic detergent for 120 seconds and pure water in sequence;

[0154] S3: etching the zirconia ceramic after washing with pure water in step S2 (temperature is 20° C., time is 2 h), and then sequentially performing alkali washing, acid washing, pure water washing and drying to obtain etched zirconia ceramic.

[0155] 2. Each etched zirconia ceramic obtained in Test Example 1 was injection molded with plastic (specifically 50% glass fiber reinforced polyamide-6) (injection molding area 5*10mm). The combined samples were subjected to a pull-out force test using an Instron push-pull tester (test speed 10mm / min, 3 parallel runs, and the results were averaged). The results are shown in Table 2 (post-injection molding performance standard: basic pull-out force > 1000N was considered qualified):

[0156] Table 2

[0157]

[0158]

[0159] 3. The morphologies of the unetched zirconia ceramic and the etched zirconia ceramic obtained in Example 1 of Test Example 1 were analyzed using a scanning electron microscope. The results were as follows: Figure 2 and Figure 3 As shown in:

[0160] pass Figure 2 and Figure 3 It can be seen that before etching, the zirconia ceramics have almost no pores, and after etching, the surface structure presents a honeycomb shape.

[0161] 4. The pore size (diameter) of the micropores in the zirconia ceramic after etching obtained in Example 1 of Test Example 1 was analyzed using FIB (focused ion beam, microdissection instrument). The results are as follows: Figure 4 As shown:

[0162] pass Figure 4 It can be seen that the diameter of the holes after etching with the ceramic etching solution is between 540-1300 nm, thus ensuring that the etched zirconia ceramics are tightly bonded to the plastic.

[0163] From the above results, it can be seen that the ceramic etching solution provided by the present invention can form a suitable microporous structure on the ceramic surface through only one etching reaction, and can make the ceramic corroded evenly, and is particularly suitable for etching zirconia ceramics.

[0164] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A ceramic etching solution, characterized in that The etching solution contains H + NH4 + , anions and polysaccharides; The etching solution contains H + The molar concentration is 3.0-5.1 mol / L, NH4 + The molar concentration is 5.6-10.0 mol / L, and the mass fraction of polysaccharide is 3-8 wt%; The H + Provided by inorganic acids; The main chain basic unit of the polysaccharide is a six-membered ring, and the side chain contains a hydroxyl group.

2. The ceramic etching solution according to claim 1, characterized in that The polysaccharide is selected from at least one of xanthan gum, starch and gum arabic.

3. The ceramic etching solution according to claim 1, characterized in that The anions include F - , and F in the etching solution - The molar concentration is 8.2-13.6 mol / L.

4. The ceramic etching solution according to claim 1, wherein The inorganic acid includes HF and HCl; and / or, the NH4 + It is provided by at least one selected from ammonium bifluoride, ammonium fluorosilicate, ammonium fluoride, and ammonium chloride.

5. The ceramic etching solution according to claim 4, characterized in that The inorganic acids include H2SO4 and H3PO4.

6. The ceramic etching solution according to claim 5, wherein The molar ratio of the HF to the HCl in the ceramic etching solution is (0.8-2.0):1; And / or, the molar ratio of the H2SO4 to the H3PO4 in the ceramic etching solution is 1:(1.3-3.2).

7. A method for preparing the ceramic etching solution according to any one of claims 1 to 6, characterized in that: The method includes: In the presence of water, the inorganic acid, NH4 + The compound and the polysaccharide are subjected to a aging treatment to obtain a ceramic etching solution.

8. Use of the ceramic etching solution according to any one of claims 1 to 6 in etching ceramics.

9. The use according to claim 8, characterized in that The application is performed by a method comprising the following steps: The ceramic etching liquid is used to etch the area to be etched in the ceramic to obtain the etched ceramic.

10. Etched ceramics obtained by the use according to claim 8 or 9.

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