阅读说明：本技术 一种无机材料充填翡翠的方法 (Method for filling inorganic material into jadeite ) 是由 杨春梅 陆太进 潘迪 陶震东 于 2021-09-23 设计创作，主要内容包括：本发明公开了一种无机材料充填翡翠的方法,属于翡翠充填领域。该方法包括以下步骤：(1)将固化剂加入硅酸钠水溶液中,搅拌均匀,得到混合液；(2)将经过酸洗碱洗后的翡翠浸入混合液中,室温静置后在120-130℃温度下固化或直接置于真空箱中抽真空,室温静置固化；其中,所述固化剂为氯化钙和氟硅酸钠的混合物、聚合磷酸铝、磷酸硅三者中的至少一种。本发明采用配制的无机材料充填翡翠,提高了翡翠的品质,原本低档的翡翠经过无机材料的充填处理后,使结构松散的翡翠变得更加致密,经过抛光后,翡翠的光泽增强,起到改善外观的作用,同时弥补了有机物充填翡翠不具备抗氧化性及耐火性的缺陷。(The invention discloses a method for filling jadeite with inorganic materials, and belongs to the field of jadeite filling. The method comprises the following steps: (1) adding a curing agent into a sodium silicate aqueous solution, and uniformly stirring to obtain a mixed solution; (2) immersing jade washed by acid-washing alkali into the mixed solution, standing at room temperature, curing at the temperature of 120-130 ℃ or directly placing in a vacuum box for vacuumizing, and standing and curing at room temperature; wherein the curing agent is at least one of a mixture of calcium chloride and sodium fluosilicate, polymerized aluminum phosphate and silicon phosphate. According to the invention, the prepared inorganic material is adopted to fill the jadeite, so that the quality of the jadeite is improved, the originally low-grade jadeite is subjected to filling treatment of the inorganic material, so that the jadeite with a loose structure becomes more compact, the luster of the jadeite is enhanced after polishing, the effect of improving the appearance is achieved, and the defects that the organic matter filled jadeite does not have oxidation resistance and fire resistance are overcome.)

1. A method for filling jade with inorganic materials is characterized by comprising the following steps:

(1) adding a curing agent into a sodium silicate aqueous solution, and uniformly stirring to obtain a mixed solution;

(2) immersing jade washed by acid-washing alkali into the mixed solution, standing at room temperature, curing at the temperature of 120-130 ℃ or directly placing in a vacuum box for vacuumizing, and standing and curing at room temperature;

wherein the curing agent is at least one of a mixture of calcium chloride and sodium fluosilicate, polymerized aluminum phosphate and silicon phosphate.

2. The method for filling emerald with inorganic materials according to claim 1, wherein the mass of the calcium chloride is 2 to 8% of the mass of sodium silicate, and the mass of the sodium fluorosilicate is 4 to 6% of the mass of sodium silicate.

3. The method for filling jade with inorganic material as claimed in claim 1, wherein said calcium chloride is 2% by mass of sodium silicate.

4. The method as claimed in claim 1, wherein the mass of the polymerized aluminum phosphate or silicon phosphate is 3-6% of the mass of the sodium silicate.

5. The method for filling emerald with inorganic materials according to claim 1, wherein the mass fraction of sodium silicate in the aqueous solution of sodium silicate is 30-40%.

6. The method for filling jade with inorganic material as claimed in claim 1, wherein said standing at room temperature is carried out for 24-48 hours.

Technical Field

The invention relates to a preparation method of inorganic material filled jadeite, belonging to the field of jadeite filling.

Background

The acid pickling filling treatment of the jadeite means that the jadeite with poor seed water and color is soaked by strong acid and strong alkali, so that the seed water and the color of the jadeite are improved, and meanwhile, the original rock structure of the jadeite is also damaged. In order to cover up the damaged structure and increase the strength of jadeite, the jadeite is often filled with paraffin oil, paraffin, epoxy resin and their mixture after acid washing. The organic filling material has good viscosity and strong toughness, and the organic filling agent is immersed into the jade in vacuum to achieve the purposes of filling gaps and enhancing the transparency and durability of the jade. However, the main chemical components of the organic filler are different from the main chemical components of the jade, and have different gloss, and the organic filler is not resistant to oxidation and fire, so that the jade filled with the organic filler is easy to yellow and age, and the appearance quality and the preservation value of the jade are influenced.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide a method for filling jadeite with inorganic materials, which adds a new filling mode to the single mode of filling organic materials into the existing jadeite, wherein the inorganic materials and the jadeite have similar main chemical composition elements, have high-temperature drying property, oxidation resistance and fire resistance, and can play a role in solidifying the jadeite with a loose structure.

In order to achieve the purpose, the invention adopts the technical scheme that: a method for filling jade with inorganic materials comprises the following steps:

(1) adding a curing agent into a sodium silicate aqueous solution, and uniformly stirring to obtain a mixed solution;

(2) immersing jade washed by acid-washing alkali into the mixed solution, standing at room temperature, and curing at the temperature of 120-130 ℃;

wherein the curing agent is at least one of a mixture of calcium chloride and sodium fluosilicate, polymerized aluminum phosphate and silicon phosphate.

The aqueous sodium silicate solution is commonly called sodium silicate, the poor water resistance of sodium silicate is caused by the water solubility of Na, and the most direct effective method for improving the water resistance is to use hydrophobic groups or ions such as condensed phosphates, fluoridesSubstances, replacing Na, adding calcium chloride into sodium silicate aqueous solution to enhance water resistance of sodium silicate after consolidation, and OH in water glass gel^-And Na⁺All have certain hydrophilicity, but are due to Na⁺Is more hydrophilic than OH^-Much stronger, so its hygroscopicity is mainly determined by Na⁺Existence of (c) and the number thereof. However, Na is unavoidable in the water glass gel⁺So that we can only introduce Ca into water glass²+ addition substance makes the addition substance introduced by water glass binder during film-forming hardening adsorb on the surface of polysilicic acid and make Na in inner layer⁺Shielding to reduce the hygroscopicity of the latter, thereby achieving the purpose of improving the hygroscopicity resistance of the water glass.

Similarly, the polymerized aluminum phosphate and the silicon phosphate can provide H, Na is replaced by H, the gelation of sodium silicate is promoted, H + is generated by hydrolyzing the polymerized aluminum phosphate with the polymerization degree of 3 in the experiment, and Al is mainly reacted with the polymerized aluminum phosphate³⁺The ions deprive alkali in the water glass, so that the water glass loses water to generate silica gel:

Na₂SiO₃+2H⁺+H₂O→2Na⁺+Si(OH)₄

evaporating water from water glass sol at normal temperature, and collecting silicate anion in water glass to form film Na⁺Randomly distributed in the filling material. The water glass gel has more Si-OH bonds, and the condensate is easily dissolved in water and then is damaged. When the temperature is increased (80 ℃), water molecules are rearranged and have catalysis effect on condensation between adjacent silanol groups, the reaction is further heated to more than 120-130 ℃, residual water molecules promote the condensation of the silanol groups, Si-OH bonds are mutually dehydrated and associated to form Si-O-Si bonds, and finally, a silicon-containing block polymer is further generated, so that the silicon-containing block polymer is a curing system with a three-dimensional structure with excellent water resistance, and is specifically shown in the following reaction formula and structural formula.

As a preferred embodiment of the method for filling jade with inorganic material of the present invention, the curing agent is calcium chloride in combination with sodium fluorosilicate.

As a preferred embodiment of the method for filling emerald with the inorganic material, the mass of the calcium chloride is 2-8% of that of sodium silicate, and the mass of the sodium fluosilicate is 4-6% of that of sodium silicate. The inventors found that when the amounts of calcium chloride and sodium fluorosilicate are equal to the above amounts, the filling effect of jade is good. The inventor further researches and discovers that the mass ratio of the calcium chloride to the sodium fluosilicate influences the filling effect of the jade, and when the mass ratio of the calcium chloride to the sodium fluosilicate is 1: 2-1: 1, the appearance effect and the water resistance of the jade are good.

As a preferred embodiment of the method for filling jade with the inorganic material of the present invention, the mass of calcium chloride is 2% of the mass of sodium silicate. The inventor finds that the more the calcium chloride content is, the poorer the transparency of the filled jade is, and when the calcium chloride content is 2% of the sodium silicate by mass, the effect of filling the jade is the best.

As a preferred embodiment of the method for filling jade with the inorganic material, the mass of the polymerized aluminum phosphate or silicon phosphate is 3-6% of that of the sodium silicate. The inventors have found that when the curing agent is polymerized aluminum phosphate or silicon phosphate, the effect of filling jade with the above-mentioned mass is good.

As a preferred embodiment of the method for filling emerald with the inorganic material of the present invention, the mass fraction of sodium silicate in the aqueous sodium silicate solution is 30 to 40%.

As a preferred embodiment of the method for filling jade with the inorganic material, the standing time at room temperature is 24-48 h.

Compared with the prior art, the invention has the beneficial effects that: according to the invention, the prepared inorganic material is adopted to fill the jadeite, so that the quality of the jadeite is improved, the originally low-grade jadeite is subjected to filling treatment of the inorganic material, so that the jadeite with a loose structure becomes more compact, the luster of the jadeite is enhanced after polishing, the effect of improving the appearance is achieved, and the defects that the organic matter filled jadeite does not have ageing resistance and fire resistance are overcome.

Drawings

Fig. 1 is a comparison graph of jadeite filled with inorganic materials and jadeite not filled with inorganic materials obtained in examples 1 and 2;

fig. 2 is a comparison graph of jadeite filled with inorganic materials and jadeite not filled with inorganic materials obtained in examples 7 and 8.

Detailed Description

To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to the following detailed description and accompanying drawings.

Example 1

The embodiment provides a method for filling jadeite with inorganic material, which comprises the following steps:

(1) adding calcium chloride into a sodium silicate aqueous solution, uniformly stirring to obtain a mixed solution 1, then adding sodium fluosilicate into the mixed solution 1, and uniformly stirring to obtain a mixed solution 2;

(2) putting the jade into a container filled with strong acid, cleaning, then putting the acid-washed jade into a container filled with alkaline water, and cleaning to obtain the acid-washed and alkaline-washed jade; immersing the jade washed by the acid-washing alkali into the mixed solution 2, standing at room temperature for 24h, and curing at 120 ℃ to obtain inorganic material filled jade;

the mass fraction of sodium silicate in the sodium silicate aqueous solution is 35 percent; the mass of the calcium chloride is 2% of that of the sodium silicate; the mass of the sodium fluosilicate is 4 percent of that of the sodium silicate.

Example 2

The embodiment provides a method for filling jadeite with inorganic material, which comprises the following steps:

(1) adding calcium chloride into a sodium silicate aqueous solution, uniformly stirring to obtain a mixed solution 1, then adding sodium fluosilicate into the mixed solution 1, and uniformly stirring to obtain a mixed solution 2;

(2) putting the jade into a container filled with strong acid, cleaning, then putting the acid-washed jade into a container filled with alkaline water, and cleaning to obtain the acid-washed and alkaline-washed jade; immersing the jade washed by the acid-washing alkali into the mixed solution 2, standing at room temperature for 24h, and curing at 120 ℃ to obtain inorganic material filled jade;

the mass fraction of sodium silicate in the sodium silicate aqueous solution is 35 percent; the mass of the calcium chloride is 5% of that of the sodium silicate; the mass of the sodium fluosilicate is 5 percent of that of the sodium silicate.

Example 3

The embodiment provides a method for filling jadeite with inorganic material, which comprises the following steps:

(1) adding calcium chloride into a sodium silicate aqueous solution, uniformly stirring to obtain a mixed solution 1, then adding sodium fluosilicate into the mixed solution 1, and uniformly stirring to obtain a mixed solution 2;

(2) putting the jade into a container filled with strong acid, cleaning, then putting the acid-washed jade into a container filled with alkaline water, and cleaning to obtain the acid-washed and alkaline-washed jade; immersing the jade washed by the acid-washing alkali into the mixed solution 2, standing at room temperature for 24h, and curing at 120 ℃ to obtain inorganic material filled jade;

the mass fraction of sodium silicate in the sodium silicate aqueous solution is 35 percent; the mass of the calcium chloride is 8% of that of the sodium silicate; the mass of the sodium fluosilicate is 6 percent of that of the sodium silicate.

Comparative example 1

The comparative example provides a method for filling jadeite with an inorganic material, comprising the following steps:

(1) adding calcium chloride into a sodium silicate aqueous solution, uniformly stirring to obtain a mixed solution 1, then adding sodium fluosilicate into the mixed solution 1, uniformly stirring to obtain a mixed solution 2, and then adding a defoaming agent;

(2) putting the jade into a container filled with strong acid, cleaning, then putting the acid-washed jade into a container filled with alkaline water, and cleaning to obtain the acid-washed and alkaline-washed jade; immersing the jade washed by the acid-washing alkali into the mixed solution 2, standing at room temperature for 24h, and curing at 120 ℃ to obtain inorganic material filled jade;

the mass fraction of sodium silicate in the sodium silicate aqueous solution is 35 percent; the mass of the calcium chloride is 8% of that of the sodium silicate; the mass of the sodium fluosilicate is 6% of that of the sodium silicate, the defoaming agent is DOW polysiloxane mixed liquor, and the mass of the defoaming agent is 2% of that of the sodium silicate.

Effect example 1

The inorganic material-filled jades obtained in examples 1 to 3 and comparative example 1 were simultaneously placed in an oven and heated to turn the inorganic material-filled jades into white powders, and then the white powders were left at room temperature for one month to observe the transparency and color of the jades while the inorganic material-filled jades were subjected to a contact angle test, wherein comparative example 2 was an unfilled bleached jades, and the results were shown in table 1 and fig. 1.

Contact angle test method: an optical contact angle measuring instrument (Biolin, Theta Flex) is utilized, the measuring range is 0-180 degrees, and the precision is +/-0.1. The contact angle between the cut polished bleached jadeite and the polished sodium silicate filled jadeite of the same block was measured and compared with the hydrophilic and hydrophobic properties.

TABLE 1

As can be seen from Table 1, the method for filling jadeite with inorganic material of the present invention has a good filling effect on jadeite, and the jadeite filled with inorganic material has similar water resistance; fig. 1 is a comparison graph of jadeite filled with inorganic material obtained in examples 1 and 2 and jadeite not filled with inorganic material, and it can be seen from the graph that the jadeite filled with inorganic material obtained in example 1 has better transparency and more prominent color root; in example 3, it is known that the increase of calcium chloride can promote the consolidation effect by combining the appearance effect of jade, but the more the content of jade, the poorer the transparency of jade filled with the calcium chloride. Therefore, in summary, the filling effect of jadeite is best when the mass ratio of calcium chloride to sodium fluosilicate is 1: 2.

Example 4

The embodiment provides a method for filling jadeite with inorganic material, which comprises the following steps:

(1) adding calcium chloride into a sodium silicate aqueous solution, uniformly stirring to obtain a mixed solution 1, then adding sodium fluosilicate into the mixed solution 1, and uniformly stirring to obtain a mixed solution 2;

(2) putting the jade into a container filled with strong acid, cleaning, then putting the acid-washed jade into a container filled with alkaline water, and cleaning to obtain the acid-washed and alkaline-washed jade; immersing the jade washed by the acid-washing alkali into the mixed solution 2, standing at room temperature for 24h, and curing at 120 ℃ to obtain inorganic material filled jade;

the mass fraction of sodium silicate in the sodium silicate aqueous solution is 30%; the mass of the calcium chloride is 5% of that of the sodium silicate; the mass of the sodium fluosilicate is 5 percent of that of the sodium silicate.

Example 5

The embodiment provides a method for filling jadeite with inorganic material, which comprises the following steps:

(1) adding calcium chloride into a sodium silicate aqueous solution, uniformly stirring to obtain a mixed solution 1, then adding sodium fluosilicate into the mixed solution 1, and uniformly stirring to obtain a mixed solution 2;

(2) putting the jade into a container filled with strong acid, cleaning, then putting the acid-washed jade into a container filled with alkaline water, and cleaning to obtain the acid-washed and alkaline-washed jade; immersing the jade washed by the acid-washing alkali into the mixed solution 2, standing at room temperature for 24h, and curing at 120 ℃ to obtain inorganic material filled jade;

the mass fraction of sodium silicate in the sodium silicate aqueous solution is 40%; the mass of the calcium chloride is 8% of that of the sodium silicate; the mass of the sodium fluosilicate is 6 percent of that of the sodium silicate.

Example 6

The embodiment provides a method for filling jadeite with inorganic material, which comprises the following steps:

(1) adding calcium chloride into a sodium silicate aqueous solution, uniformly stirring to obtain a mixed solution 1, then adding sodium fluosilicate into the mixed solution 1, and uniformly stirring to obtain a mixed solution 2;

(2) putting the jade into a container filled with strong acid, cleaning, then putting the acid-washed jade into a container filled with alkaline water, and cleaning to obtain the acid-washed and alkaline-washed jade; immersing the jade washed by the acid-washing alkali into the mixed solution 2, standing at room temperature for 24h, and curing at 120 ℃ to obtain inorganic material filled jade;

the mass fraction of sodium silicate in the sodium silicate aqueous solution is 35 percent; the mass of the calcium chloride is 5% of that of the sodium silicate; the mass of the sodium fluosilicate is 6 percent of that of the sodium silicate.

Effect example 2

The inorganic material-filled jades obtained in examples 4 to 6 were simultaneously placed in an oven and heated to solidify the inorganic material filler of jades, and then the filled jades were placed at room temperature for one month to observe the appearance of jades while subjecting the inorganic material-filled jades to a contact angle test, wherein comparative example 3 was an unfilled jades, and the results are shown in table 2.

Contact angle test method: an optical contact angle measuring instrument (Biolin, Theta Flex) is utilized, the measuring range is 0-180 degrees, and the precision is +/-0.1. The contact angle between the cut polished bleached jadeite and the polished sodium silicate filled jadeite of the same block was measured and compared with the hydrophilic and hydrophobic properties.

TABLE 2

As can be seen from table 2, the method for filling jadeite with inorganic material according to the present invention has a better filling effect on jadeite.

Example 7

The embodiment provides a method for filling jadeite with inorganic material, which comprises the following steps:

(1) adding silicon phosphate into a sodium silicate aqueous solution, and uniformly stirring to obtain a mixed solution;

(2) putting the jade into a container filled with strong acid, cleaning, then putting the acid-washed jade into a container filled with alkaline water, and cleaning to obtain the acid-washed and alkaline-washed jade; immersing the jade washed by acid-washing and alkali into the mixed solution, placing the mixture in a vacuum box for vacuumizing, wherein the vacuum degree is less than-0.1 MPa, and standing the mixture at room temperature for 48 hours to obtain inorganic material-filled jade;

the mass fraction of sodium silicate in the sodium silicate aqueous solution is 35 percent; the mass of the silicon phosphate is 3.8 percent of that of the sodium silicate.

Example 8

The embodiment provides a method for filling jadeite with inorganic material, which comprises the following steps:

(1) adding polymerized aluminum phosphate into a sodium silicate aqueous solution, and uniformly stirring to obtain a mixed solution;

(2) putting the jade into a container filled with strong acid, cleaning, then putting the acid-washed jade into a container filled with alkaline water, and cleaning to obtain the acid-washed and alkaline-washed jade; immersing the jade washed by the acid-washing alkali into the mixed solution, placing the mixture in a vacuum box, vacuumizing to less than-0.1 MPa, and standing at room temperature for 48 hours to obtain inorganic material-filled jade;

the mass fraction of sodium silicate in the sodium silicate aqueous solution is 35 percent; the mass of the polymerized aluminum phosphate is 3.8% of that of the sodium silicate, and the polymerization degree of the polymerized aluminum phosphate is 3.

Effect example 3

The surfaces of the inorganic material-filled jades obtained in examples 7 to 8 were observed at room temperature, and the inorganic material-filled jades obtained in examples 7 to 8 were tested for aging resistance and acid resistance, and the results are shown in table 3 and fig. 2.

Aging resistance test method: and (3) utilizing a xenon lamp aging test box, irradiating the filled jade sample by ultraviolet light, and observing the aging resistance of the filled jade sample. The condition parameters are that the lamp tube is UVA-340nm, and the irradiance (0.76 +/-0.02) w/m²Nm, illumination 65 ℃. The state of the sample was observed after 24 hours of irradiation with an ultraviolet lamp.

The test method of acid resistance comprises the following steps: the samples are subjected to a salt-resistant acid soaking experiment for 24 hours, and no foaming, no slag falling and no cracking phenomenon are observed in hydrochloric acid with the concentration of 5%.

TABLE 3

As can be seen from Table 3, silicon phosphate and polymerized aluminum phosphate as curing agents also have a good effect of filling jadeite, and the polymerized aluminum phosphate has a better effect than silicon phosphate.

Fig. 2 is a comparison graph of jadeite filled with inorganic materials and jadeite not filled with inorganic materials obtained in examples 7 and 8. As can be seen from fig. 2, the effect of the silicon phosphate and the polymerized aluminum phosphate filled jadeite is not very different, but compared with the unfilled jadeite, the silicon phosphate and the polymerized aluminum phosphate filled jadeite have better transparency, more prominent color roots and more uniform color concentration.

Example 9

The embodiment provides a method for filling jadeite with inorganic material, which comprises the following steps:

(1) adding polymerized aluminum phosphate into a sodium silicate aqueous solution, and uniformly stirring to obtain a mixed solution;

(2) putting the jade into a container filled with strong acid, cleaning, then putting the acid-washed jade into a container filled with alkaline water, and cleaning to obtain the acid-washed and alkaline-washed jade; immersing the jade washed by the acid-washing alkali into the mixed solution, placing the mixture in a vacuum box, vacuumizing to less than-0.1 MPa, and standing at room temperature for 48 hours to obtain inorganic material-filled jade;

the mass fraction of sodium silicate in the sodium silicate aqueous solution is 35 percent; the mass of the polymerized aluminum phosphate is 6% of that of the sodium silicate, and the polymerization degree of the polymerized aluminum phosphate is 3.

Example 10

The embodiment provides a method for filling jadeite with inorganic material, which comprises the following steps:

(1) adding polymerized aluminum phosphate into a sodium silicate aqueous solution, and uniformly stirring to obtain a mixed solution;

(2) putting the jade into a container filled with strong acid, cleaning, then putting the acid-washed jade into a container filled with alkaline water, and cleaning to obtain the acid-washed and alkaline-washed jade; immersing the jade washed by the acid-washing alkali into the mixed solution, placing the mixture in a vacuum box, vacuumizing to less than-0.1 MPa, and standing at room temperature for 48 hours to obtain inorganic material-filled jade;

the mass fraction of sodium silicate in the sodium silicate aqueous solution is 35 percent; the mass of the polymerized aluminum phosphate is 3% of that of the sodium silicate, and the polymerization degree of the polymerized aluminum phosphate is 3.

Effect example 4

The inorganic material obtained in examples 8 to 9, in which comparative example 4 was an unfilled jade, was tested for aging resistance, acid resistance, and contact angle, and the test results were shown in table 4.

Aging resistance test method: and (3) utilizing a xenon lamp aging test box, irradiating the filled jade sample by ultraviolet light, and observing the aging resistance of the filled jade sample. The condition parameters are that the lamp tube is UVA-340nm, the irradiance (0.76 +/-0.02) w/m2.nm and the illumination is 65 ℃. The state of the sample was observed after 24 hours of irradiation with an ultraviolet lamp.

The test method of acid resistance comprises the following steps: the samples are subjected to a salt-resistant acid soaking experiment for 24 hours, and no foaming, no slag falling and no cracking phenomenon are observed in hydrochloric acid with the concentration of 5%.

Contact angle test method: an optical contact angle measuring instrument (Biolin, Theta Flex) is utilized, the measuring range is 0-180 degrees, and the precision is +/-0.1. The contact angle between the cut polished bleached jadeite and the polished sodium silicate filled jadeite of the same block was measured and compared with the hydrophilic and hydrophobic properties.

TABLE 4

As can be seen from Table 4, when the mass of the polymerized aluminum phosphate is 3-6% of that of the sodium silicate, the filling effect of the jadeite is better, and particularly, when the mass of the polymerized aluminum phosphate is 3.8% of that of the sodium silicate, the filling effect of the jadeite is the best.

Finally, it should be noted that the above embodiments are intended to illustrate the technical solutions of the present invention and not to limit the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.