CN106082682A - Glass air brushing bismuth silicon boron system's low-melting-point nano glass dust suspension and preparation method - Google Patents

Abstract

The invention belongs to the field of glass decoration, is especially suitable for the field of glass spray painting, and particularly relates to a suspension of bismuth-silicon-boron-based low-melting nano-glass powder for glass spray painting and a preparation method thereof. It is characterized in that: the raw materials of solid phase components are bismuth oxide, amorphous silicon oxide, boric acid or boron oxide, lithium nitrate, aluminum oxide, zirconium oxide; After the zirconium is evenly mixed, carry out high-energy ball milling for preliminary mechanical alloying, and then mix the powder obtained by ball milling with boric acid, boron oxide, and lithium nitrate for ball milling, and then add solvent for wet milling. The suspension provided by the invention has a solid phase particle size of submicron or nanometer level, and the starting temperature of melting a large amount of low-melting point glass powder is 580-650°C. After sintering on glass, it is in a colorless glass state and has a high bonding force with glass. , has broad application prospects in the field of glass digital inkjet printing.

Description

Bismuth-silicon-boron-based low-melting-point nano-glass powder suspension for glass inkjet painting and its preparation method

technical field

The invention belongs to the field of glass decoration, is especially suitable for the field of glass spray painting, and particularly relates to a suspension of bismuth-silicon-boron-based low-melting nano-glass powder for glass spray painting and a preparation method thereof.

Background technique

With the development of construction, automobile, decoration, furniture and other industries and the improvement of people's living environment requirements, people's demand for the beauty of glass products is also increasing. Glass decoration is following the fashion, personalization, artistic, The trend of small batch, multi-color, low-carbon and environmental protection is developing. There are many kinds of inks for glass decoration, which are mainly divided into low-temperature quick-drying type and high-temperature sintering type. The usage of low-temperature quick-drying glass ink is to apply the ink to the glass and bake it at 50℃～200℃. Glass ink is solidified on the glass, but this glass ink has many problems, such as poor adhesion, not resistant to dirt, easy to be corroded by acid and alkali, and easy to fade. The usage of high-temperature sintering ink is to apply glass ink to glass, and then sinter the glass ink on the glass at a high temperature of 500°C to 700°C. Dirty, not easy to be corroded by acid and alkali, not easy to fade, etc. Therefore, the market demand for this glass ink is increasing.

The main component of high temperature sintered glass ink is low melting point glass powder, and the preparation of low melting point glass powder is also the key technical difficulty of high temperature sintered glass ink.

Chinese patent CN104893418 discloses a lead-free environmentally friendly glass ink and its preparation method, which includes the preparation method of low-melting point glass powder. Water quenching, ball milling and other processes finally produce low melting point glass powder. Chinese patent CN104893410, U.S. patents U.S4892847, U.S5468695, U.S4554258, and U.S4892847 all disclose similar high-temperature smelting methods for preparing low-melting glass powders. 700°C glass powder, but this method requires a melting temperature above 1000°C to fully alloy the raw materials, which results in high energy consumption and high preparation costs. Moreover, the particle size of the prepared glass powder is coarse, generally above 2 μm, which is only suitable for traditional printing such as screen printing, not suitable for glass digital inkjet printing, which requires an ink particle size below 2 μm. Advanced glass printing technology, scope of application narrower.

U.S. Patent US 20120138215 discloses a method for preparing low-melting glass powder by sol-gel method (sol-gel). This preparation method can prepare nano-scale glass powder, but this preparation method requires the use of Chemical reagents such as NH ₄ OH are easy to form a large amount of chemical waste, which is harmful to the environment, and this method also has high requirements for production equipment, and the production cost is relatively high.

Contents of the invention

The object of the present invention is to provide a bismuth-silicon-boron-based low-melting-point nano-glass powder suspension for glass spray painting and a preparation method for the above-mentioned deficiencies in the prior art.

The technical scheme that the present invention takes is:

Bismuth-silicon-boron low-melting-point nano-glass powder suspension liquid for glass inkjet painting is characterized in that its solid-phase component, that is, the raw material of low-melting-point glass powder is bismuth oxide (α-type Bi ₂ O ₃ ), amorphous silicon oxide ( SiO ₂ ), boric acid (H ₃ BO ₃ ) or boron oxide (B ₂ O ₃ ), lithium nitrate (LiNO ₃ ), aluminum oxide (Al ₂ O ₃ ), zirconium oxide (ZrO ₂ ).

The formula containing boric acid (H ₃ BO ₃ ) is as follows: the mass percentage of bismuth oxide (α-type Bi ₂ O ₃ ) is 27-32%, the mass percentage of amorphous silicon oxide (SiO ₂ ) is 8-11%, The mass percentage of boric acid (H ₃ BO ₃ ) is 21-30%, the mass percentage of lithium nitrate (LiNO ₃ ) is 29-33%, the mass percentage of aluminum oxide (Al ₂ O ₃ ) is 2-3%, and the mass percentage of zirconia The mass percentage of (ZrO ₂ ) is 0.5-2%, and the sum of each component is 100%.

The formula containing boron oxide (B ₂ O ₃ ) is as follows: the mass percentage of bismuth oxide (α-type Bi ₂ O ₃ ) is 34.9-43.3%, and the mass percentage of amorphous silicon oxide (SiO ₂ ) is 12.2-14.5% , the mass percentage of boron oxide (B ₂ O ₃ ) is 8-13.7%, the mass percentage of lithium nitrate (LiNO ₃ ) is 29.3-37%, the mass percentage of aluminum oxide (Al ₂ O ₃ ) is 2.7-3.4%, The mass percentage of zirconium oxide (ZrO ₂ ) is 1.2-1.5%, and the sum of each component is 100%.

The maximum particle size of bismuth oxide (α-type Bi ₂ O ₃ ), amorphous silicon oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), and zirconia (ZrO ₂ ) in the low melting point glass powder raw material The diameter should be less than 1 μm.

The bismuth-silicon-boron series low-melting-point nano-glass powder suspension for glass digital inkjet printing is characterized in that its liquid phase solution is 1,2-propylene glycol dimethyl ether, ethylene glycol monoethyl ether and cyclohexanone One or any mixture of several.

The method for preparing the bismuth-silicon-boron-based low-melting-point nano-glass powder suspension for glass digital inkjet printing is characterized in that it is mainly divided into a low-melting-point glass powder preparation process and a solid-liquid mixing process.

The preparation method of the low melting point glass powder belongs to the mechanical alloying method, that is, the mechanical alloying of each raw material is made by purely mechanical ball milling, and mainly includes the following three steps:

1) Weigh bismuth oxide (α-type Bi ₂ O ₃ ), amorphous silicon oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ) and zirconia (ZrO ₂ ) according to a certain mass percentage, and stir and mix uniform;

2) Put the prepared above-mentioned raw materials in a high-energy ball mill and carry out high-energy ball milling according to certain ball milling parameters, so as to make preliminary mechanical alloying between the components of the above four kinds of raw materials, and take out the obtained powder after ball milling for a certain period of time. For different types of ball mills , the milling parameters changed accordingly.

3) Mix the powder obtained in the previous step with a certain mass percentage of boric acid (H ₃ BO ₃ ) or boron oxide (B ₂ O ₃ ), lithium nitrate (LiNO ₃ ), and put it into a high-energy ball mill for ball milling according to certain ball milling parameters After a certain period of time, the low melting point glass powder can be obtained.

The described solid-liquid mixing process is a wet grinding method, which mainly includes the following two steps carried out in sequence:

1) Put the prepared low-melting point glass powder into a ball mill jar, and then pour a certain amount of liquid phase solution. The mass ratio of liquid phase solution and low melting point glass powder is 2-4:1. Wet mill for a certain period of time to obtain glass powder suspension.

2) Take out the glass frit suspension obtained in the previous step, and filter to obtain the low melting point nano glass frit suspension.

In step 2) of the preparation method of the low-melting point glass powder, the setting standard of the ball milling parameters is that the ball milling time is 8-24 hours, and the ball milling parameters are generally set as: rotating speed 400-600r/min, ball-to-material ratio setting 6 -15:1.

In step 3) of the preparation method of the low-melting point glass powder, the setting standard of the ball milling parameters is that the ball milling time is 12-24 hours, and the ball milling parameters are generally set as: the rotating speed is 400-600r/min, and the ball-to-material ratio is set to 6 -15:1.

The setting standard for the wet milling parameters in step 1) of the solid-liquid mixing process is that the ball milling time is 12-48 hours, the ball milling parameters are generally set as: rotating speed 400-600r/min, and the ball-to-material ratio is set to 5- 10:1.

The temperature at which the low-melting-point glass powder starts to melt in large quantities is 580-650°C.

The beneficial effects of the present invention are:

(1) The bismuth-silicon-boron-based low-melting-point nano-glass powder suspension for glass digital inkjet printing provided by the present invention, the present invention innovatively designs a low-melting-point glass powder formula, the biggest difference from the prior art is that it is the first time Use the ternary system of bismuth oxide (α-type Bi ₂ O ₃ ), amorphous silicon oxide (SiO ₂ ), boric acid (H ₃ BO ₃ ) or boron oxide (B ₂ O ₃ ) to prepare low melting point glass powder, And for the first time, lithium nitrate (LiNO ₃ ) was used as a flux for low-melting glass powder. It does not contain any harmful substances such as lead and thallium, which is healthy and environmentally friendly.

(2) The bismuth-silicon-boron series low-melting-point nano-glass powder suspension liquid provided by the invention for glass digital inkjet printing, wherein the particle size of the glass powder is small, the glass powder of the boric acid formula is at the submicron level, and the glass powder of the boron oxide formula can Reaching the nanometer level, the glass powder has good suspension in the solution and is not easy to settle. It is used in the field of glass inkjet printing and can greatly reduce the phenomenon of ink blocking the inkjet head.

(3) The bismuth-silicon-boron low-melting-point nano-glass powder suspension liquid for digital inkjet printing of glass provided by the present invention has a low-melting-point glass powder starting temperature of melting in a large amount at 580-650° C., low melting temperature, and spraying and sintering on the glass Finally, it is in a colorless glass state and has a high binding force with glass.

(4) The preparation method of the low-melting-point glass powder in the bismuth-silicon-boron-based low-melting-point nano-glass powder suspension for glass digital inkjet printing provided by the present invention is a mechanical alloying method, which overcomes the prior art melting method and sol-gel Insufficiency of the method, does not contain high temperature treatment, low energy consumption, low production cost, and does not produce environmentally harmful waste in the production process, and is environmentally friendly.

Description of drawings

Fig. 1 is a DSC chart of the low-melting glass powder prepared in Example 1 of the present invention.

Fig. 2 is a laser particle size analyzer diagram of a bismuth-silicon-boron-based low-melting-point nano-glass powder suspension prepared for glass digital inkjet printing according to an example of the present invention.

Fig. 3 is an XRD pattern of the low-melting glass powder prepared in Example 1 of the present invention.

Fig. 4 is a DSC chart of the low-melting glass powder prepared in Example 2 of the present invention.

Fig. 5 is a laser particle size analyzer diagram of a bismuth-silicon-boron-based low-melting-point nano-glass powder suspension prepared in Example 2 of the present invention for digital inkjet printing on glass.

Fig. 6 is an XRD pattern of the low-melting glass powder prepared in Example 2 of the present invention.

Fig. 7 is a DSC chart of the low-melting glass powder prepared in Example 3 of the present invention.

Fig. 8 is a laser particle size analyzer diagram of a bismuth-silicon-boron-based low-melting-point nano-glass powder suspension prepared for glass digital inkjet printing in three examples of the present invention.

Fig. 9 is an XRD pattern of the low-melting glass powder prepared in Example 3 of the present invention.

Fig. 10 is a DSC chart of the low-melting glass powder prepared in Example 4 of the present invention.

Fig. 11 is a laser particle size analyzer diagram of a suspension of bismuth-silicon-boron-based low-melting-point nano-glass powder for glass digital inkjet printing prepared in four examples of the present invention.

Fig. 12 is an XRD pattern of the low-melting glass powder prepared in Example 4 of the present invention.

Fig. 13 is a photo before coating the suspension prepared in Example 1 on glass before sintering.

Fig. 14 is a photo of the suspension prepared in Example 1 coated on glass and sintered.

Fig. 15 is a photo before coating the suspension prepared in Example 4 on glass before sintering.

Fig. 16 is a photo of the suspension prepared in Example 4 coated on glass and sintered.

detailed description

The present invention will be further described below in conjunction with the accompanying drawings and embodiments.

Embodiment one

Bismuth-silicon-boron series low-melting-point nano-glass powder suspension for glass printing, the preparation method of which is as follows:

This embodiment uses a 500ml nylon ball mill jar, and _{grinds 40g of} low _- melting point glass powder each time. BO ₃ ) 22%, Lithium Nitrate (LiNO ₃ ) 32.3%, Aluminum Oxide (Al ₂ O ₃ ) 2.5%, Zirconia (ZrO ₂ ) 1.1% by mass percentage, calculate the required amount of ball milling 40g low melting point glass powder Raw material quality, bismuth oxide (α-type Bi ₂ O ₃ ) 12.56 grams, amorphous silicon oxide (SiO ₂ ) 4.28 grams, boric acid (H ₃ BO ₃ ) 8.8 grams, lithium nitrate (LiNO ₃ ) 12.92 grams, aluminum oxide (Al ₂ O ₃ ) 1 gram, zirconia (ZrO ₂ ) 0.44 gram and then weighed according to the calculation results.

Secondly, the weighed raw materials bismuth oxide (α-type Bi ₂ O ₃ ), amorphous silicon oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ) and zirconia (ZrO ₂ ) were placed in a beaker, Stir well, and then weigh about 237g of agate balls according to the ball-to-material ratio of 13:1.

Then, pour the above-mentioned four kinds of raw materials and agate balls into a ball mill jar together, and start ball milling. During the ball milling process, the rotating speed is 500r/min, and the ball mill is 10h, and the powder obtained in the ball mill jar is taken out.

Then, mix the powder obtained in the previous step with the weighed boric acid (H ₃ BO ₃ ) and lithium nitrate (LiNO ₃ ) evenly, then weigh 240g of agate balls according to the ball-to-material ratio of 6:1, mix the above raw materials and Agate balls are poured into the ball mill jar together, and ball milling is started. During the ball milling process, the rotating speed is 500r/min. After ball milling for 10 hours, the ball milling is stopped to obtain the low-melting glass powder;

Finally, add 120ml of 1,2-propylene glycol dimethyl ether to the glass powder obtained in the previous step, rotate at a speed of 500r/min, ball mill for 48h, stop ball milling, and filter the glass powder suspension obtained, that is, to the Bismuth silicon boron series low melting point nano glass powder suspension.

The low-melting-point nano-glass powder suspension obtained in this example is white in color. The sedimentation experiment found that after the suspension is prepared, it will settle for more than one month, and after the settlement, it only needs to be properly stirred to return to suspension. Liquid, so the glass powder of this product has good suspension in the solution and is not easy to settle.

Figure 1 shows the DSC chart of the finished low-melting-point glass powder obtained in this example. After analysis, it can be obtained that the low-melting-point glass powder prepared in this example begins to melt in large quantities at a temperature of 637°C.

The finished low-melting-point glass powder obtained in this embodiment was tested with a laser particle size analyzer, and the result is shown in Figure 2. From the figure, it can be seen that the average particle size of the glass powder obtained in this embodiment is about 838nm, which belongs to the submicron level.

Fig. 3 shows the XRD spectrum of the finished low-melting glass powder obtained in this example. After analysis, phases such as Bi ₂ Zr, Al _1.67 B ₂₂ , Al ₂ Zr, B ₁₂ Zr, and Si ₃ Zr ₅ were found. It can be inferred that each raw material component has been sufficiently mechanically alloyed.

Embodiment two

The experimental method of this embodiment is similar to that of the first embodiment, except that the mass percentages of the raw materials are different. Based on bismuth oxide (α-type Bi ₂ O ₃ ) 29.8%, amorphous silicon oxide (SiO ₂ ) 10.1%, boric acid (H ₃ BO ₃ ) 26.2%, lithium nitrate (LiNO ₃ ) 30.6%, aluminum oxide (Al ₂ O ₃ ) 2.3%, zirconia (ZrO ₂ ) 1% mass percent, calculate the quality of each raw material needed for ball milling 40g low-melting point glass powder, bismuth oxide (α-type Bi ₂ O ₃ ) 11.92 grams, amorphous State silicon oxide (SiO ₂ ) 4.04 grams, boric acid (H ₃ BO ₃ ) 10.48 grams, lithium nitrate (LiNO ₃ ) 12.24 grams, aluminum oxide (Al ₂ O ₃ ) 0.92 grams, zirconia (ZrO ₂ ) 0.4 grams, and then Weighing according to the calculation result, the following steps are completely consistent with Example 1.

The low-melting point nano-glass powder suspension obtained in this embodiment is white in color, similar in color and suspendability to the glass powder obtained in Example 1.

Figure 4 shows the DSC chart of the finished low-melting glass powder obtained in this example. After analysis, it can be obtained that the starting temperature of a large amount of melting of the low-melting glass powder prepared in this example is 608°C.

The finished low-melting-point glass powder obtained in this embodiment was tested with a laser particle size analyzer, and the result is shown in Figure 5. It can be seen from the figure that the particle size of the glass powder obtained in this embodiment is about 465nm, which belongs to the submicron level.

Figure 6 shows the XRD spectrum of the finished low-melting glass powder obtained in this example. After analysis, phases such as Bi ₂ Zr, Al _1.67 B ₂₂ , Al ₂ Zr, B ₁₂ Zr, and Si ₃ Zr ₅ were found. It can be inferred that each raw material component has been sufficiently mechanically alloyed.

Embodiment Three

The experimental method of this embodiment is similar to that of the first embodiment, except that the mass percentages of the raw materials are different. Based on bismuth oxide (α-type Bi ₂ O ₃ ) 28.3%, amorphous silicon oxide (SiO ₂ ) 9.6%, boric acid (H ₃ BO ₃ ) 29.8%, lithium nitrate (LiNO ₃ ) 29.1%, aluminum oxide (Al ₂ O ₃ ) 2.2%, zirconia (ZrO ₂ ) 1% mass percent, calculate the quality of each raw material needed for ball milling 40g low-melting point glass powder, bismuth oxide (α-type Bi ₂ O ₃ ) 11.32 grams, amorphous State silicon oxide (SiO ₂ ) 3.84 grams, boric acid (H ₃ BO ₃ ) 11.92 grams, lithium nitrate (LiNO ₃ ) 11.64 grams, aluminum oxide (Al ₂ O ₃ ) 0.88 grams, zirconia (ZrO ₂ ) 0.4 grams, and then Weighing according to the calculation result, the following steps are completely consistent with Example 1.

The low-melting point nano-glass powder suspension obtained in this embodiment is white in color and similar in suspending property, which is similar in color to the glass powder obtained in Example 1.

Figure 7 shows the DSC chart of the finished low-melting glass powder obtained in this example. After analysis, it can be obtained that the starting temperature of a large amount of melting of the low-melting glass powder prepared in this example is 580°C.

The finished low-melting glass powder obtained in this example was tested with a laser particle size analyzer, and the result is shown in Figure 8. From the figure, it can be seen that the average particle size of the glass powder obtained in this example is about 721nm, which belongs to the submicron level.

Figure 9 shows the XRD spectrum of the finished low-melting glass powder obtained in this example. After analysis, phases such as Bi ₂ Zr, Al _1.67 B ₂₂ , Al ₂ Zr, B ₁₂ Zr, and Si ₃ Zr ₅ were found. It can be inferred that each raw material component has been sufficiently mechanically alloyed.

Embodiment Four

The preparation method of this example is similar to Example 1, but there are two differences: (1) boric acid (H ₃ BO ₃ ) in the raw material is replaced by boron oxide (B ₂ O ₃ ); (2) the proportion of each raw material The mass percentages are different.

Based on bismuth oxide (α-type Bi ₂ O ₃ ) 36%, amorphous silicon oxide (SiO ₂ ) 12.2%, boron oxide (B ₂ O ₃ ) 10.7%, lithium nitrate (LiNO ₃ ) 37%, aluminum oxide ( Al ₂ O ₃ ) 2.8%, zirconia (ZrO ₂ ) 1.3% mass percent, calculate the quality of each raw material needed for ball milling 35g low melting point glass powder, bismuth oxide (α-type Bi ₂ O ₃ ) 12.6 grams, non- Crystalline silicon oxide (SiO ₂ ) 4.27 grams, boron oxide (B ₂ O ₃ ) 3.75 grams, lithium nitrate (LiNO ₃ ) 12.95 grams, aluminum oxide (Al ₂ O ₃ ) 0.98 grams, zirconia (ZrO ₂ ) 0.45 grams , then weighed according to the calculation results, the following steps are completely consistent with Example 1.

The low-melting point nano-glass powder suspension obtained in this embodiment is yellow in color, which is different from the glass powder obtained in Example 1, but the suspending property is similar.

Figure 10 shows the DSC chart of the finished low-melting glass powder obtained in this example. After analysis, it can be obtained that the starting temperature of a large amount of melting of the low-melting glass powder prepared in this example is 626°C.

The finished low-melting glass powder obtained in this example was tested with a laser particle size analyzer, and the result is shown in Figure 11. It can be seen from the figure that the particle size of the glass powder obtained in this example is about 67nm, which belongs to the nanometer level.

Figure 12 shows the XRD pattern of the finished low-melting glass powder obtained in this example. After analysis, phases such as BiZr, Al _3.24 B ₄₄ , LiAl, B ₁₂ Zr, and Zr ₅ Si ₄ were found, and it can be deduced that each The raw material components have been sufficiently mechanically alloyed.

Embodiment five

In this example, the white low-melting nano-glass powder suspension prepared in Example 1 will be sintered on the glass. The specific implementation steps are: apply the white suspension prepared in Example 1 evenly on the glass, and the glass adopts Ordinary high-gloss glass, as shown in Figure 13, then dry the white suspension on the glass, put it into a high-temperature resistance furnace with a temperature of 680°C for sintering for 3 to 4 minutes, then take it out, cool it, and the sintering effect after cooling As shown in Figure 14, it can be seen that after sintering, the low-melting-point glass powder presents a colorless glass state, which is basically integrated into the glass and has a good bonding force with the glass. The white low-melting-point nano-glass powder prepared in Examples 2 and 3 is suspended The sintering effect between liquid and glass is similar to this embodiment.

Embodiment six

In this example, the yellow low-melting nano-glass powder suspension prepared in Example 4 will be sintered on the glass. The specific implementation steps are: apply the yellow suspension prepared in Example 4 evenly on the glass, and the glass adopts Ordinary high-gloss glass, as shown in Figure 15, then dry the yellow suspension on the glass, put it into a high-temperature resistance furnace with a temperature of 680°C and sinter for 3 to 4 minutes, then take it out, cool it, and sinter it with a low melting point The glass powder is in the state of colorless glass, which is basically integrated into the glass, as shown in Figure 16, and has a very good bonding force with the glass.

The above only lists some formulas. In practical application, the mass percentage of each raw material in the formula of low melting point glass powder can be changed within a certain range. Cooperating with the change of ball milling time, low melting point glass powder with different softening temperatures can be produced. .

The parts not involved in the present invention are the same as the prior art or can be realized by adopting the prior art.

Claims (9)

1. glass air brushing bismuth silicon boron system low-melting-point nano glass dust suspension, is mixed by glass powder with low melting point and liquid solution solid-liquid Conjunction forms, it is characterised in that: the component of described glass powder with low melting point is: α-type Bi₂O₃, amorphous silica, boric acid or oxidation Boron, lithium nitrate, aluminium oxide, zirconium oxide；

Formula containing boric acid is as follows: α-type Bi₂O₃Mass percent be 27～32%, the percent mass of amorphous silica Ratio is 8～11%, and the mass percent of boric acid is 21～30%, and the mass percent of lithium nitrate is 29～33%, aluminium oxide Mass percent is 2～3%, and zirconic mass percent is 0.5～2%, and each component sum is 100%；

Formula containing boron oxide is as follows: α-type Bi₂O₃Mass percent be 34.9～43.3%, the matter of amorphous silica Amount percentage ratio is 12.2～14.5%, and the mass percent of boron oxide is 8～13.7%, and the mass percent of lithium nitrate is 29.3 ～37%, the mass percent of aluminium oxide is 2.7～3.4%, and zirconic mass percent is 1.2～1.5%, each component it With for 100%.

2. glass air brushing as claimed in claim 1 bismuth silicon boron system low-melting-point nano glass dust suspension, it is characterised in that: institute α-type Bi in the low-melting glass powder raw material stated₂O₃, amorphous silica, aluminium oxide, zirconic maximum particle diameter be both needed to be less than 1μm。

3. glass air brushing as claimed in claim 1 bismuth silicon boron system low-melting-point nano glass dust suspension, it is characterised in that: institute Stating liquid solution is a kind of or the most several mixture in 1,2-PD dimethyl ether, ethylene glycol monoethyl ether and Ketohexamethylene.

4. glass air brushing as claimed in claim 1 bismuth silicon boron system low-melting-point nano glass dust suspension, it is characterised in that: institute Stating the beginning temperature that glass powder with low melting point melts in a large number is 580～650 DEG C.

5. glass air brushing as claimed in claim 1 bismuth silicon boron system low-melting-point nano glass dust suspension, it is characterised in that: contain The glass dust particle diameter having boric acid formula can reach Nano grade at submicron rank, the glass dust particle diameter containing boron oxide formula, Glass dust suspension in the solution is good, not free settling, within more than one month, just can settle, and only needs agitation as appropriate, with regard to energy after sedimentation Revert to suspension.

6. the glass air brushing as claimed in claim 1 preparation method of bismuth silicon boron system low-melting-point nano glass dust suspension, its It is characterised by, specifically comprises the following steps that

1) α-type Bi is weighed by mass percentage₂O₃, amorphous silica, aluminium oxide and zirconium oxide, and be uniformly mixed；

2) above-mentioned raw materials prepared is placed in high energy ball mill carries out high-energy ball milling, make between above-mentioned four kinds of raw material each components preliminary Mechanical alloying, takes out the powder of gained after ball milling；

3) by step 2) powder that obtains and boric acid or boron oxide, lithium nitrate mix homogeneously, and puts into ball milling in high energy ball mill, Obtain described glass powder with low melting point；

4) glass powder with low melting point prepared is put in ball grinder, then pour liquid solution into, liquid solution and low melting point glass The mass ratio of glass powder is 2-4:1, and wet grinding obtains glass dust suspension；

5) by step 4) the glass dust suspension that obtains takes out, filters, and i.e. available described low-melting-point nano glass dust is suspended Liquid.

7. the glass air brushing as claimed in claim 6 preparation method of bismuth silicon boron system low-melting-point nano glass dust suspension, its It is characterised by: step 2) in, Ball-milling Time is 8～24h, rotating speed 400～600r/min, and ratio of grinding media to material sets 6-15:1.

8. the glass air brushing as claimed in claim 6 preparation method of bismuth silicon boron system low-melting-point nano glass dust suspension, its It is characterised by: step 3) in, Ball-milling Time is 12～24h, rotating speed 400～600r/min, and ratio of grinding media to material sets 6-15:1.

9. the glass air brushing as claimed in claim 6 preparation method of bismuth silicon boron system low-melting-point nano glass dust suspension, its It is characterised by: step 4) in, the Ball-milling Time of wet grinding is 12～48h, rotating speed 400～600r/min, and ratio of grinding media to material is set as 5-10: 1。