CN114538776B - Boron-free aluminosilicate glass ampoule bottle and post-treatment method thereof - Google Patents

Abstract

The invention relates to the technical field of glass treatment, in particular to a boron-free aluminosilicate glass ampoule bottle and a post-treatment method thereof. The boron-free aluminosilicate glass ampoule bottle is prepared by melting the following raw materials in mole fraction: siO 2 ₂ :40-60 parts; na (Na) ₂ O:5-8 parts; k is ₂ O:5-8 parts; al (Al) ₂ O ₃ :10-13 parts; caO:10-15 parts; baO:4-10 parts; tiO 2 ₂ :0-3 parts of a solvent; after glass is melted and molded, mixed solution of tetramethyl guanidine, triethylamine and ammonia water is used for erosion treatment. The transmittance of the boron-free aluminosilicate glass ampoule bottle after post-treatment is obviously enhanced, the wetting angle is obviously increased, and the post-treatment is very beneficial to the printing procedure of the ink.

Description

Boron-free aluminosilicate glass ampoule bottle and post-treatment method thereof

Technical Field

The invention relates to the technical field of glass treatment, in particular to a boron-free aluminosilicate glass ampoule bottle and a post-treatment method thereof.

Background

The ampoule bottle is a small glass container for containing liquid medicine, the capacity of the ampoule bottle is generally 1-25ml, and the ampoule bottle is commonly used for liquid medicine for injection and is also used for packaging oral liquid.

Glass ampoule bottles for small-volume injections are classified into low borosilicate glass ampoule bottles, medium borosilicate glass ampoule bottles and high borosilicate glass ampoule bottles according to the material. The utility model provides a low borosilicate glass ampoule that current enterprise generally used, general liquid medicine uses low borosilicate glass ampoule enough, but to some acidity, the liquid medicine that the basicity is stronger, low borosilicate glass ampoule is because the acid and alkali resistance performance is relatively poor, can take place to take off the piece scheduling problem usually, it indicates that the liquid medicine reacts with the ion emergence in the glass bottle to take off the piece, ion migration in the glass bottle goes into in the liquid medicine, make the glass internal surface produce and take off the piece phenomenon, the emergence of taking off the piece phenomenon makes the liquid medicine take place muddy phenomenon, and there is the hidden danger of thrombus, and medium-sized silicon glass's acid and alkali resistance is stronger, therefore, neutral borosilicate glass is applicable to the ampoule more.

Boron plays a very important role in glass melting, the addition of boron can obviously improve the glass melting performance and reduce the melting temperature, but boron has a serious boron volatilization phenomenon in the melting process, a silicon-rich phase is formed on the upper layer of glass liquid due to the volatilization of boron, boron enrichment exists on the lower layer of glass liquid due to the precipitation of boron, the upper layer of glass liquid and the lower layer of glass liquid can not be used as raw materials of ampoule bottles, only the middle layer of glass liquid can be used for producing the ampoule bottles, and therefore, the research of boron-free ampoule bottle raw materials becomes the current popular research and development direction.

The mechanism of the corrosion of the inner surface of the borosilicate glass is a network structure of ion exchange reaction and acid-base corrosion glass, water enables certain alkali metal ions in a glass framework to migrate into a solution and simultaneously generate hydroxyl ions, and the corrosion degree of the glass is continuously deepened along with the continuous increase of the concentrations of the alkali metal ions and the hydroxyl ions in an etching solution. The continuous increase of the silicon migration quantity enables the framework structure of the glass network to become loose, so that the phenomenon of glass flaking occurs. Since the flaking phenomenon is a serious problem in the observation of the glass transmittance, the study of ampoules with high transmittance is helpful for clinical observation of the flaking problem of ampoules.

In addition, after the ampoule bottle is fired, marks, scale marks and the like need to be made on the bottle body by using ink, however, the existence of alkali ions on the glass surface forms Na-O bonds, the bonds are easily broken in air and water, so that the ink is difficult to adhere, and certain ink is difficult to adhere or decolor, so that the observation effect of the solution in the ampoule bottle is influenced.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a boron-aluminum silicate glass ampoule bottle and a post-treatment method thereof, which are used for solving the problems of low transmittance and poor ink adhesion of the ampoule bottle in the prior art.

In order to solve the above problems, the technical solution provided by the present invention is:

a boron-free aluminosilicate glass ampoule bottle is prepared by melting the following raw materials in mole fraction:

SiO ₂ :40-60 parts;

Na ₂ o:5-8 parts;

K ₂ o:5-8 parts;

Al ₂ O ₃ :10-13 parts;

CaO:10-15 parts;

BaO:4-10 parts;

TiO ₂ :0-3 parts of a solvent;

after glass is melted and molded, mixed solution of tetramethyl guanidine, triethylamine and ammonia water is used for erosion treatment.

Further, in the present invention,

the glass is prepared by melting the following raw materials in mole fraction:

SiO ₂ :45 parts of (1);

Na ₂ o:5-6 parts;

Al ₂ O ₃ :10-12.5 parts;

CaO:10-15 parts;

BaO:4-9 parts;

TiO ₂ :0-3 parts of.

Further, in the case of a liquid crystal display device,

Na ₂ o and CaO are respectively Na ₂ CO ₃ ,CaCO ₃ The introduced grain sizes are respectively 1-0.2mm and 0.2-1mm.

Further, in the present invention,

the molar ratio of tetramethylguanidine to triethylamine to ammonia was 6.

A post-treatment method for preparing the boron-free aluminosilicate glass ampoule bottle comprises the following steps:

1) Preparing a mixed solution of tetramethylguanidine, triethylamine and ammonia water as an etching solution, and putting a glass ampoule bottle into the etching solution to prepare etched glass;

2) Cleaning and drying the etched glass ampoule bottle, and then performing screen printing to obtain a preset mark;

3) Irradiating the printing part by using a UV lamp to solidify the ink;

further, in the present invention,

the glass pretreatment process comprises ultrasonic cleaning in an ethanol solution for 5-10min to remove impurities remained on the surface of the glass, then washing with deionized water, and drying with dry nitrogen for later use.

Further, in the present invention,

and cleaning the etched ampoule bottle by using alcohol again to remove the residual etching solution on the surface of the glass.

Further, in the case of a liquid crystal display device,

etching the body part of the ampoule bottle before injecting the liquid medicine into the ampoule bottle, packaging the opening of the body before etching the body part of the ampoule bottle, and then putting the packaged ampoule bottle body into the etching liquid;

and after the bottle body of the ampoule bottle is sealed and etched, printing ink is printed.

After the printing of the body of the ampoule is completed, the head of the ampoule is blown and the head is fused with the body.

The technical scheme provided by the invention can realize the following technical effects:

the scheme is suitable for post-treatment of boron-free aluminosilicate glass, and B is not added in glass components ₂ O ₃ In order to optimize the melting behavior of the glass and to improve the working up, na is added correspondingly ₂ O content but Na ₂ An excessively high O content leads to a reduction in the mechanical strength of the ampoule and a corresponding increase in Al ₂ O ₃ The proportion of the glass is as follows.

Tetramethylguanidine contains CH ₃ The functional group, namely the C = N bond in the tetramethylguanidine organic group, can activate some alkali metal ions in the glass skeleton and accelerate the alkali metal ions to migrate into the etching solution, so that the tetramethylguanidine can accelerate the corrosion of the glass surface, and the glass surface is corroded. Triethylamine and ammonia water can combine with alkali metal ion, and the erosion on glass surface is accelerated, and after the erosion phenomenon takes place, the surface can form the groove structure, because surface roughness increases, consequently can reduce the reflection on glass surface, increases the transmissivity simultaneously, consequently, can show the transmissivity that improves glass.

Due to the corrosion phenomenon of the glass surface, the wetting angle of the ink can be obviously increased, so that the ink is very easy to attach to the glass surface, and the printing process of the ink in the later period is very favorable.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention or related technologies, the drawings used in the description of the embodiments or related technologies will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.

FIG. 1 is a schematic illustration of the surface structure of glass provided in example 1 without post-treatment;

FIG. 2 is a schematic view of the surface structure of the post-treated glass provided in example 7.

Detailed Description

The components in the embodiments 1 to 6 are accurately weighed, ground and uniformly mixed, and then the mixture is placed in a silicon-molybdenum furnace for high-temperature melting, and the temperature is kept for 4 hours at 1620 ℃. And pouring the molten glass on a graphite mold, transferring the molded glass to a muffle furnace, and annealing at 560 ℃ for 1h to eliminate internal stress to obtain the glass block.

And (3) processing the processed glass block according to the performance test requirements for structure and performance tests, wherein the structure and performance tests comprise a transmittance test, a wetting angle test and a three-point mechanical strength test.

Then, the ampoule was blown according to the formulation of examples 1 to 6, surface ink printing was performed on the ampoule, and then an adhesion test and a peeling test were performed on the printed glass ampoule.

Wherein:

the adhesion fastness of the ink is referred to the standard GB/T13217.7-2009;

detection of ink peeling force: reference standard: GB/T26394-2011.

Table-different raw material ratios

	SiO 2	Na 2 O	K 2 O	Al 2 O 3	CaO	BaO	TiO 2
								Example 1	45	5	5	10	10	4	0
Example 2	45	5	6	10.5	11	5	1
								Example 3	45	5	7	11	12	6	1
Example 4	45	5	8	11.5	13	7	2
								Example 5	45	6	5	12	14	8	2
Example 6	45	6	8	12.5	15	9	3

Table two performance test results of ampoule bottles with different raw material ratios

	Transmittance of light	Wetting Angle/° C	Mechanical Strength/10 6 Pa	Fastness to adhesion%	Peel force (N/15 mm)
						Example 1	92.94％	2.54	12.51	93.1	0.91
Example 2	92.61％	2.57	12.67	93.2	0.89
						Example 3	92.08％	2.63	12.69	92.9	0.87
Example 4	92.09％	2.61	13.10	93.5	0.92
						Example 5	92.57％	2.15	13.05	92.7	0.87
Example 6	92.55％	2.49	13.29	92.8	0.88

As can be seen from Table II:

1) In examples 1-6, the transmittance of the glass material ranged from 92.09% to 92.94%;

2) In examples 1 to 6, the wetting angle of the glass raw material was in the range of 2.15 to 2.63 °;

3) In examples 1 to 6, the mechanical strength of the glass material ranged from (12.51 to 13.29). Times.10 ⁶ Pa

4) In examples 1 to 6, the ink adhesion fastness in the glass base material was in the range of (92.7% to 93.1%);

5) In examples 1 to 6, the peeling force of the ink in the glass raw material fluctuated in the range of (0.87 to 0.92) N/15 mm;

the glass in the glass proportioning in the embodiment 1 is taken as a base material, the glass is pretreated, the glass pretreatment procedure comprises the steps of ultrasonically cleaning the base material in an ethanol solution for 5-10min to remove impurities remained on the surface of the glass, then washing the base material with deionized water, and drying the base material with dry nitrogen for later use. Then preparing erosion liquids with different concentration gradients respectively corresponding to example 7, example 8, example 9, example 10 and example 11; and (3) putting the pretreated glass into a reaction container filled with etching liquid, carrying out oil bath treatment at the temperature of 100 ℃ for 60min, repeatedly washing with water and ethanol, and drying with dry nitrogen.

Erosion liquid with different proportions in table III

	Tetramethylguanidine concentration mol/L	Triethylamine concentration mol/L	Ammonia water concentration mol/L
				Example 7	0.12	0.06	0.02
Example 8	0.3	0.15	0.05
				Example 9	0.48	0.24	0.08
Example 10	0.72	0.36	0.12
				Example 11	0.9	0.45	0.15

In examples 7 to 11, the transmittance test, the wetting angle test, and the glass strength test were performed on a glass block, the adhesion test and the peeling force test were performed on an ink-printed ampoule, and the ink-printed ampoule was prepared by the following steps:

before etching the body part of the ampoule bottle, packaging the opening of the bottle body, and then putting the packaged ampoule bottle body into etching liquid to prepare an etched ampoule bottle; cleaning and drying the etched glass, and then carrying out screen printing to obtain a preset mark; irradiating the printing part by using a UV lamp to solidify the ink; then, an adhesion test and a peel force test were performed.

TABLE IV various Properties of the etched glass ampoules

	Transmittance of light	Wetting Angle/°	Mechanical Strength/10 6 Pa	Fastness to adhesion%	Peel force (N/15 mm)
						Example 7	93.01％	2.64	12.4	94.1	0.90
Example 8	94.21％	2.96	10.1	94.2	0.92
						Example 9	94.75％	3.12	8.9	94.2	0.92
Example 10	95.64％	3.19	8.1	94.5	0.93
						Example 11	95.8％	3.24	7.29	94.7	0.93

From examples 7 to 11, it can be seen that, before etching, the glass surface is smooth (see fig. 1), after etching, a fine groove structure is formed on the glass surface (see fig. 2), the surface roughness is increased, the existence of the surface roughness greatly improves the contact area between the liquid drop and the glass surface, so that the surface is more hydrophilic, and a super-hydrophilic surface structure is formed, and the following experimental results can be obtained through examples 7 to 11:

1) The contact angle is gradually increased along with the gradual increase of the concentration of the erosion liquid, and can be increased to 3.24 degrees.

2) After the corrosion of the corrosion liquid with different concentrations, the transmittance is obviously increased, and when the concentration of the tetramethylguanidine is 0.9mol/L, the concentration of the triethylamine is 0.45mol/L and the concentration of the ammonia water is 0.15mol/L, the highest transmittance can reach 95.8 percent.

3) After the corrosion of the corrosion liquid with different concentrations, the mechanical strength is gradually reduced, and the mechanical strength can be maintained at 12.4 multiplied by 10 under the test conditions that the concentration of the tetramethylguanidine is 0.12mol/L, the concentration of the triethylamine is 0.06mol/L and the concentration of the ammonia water is 0.02mol/L ⁶ Pa。

4) After the corrosion of the corrosion liquid with different concentrations, the adhesion fastness is obviously enhanced along with the gradual enhancement of the concentration of the corrosion liquid, and the adhesion fastness fluctuates within the range of 94.1-94.7%;

5) After the corrosion by the corrosion liquid with different concentrations, the stripping force is gradually enhanced along with the gradual enhancement of the concentration of the corrosion liquid, and the range is 0.90-0.93 (N/15 mm).

In summary, the present solution can achieve at least the following technical effects:

1. the scheme adopts the raw material proportion without boron, prepares and forms the boron-free aluminosilicate glass, greatly saves the raw material cost and improves the production efficiency.

2. According to the scheme, the corrosion treatment of tetramethylguanidine, triethylamine and ammonia water is carried out on the basis of boron-free aluminosilicate, so that the mechanical strength can be ensured, the wetting angle of the glass surface can be increased, the transmittance can be obviously improved, and the beneficial effects of improving the ink adhesion fastness and the stripping force can be brought.

Finally, it should be noted that: the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (5)

1. A boron-free aluminosilicate glass ampoule bottle is characterized in that: the alloy is prepared by melting the following raw materials in mole fraction:

SiO ₂ :40-60 parts;

Na ₂ o:5-8 parts;

K ₂ o:5-8 parts;

Al ₂ O ₃ :10-13 parts;

CaO:10-15 parts;

BaO:4-10 parts;

TiO ₂ :0-3 parts of a solvent;

after glass is melted and molded, carrying out erosion treatment on a mixed solution of tetramethylguanidine, triethylamine and ammonia water, wherein the molar ratio of the tetramethylguanidine to the triethylamine to the ammonia water is 6;

the concentration of tetramethylguanidine is 0.9mol/L, the concentration of triethylamine is 0.45mol/L and the concentration of ammonia water is 0.15 mol/L;

pretreating glass, wherein the glass pretreatment procedure comprises ultrasonic cleaning in an ethanol solution for 5-10min to remove impurities remained on the surface of the glass, then washing with deionized water, and drying with dry nitrogen for later use;

placing the pretreated glass into a reaction vessel filled with etching liquid, carrying out oil bath treatment at the temperature of 100 ℃ for 60min, repeatedly washing with water and ethanol, and drying with dry nitrogen;

before etching the body part of the ampoule bottle, packaging the opening of the body, and then putting the packaged ampoule bottle body into etching liquid to prepare an etched ampoule bottle; cleaning and drying the etched glass, and then carrying out screen printing to obtain a preset mark; irradiating the printing part by using a UV lamp to solidify the printing ink; then, an adhesion test and a peeling force test were performed.

2. The boron-free aluminosilicate glass ampoule of claim 1,

Na ₂ o and CaO are respectively made of Na ₂ CO ₃ ,CaCO ₃ The introduced grain sizes are respectively 1-0.2mm and 0.2-1mm.

3. A post-treatment process for the preparation of a boron-free aluminosilicate glass ampoule according to claim 1 or 2, comprising the steps of:

1) Preparing a mixed solution of tetramethylguanidine, triethylamine and ammonia water as an etching solution, and putting the glass ampoule bottle into the etching solution to prepare an etched glass ampoule bottle;

2) Cleaning and drying the etched glass ampoule bottle, and then performing screen printing to obtain a preset mark;

3) The printed portion was irradiated with UV light to cure the ink.

4. The method of claim 3, wherein the post-treatment of the boron-free aluminosilicate glass ampoule,

and cleaning the etched ampoule bottle by using alcohol again to remove the residual etching solution on the surface of the glass.

5. The method of claim 4, wherein the post-treatment of the boron-free aluminosilicate glass ampoule,

after the printing of the body of the ampoule is completed, the head of the ampoule is blown and the head is fused with the body.

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