CN1038126C

CN1038126C - Method for manufacturing reinforced glass road sign

Info

Publication number: CN1038126C
Application number: CN92109713A
Authority: CN
Inventors: 叶均蔚
Original assignee: Individual
Current assignee: Individual
Priority date: 1992-08-21
Filing date: 1992-08-21
Publication date: 1998-04-22
Anticipated expiration: 2007-08-21
Also published as: CN1083027A

Abstract

The present invention relates to a method for manufacturing a reinforced glass road sign. A road sign is a marking body which is used for dividing a vehicle way on the road surface or is used as a warning indicator; a yellow reinforced glass road sign can be manufactured by the special manufacturing method which is provided by the present invention, and a yellow or colorless reinforced glass road sign with a high refractive index can also be manufactured. The method of the present invention comprises the following steps: cerium oxide and titanium oxide are added into the main component of the glass, and then, the glass is melted by heat, shaped and reinforced to obtain the yellow reinforced glass road sign; the refractive index of a product can be provided by controlling the proportion of barium oxide or lead oxide in the component of the glass.

Description

Method for manufacturing reinforced glass road button

The invention relates to a method for manufacturing a road button, in particular to a method for manufacturing a reinforced glass road button.

The road button is used on the road to be used as a mark body for distinguishing lanes or warning marks. The development phases for road buttonsare roughly as follows:

1. age without buttons

In the plane painting type era, white lines or yellow lines are drawn on roads to be used as marking lines for distinguishing lanes or warning, the method is simple and cheap, and is still generally used until now, but the marking method has poor warning effect and visual effect due to no bulge, has no obvious visual effect on drivers, cannot provide proper safety warning effect particularly in dangerous curves, at night, in rainy days and in dense fog, and the applied paint gradually wears due to rolling of vehicles after a period of time and loses the necessary marking effect.

2. Plastic road button and aluminum alloy road button times

The road buttons are adopted on expressways of Taiwan and some special road surfaces, convex roads made of plastic or aluminum alloy structural bodies are adapted to the road signs with high heights, and the reflecting sheets are adhered according to the front and back of the convex roads and have a reflecting effect on vehicle light, so that the warning effect of the road signs is increased, although the method is superior to the method for marking paint in light reflection performance, the method still has the following practical defects:

(A) the aluminum alloy or plastic structure has a compressive strength of 1 ton or less and a breaking strength of about 3 tons, and is therefore easily deformed and broken by pressure, and therefore, it is frequently replaced and supplemented, and may puncture a tire.

(B) The reflecting sheet of the reflecting road sign is exposed, so that dust is easily accumulated and is easily pulled off and crushed to lose the reflecting function.

3. Green cat eye type road button times

The button is made of tempered glass. A cat-eye type road marker of pelkington corporation in south africa, which is shown in fig. 1, is composed of a disc-shaped embedded part B and a hemispherical convex part a, wherein a metal film such as aluminum or zinc is plated on the peripheral surface of the embedded part as a reflecting surface C, and the convex part is used for gathering the projected light and reflecting the light again through the reflecting surface, so as to form a road button capable of gathering light and reflecting light for warning the position of a road dividing line of a driver; furthermore, in order to increase the compressive strength of the road sign to withstand the loads and friction of the vehicle during driving, the glass road sign is strengthened to obtain a high strength and surface hardness, the compressive strength being set at 20 tons or more on average, while the unreinforced glass is about 5 tons.

However, the cat-eye type road stud is light green due to the influence of the glass material composition, and the color of the light green is reflected no matter the light green is used for yellow or white marking lines, the colors are obviously not accordant with the color of the original separation lines, particularly the yellow marking lines easily cause the confusion of drivers to influence the traffic order, in addition, the refractive index of the road stud is not high, and the reflection brightness of the light is not ideal, so the cat-eye type road stud is difficult to be further widely applied after being tried for a period of time.

In fact, the green cat eye type road button is a failed road button, which is not accepted in the market, and the subsequent improvements cannot be technically broken through, such as the refractive index cannot be increased, and the color cannot be improved; the industry abandoned the development of green cat-eye buttons, and strengthened glass was used as the button material, and was therefore completely eliminated.

Therefore, the present invention develops a strengthened glass road button which can obtain high refractive index yellow transparent (yellow reflection) or colorless transparent (white reflection) and is suitable for being used as a yellow or white marking line.

In the case of yellow glass, the method commonly used in industry is a colloidal chromophoric method, which can be classified into a metal colloidal chromophoric method and a compound colloidal chromophoric method; the former metal colloid coloring method is to add a silver compound such as silver chloride (AgCl) to a glass raw material and to add a reducing agent such as tin oxide (SnO)₂) During slow cooling after taking out, tinThe ions reduce silver ions and crystallize out to obtain yellow color, and the basic reaction formula is as follows:

the latter compound colloid color development method is characterized by adding cadmium sulfide (CdS) into glass raw material, and after melting and cooling, the cadmium sulfide (CdS) is crystallized out due to over-saturation and is yellow.

However, the two color development methods are not suitable for the manufacture of quench-strengthened glass, because the nucleation and growth of crystals in the above-mentioned colloid color development method must be completed by chemical reaction and diffusion process, i.e. slow cooling is required to obtain the desired color development of crystals, and in the quenching process, the glass product is cooled to a temperature below the softening point within minutes after molding, and thus the colloid particles are not fully formed, and only colorless or very pale color effect can be obtained. If the color is reproduced again after the strengthening by heating above the softening point for a period of time, the strengthening effect is obviously eliminated due to the softening by heating; furthermore, if the glass is first precipitated at a high temperature to develop color, the strength of the base material is lowered due to the dispersion of the colloidal particles, and the formed glass is liable to undergo spontaneous explosion when it is not subjected to internal tensile stress after rapid cooling. Therefore, the above colloidal coloring method hardly provides strengthening treatment and cannot provide high strength.

In view of the above problems, the present inventors have studied and developed a glass composition additive which develops a color by a non-colloidal color development method, is rapidly quenched and strengthened as thick glass, and has a yellow color. Which is added with cerium oxide (CeO)₂) And titanium oxide (TiO)₂) The components, etc., are colored yellow by the interaction of their ions, and since this color development does not contradict the quenching strengthening operation, the quenching strengthening treatment can be performed.

The invention relates to a method for manufacturing a yellow transparent strengthened glass road button, which comprises the following steps:

(a) adding 1-5% by weight of cerium oxide (CeO) into the main component of the glass₂) And 1-5% of titanium oxide (TiO)₂) Heating and melting into glass paste;

(b) taking out the glass paste and forming the glass paste into a road button in a model; and

(c) the molded road button is reinforced by a rapid cooling and reinforcing method.

The invention relates to a method for manufacturing a high-refractive-index colorless transparent strengthened glass road button, which comprises the following steps:

(a) barium oxide (BaO) and/or lead oxide (PbO) with the weight percent of 1-8 percent are contained in the main component of the glass, and the glass is heated and melted into glass paste;

In addition, in view of the importance of the refractive index of the tempered glass road button on light condensation and reflection, the invention utilizes barium oxide (BaO) or lead oxide (PbO) to increase the refractive index and applies quenching strengthening treatment, and the experimental result proves that the improvement effect of the refractive index and the reflection degree can be obtained after the strengthening process.

The invention can produce the high-refractivity colorless transparent strengthened glass road button by controlling the adding amount of barium oxide (BaO) and/or lead oxide (PbO) in the glass components, and can be used in the manufacture of yellow strengthened glass to produce the high-refractivity yellow transparent strengthened glass road button.

The road button of the present invention is subjected to a strengthening treatment after being molded in a mold, and there are many methods for improving the strength and impact resistance thereof, wherein the methods commonly used in industry are classified into a chemical strengthening method and a quenching strengthening method; the chemical strengthening method is usually to add sodium (Na)⁺) Is dipped into a glass containing potassium (K)⁺) The salt bath of (1) is treated at 400-500 deg.C for 1 or several hours, then slowly cooled, because the potassium ions and sodium ions are exchanged on the surface ions by diffusion in the salt bath, the surface of the salt bath has high concentration of potassium ions, the concentration of which isgradually decreased from outside to inside, because the radius of potassium ions is larger than that of sodium ions, the surface layer generates a compressive stress state to form a strengthening effect, and the compressive stress is also gradually decreased from the surface to inside along with the decrease of potassium ion concentration, but the diffusion strengthening layer of the chemical strengthening method is not large (about several tens of microns), is not suitable for strengthening treatment of thick glass, and is usually adopted for strengthening treatment of thin glass with thickness of less than 1 mm.

The second strengthening method is a rapid cooling strengthening method in which the glass is heated to a temperature higher than the softening point, and then rapidly cooled by salt bath cooling, oil bath cooling, forced air cooling, or steam cooling, and the surface layer is brought into a compressive stress state due to the difference in the amount of shrinkage between the surface layer and the inside, and the inside is brought into a tensile stress state, so that the strength of the glass such as tensile strength, compression strength, or bending strength is increased, and the compressive stress layer is much thicker (about several millimeters) than that of the chemical strengthening method, and therefore, the method is suitable for strengthening thick glass. As the thickness of the common glass reflecting road sign is between 20mm and 40mm, the quenching and strengthening treatment method is obviously adopted to achieve the aims of improving the strength and resisting the impact; however, the strengthening of thicker glass is more difficult to implement, and besides the need to reduce the quenching temperature, the proper glass components should be selected to reduce the linear expansion coefficient and the softening point and to improve the initial strength of the glass substrate, and the principle is described below;

(1) when the linear expansion coefficient is reduced, the difference between the surface layer and the internal shrinkage can be reduced, so that the internal tensile stress is not too high; when operating a quench strengthening process, spontaneous explosion of the glass often originates from the interior, and thus reducing the internal tensile stress can greatly reduce the likelihood of cracking of the interior.

(2) Lowering the softening point helps to lower the operating temperature, which reduces the internal tensile stress and reduces the likelihood of cracking.

(3) Increasing the strength of the glass substrate increases the cracking stress and thus reduces cracking.

Example 1

With SiO₂：69.9％，Na₂O：15％，CaO：15％，As₂O₃: 0.1% of glass paste is placed in a crucible, the glass paste is clarified, the glass paste is taken out of the mold and molded into a knob shape, the mold is heated to a temperature higher than the softening point, and then the mold is rapidly cooled and strengthened, as a result, the finished product can obtain a breaking strength of 20 tons or more, but the refractive index is not higher than 1.5, and the knob is colorless.

Example 2

With SiO₂：67.8％，B₂O₃：2％，Na₂O：15％，CaO：13％，BaO：2％，As₂O₃: 0.2% of glass paste, and applying a forming button strengthening treatment, the glass paste is colorless, but the refractive index is also high at 1.53, and the breaking strength is more than 20 tons.

Example 3

With SiO₂：69.8％，B₂O₃：2％，Na₂O：13％，CaO：11％，BaO：2％，PbO：2％，As₂O₃: 0.2% of glass paste,and applying shaping button strengthening treatment, the glass paste is colorless, but has a high refractive index of 1.53 and a breaking strength of 20 tons or moreIn addition, since the compressive stress layer is much thicker (about several millimeters) than the chemical strengthening method, it is suitable for the strengthening treatment of thick glass. As the thickness of the common glass reflecting road sign is between 20mm and 40mm, the quenching and strengthening treatment method is obviously adopted to achieve the aims of improving the strength and resisting the impact; however, the strengthening of thicker glass is more difficult to implement, and besides the need to reduce the quenching temperature, the proper glass composition should be selected to reduce the linear expansion coefficient, the softening point and increase the green strength of the glass substrate, and the principle is as follows:

Example 1

With SiO₂：69.9％，Na₂O：15％，CaO：15％，As₂O₃: 0.1% of glass paste is placed in a crucible, the glass paste is clarified, the glass paste is taken out of the mold and molded into a knob shape, themold is heated to a temperature higher than the softening point, and then the mold is rapidly cooled and strengthened, as a result, the finished product can obtain a breaking strength of 20 tons or more, but the refractive index is not higher than 1.5, and the knob is colorless.

Example 2

Example 3

With SiO₂：69.8％，B₂O₃：2％，Na₂O：13％，CaO：11％，BaO：2％，PbO：2％，As₂O₃: 0.2% of glass paste, and applying shaping button strengthening treatment, the glass paste is colorless, but has a high refractive index of 1.53 and a breaking strength of 20 tons or moreThe above.

Example 4

With SiO₂：70％，B₂O₃：3％，Na₂O：15％，CaO：8％，BaO：2％，CeO₂: 2% of the composition is prepared into glass paste, and the glass paste is subjected to strengthening treatment of the molded road button, so that the glass paste is colorless, the refractive index is also high and is 1.535, and the breaking strength is more than 20 tons.

Example 5

With SiO₂：73％，Na₂O：15％，CaO：8％，BaO：2％，TiO₂: 2% of the composition is prepared into glass paste, and the glass paste is subjected to strengthening treatment of the molded road button, so that the glass paste is colorless, the refractive index is also high and is 1.52, andthe breaking strength is more than 20 tons.

Example 6

With SiO₂：71％，B₂O₃：2％，Na₂O：15％，CaO：8％，BaO：2％，CeO₂：1％，TiO₂: 1% of the composition is prepared into glass paste, and the glass paste is subjected to strengthening treatment of the molded road button, and the glass paste is light yellow, has a high refractive index of 1.53 and has a breaking strength of more than 20 tons.

Example 7

With SiO₂：67％，Na₂O：15％，CaO：8％，PbO：2％，CeO₂：4％，TiO₂: 4 percent of the composition is prepared into glass paste, and the glass paste is subjected to strengthening treatment of a formed road button, and the formed road button has yellow chromaticity which is similar to that of a common reflective sheet, the refractive index is also high by 1.55, and the breaking strength is more than 20 tons.

From the above examples, it is understood that the composition ranges shown in the above tables are such that the breaking strength is 20 tons or more when the reinforcing treatment is applied, and the appropriate yellow coloring effect can be obtained when 1% to 5% of each of cerium oxide and titanium oxide is simultaneously added (examples 6 and 7), and the refractive index of the molded road block is high when 1% to 8% of barium oxide and/or lead oxide is added (examples 2 to 7).

According to the manufacturing method of the present application, a yellow strengthened glass road button, a colorless strengthened glass road button with a high refractive index, and a yellow strengthened glass road button with a high refractive index can be successfully manufactured.

The road button can resist high pressure without considering rolling of aheavy vehicle, can be colorless and transparent (white reflection) and can be paved on a white line of a road surface, can be yellow and transparent (yellow reflection) and can be paved on a yellow line of the road surface, and can further have high refractive index, and the special excellent properties of the high refractive index can be realized, so that the beautiful dream taking the tempered glass as the road button can be really realized. The road button produced by the method completely meets the requirements of modern traffic rules and traffic safety, is durable and does not fall off after being laid and pasted, can be protruded from the road surface to increase the warning and reflecting effects, can bear heavy pressure, has high refractive index and reflects light in white or yellow, has the advantages of distinguishing lanes and warning mark bodies, and is superior to any existing road button (plastic or aluminum alloy road button). Because of the disclosure of this case, the road button is leading to another new era.

Brief description of the drawings:

fig. 1 is a schematic view of a conventional cat-eye-shaped tempered glass road button.

Claims

1. A manufacturing method of a yellow transparent strengthened glass road button comprises the following steps:

(a) adding 67-73% by weight of SiO to the main glass component₂，13～15Na₂Sodium silicate glass containing O as main component and 1-5% cerium oxide (CeO)₂) And 1-5% of titanium oxide (TiO)₂) Heating and melting into glass paste;

(b) taking out the glass paste, and forming the glass paste into a road button with a hemispherical convex part with the thickness of 20-40 cm in a model; and

(c) the molded road button is reinforced by rapid cooling from the softening point temperature or higher.

2. The production process according to claim 1, wherein the glass as the main component in (a) contains 1 to 8% by weight of barium oxide (BaO) and/or 1 to 8% by weight of lead oxide (PbO).

3. A method for manufacturing a high-refractive-index colorless transparent strengthened glass road button comprises the following steps:

(a) will contain 67-73% by weight of SiO₂，13～15％Na₂Adding 1-8% of barium oxide (BaO) and/or 1-8% of lead oxide (PbO) into sodium silicate glass taking O as a main component, and heating and melting into glass paste;

(c) the molded road button is reinforced by a rapid cooling strengthening method from the softening point temperature or higher.