CN119612935B - Low-absorption high-transmittance glass, forming method thereof and window glass - Google Patents
Low-absorption high-transmittance glass, forming method thereof and window glassInfo
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- CN119612935B CN119612935B CN202411742708.4A CN202411742708A CN119612935B CN 119612935 B CN119612935 B CN 119612935B CN 202411742708 A CN202411742708 A CN 202411742708A CN 119612935 B CN119612935 B CN 119612935B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B23/00—Re-forming shaped glass
- C03B23/02—Re-forming glass sheets
- C03B23/023—Re-forming glass sheets by bending
- C03B23/0235—Re-forming glass sheets by bending involving applying local or additional heating, cooling or insulating means
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
- B60J1/00—Windows; Windscreens; Accessories therefor
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- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Re-Forming, After-Treatment, Cutting And Transporting Of Glass Products (AREA)
Abstract
The invention provides low-absorption high-transmittance glass, a forming method thereof and vehicle window glass. The forming method comprises the steps of placing a glass raw sheet in a heating furnace for heating treatment and then pressing forming, wherein the heating furnace comprises a preheating section, a heating section and a constant temperature gradual change section which are connected in sequence, the inlet temperature of the preheating section is 548-596 ℃ and the outlet temperature of the preheating section is 571-631 ℃, the outlet temperature of the preheating section is higher than the inlet temperature, the inlet temperature of the heating section is 595-646 ℃ and the outlet temperature of the heating section is 628-673 ℃, the outlet temperature of the heating section is higher than the inlet temperature, the temperature of the constant temperature gradual change section is 628-674 ℃, the inlet temperature of the heating section is greater than or equal to the outlet temperature of the preheating section, and the difference value between the inlet temperature of the constant temperature gradual change section and the outlet temperature of the heating section is more than or equal to-3 ℃. The low-absorption high-transmittance glass can meet the requirement of an optical sensor on optical transmittance, and can be used for manufacturing the functional integrated glass.
Description
Technical Field
The invention relates to the technical field of automobile glass manufacturing, in particular to low-absorption high-transmittance glass, a forming method thereof and vehicle window glass.
Background
The raw sheets of the automobile glass, especially the front windshield glass, are generally automobile grade raw sheets produced by a float process, and the automobile grade raw sheets comprise common white glass (Clear, abbreviated as C), green glass (Green, abbreviated as G), heat absorption Green glass (SolarGreen, abbreviated as SG), super heat absorption Green glass (SolarDark, abbreviated as SD) and the like.
At present, automobile glass, especially front windshield glass, has more and more optical sensor elements such as LiDAR, infrared camera and the like integrated in a bump area, and the requirements of the optical sensors on the front windshield glass are higher and higher, so that the maximum optical transmittance is required to be realized in a corresponding near infrared band, such as 800-1600 nm. The existing automobile glass raw sheet cannot meet the requirements, and needs to have low absorption and high transmittance in corresponding wave bands. The above glass raw sheet having low absorption and high light transmittance in the corresponding wavelength band is different from the existing molding parameters of the automobile glass raw sheet, and it is necessary to provide a molding method for such glass raw sheet.
Disclosure of Invention
In order to solve the above problems, an object of the present invention is to provide a low-absorption high-transmittance glass, a molding method thereof, and a window glass. The low-absorption high-transmittance glass has low molding temperature, low absorption and high transmittance, can meet the requirement of an optical sensor on optical transmittance, and can be used for manufacturing functional integrated glass.
In order to achieve the above object, the present invention provides a molding method of low absorption high transmission glass, comprising:
The method comprises the steps of placing a glass raw sheet into a heating furnace for heating treatment, and then performing compression molding to obtain the low-absorption high-permeability glass, wherein the heating furnace comprises a preheating section, a heating section and a constant temperature gradual change section which are connected in sequence, the inlet temperature of the preheating section is 548-596 ℃, the outlet temperature of the preheating section is 571-631 ℃, the outlet temperature of the preheating section is higher than the inlet temperature of the preheating section, the inlet temperature of the heating section is 595-646 ℃, the outlet temperature of the heating section is 628-673 ℃, the outlet temperature of the heating section is higher than the inlet temperature of the heating section, the temperature of the constant temperature gradual change section is 628-674 ℃, the inlet temperature of the heating section is greater than or equal to the outlet temperature of the preheating section, and the difference between the inlet temperature of the constant temperature gradual change section and the outlet temperature of the heating section is more than or equal to-3 ℃ (namely, the inlet temperature of the constant temperature gradual change section and the outlet temperature of the heating section are more than or equal to-3 ℃).
In the forming method, the preheating section is used for heating the glass raw sheet in the first stage, the heating section is used for heating the glass raw sheet in the second stage, and the constant temperature gradual change section is used for preserving heat of the glass raw sheet and transmitting the preserved heat to the subsequent working procedure. The preheating section and the heating section can be approximately divided by the softening temperature of the glass raw sheet, the heating temperature of the glass raw sheet in the preheating section is generally lower than the softening temperature of the glass raw sheet, and the heating temperature of the glass raw sheet in the heating section is generally higher than the softening temperature of the glass raw sheet, so that the softening process of the glass raw sheet is started after the glass raw sheet enters the heating section. It will be appreciated that in actual production, the heating temperature of the heating furnace is generally not equal to the heating temperature of the glass, and therefore, the heating temperature of each section of the heating furnace can be adjusted accordingly based on the softening temperature range of the glass, so long as the heating degree is reached that the glass is heated in the preheating section but is not softened and is softened after entering the heating section.
In the present invention, the softening temperature (INTENERATE TEMPERATURE) of the glass raw sheet means a temperature at which glass begins to deform or soften under the action of its own weight, and for example, the softening temperature of the low-absorption high-transmittance glass raw sheet such as the ultra-white glass raw sheet is about 606 ℃. The softening temperature of the glass is generally less than 100-120 ℃ below its softening point. The softening point refers to the temperature at which the glass begins to deform or soften under certain conditions. The softening point can be measured by LITTLETEN glass filaments vertical extension method, and the process is that when glass filaments with a hanging density of about 2.5g/cm 3, a diameter of 0.55-0.75mm and a length of 229mm are heated, the temperature at the time of extension at a speed of 1mm/min is the softening point.
In the above molding method, the temperature rising speed of the preheating section may be controlled to be 0.07 ℃ per second to 5.4 ℃ per second.
In the above molding method, the temperature rising speed of the heating section may be controlled to be 0.01 ℃ per second to 4.0 ℃ per second.
In some embodiments, the heating rate of the preheating section may be greater than or equal to the heating rate of the heating section. The temperature change amplitude in the constant temperature gradual change section is smaller, the temperature rising speed is very small, and the temperature rising speed of the constant temperature gradual change section is generally smaller than the temperature rising speeds of the preheating section and the heating section.
In the above-described molding method, the temperature raising method in each section (preheating section, heating section, constant temperature gradient section) may be a common temperature raising method such as constant temperature raising, variable speed temperature raising, step temperature raising, etc., and the present invention is not particularly limited to the temperature raising method.
The invention divides the heating furnace into three main heating treatment sections of a preheating section, a heating section and a constant temperature gradual change section according to functions, each section can be further divided according to the actual conditions of equipment (such as the positions, the number and the like of heating components such as heating wires and the like in the heating furnace), and the invention has no special limit on the number of the further divisions of the preheating section, the heating section and the constant temperature gradual change section, so long as the heating scheme (such as heating temperature, heating speed and the like) of each section can be realized.
The molding method of the present invention will be further described below by taking a total of 9 heating zones of the heating furnace as an example:
In the molding method, the heating furnace specifically comprises 9 heating zones, wherein each heating zone is sequentially from a sheet inlet end to a sheet outlet end of the heating furnace, the first zone is a preheating section, the third zone is a preheating section, the fourth zone is a heating section, the seventh zone is a constant temperature gradual change section, the heating temperatures of the first zone are gradually increased (the whole is in an ascending trend, the situation that the temperatures of adjacent heating zones are similar is not excluded, for example, the temperatures of the seventh zone, the eighth zone and the ninth zone can be similar), the glass raw sheet is heated from the upper side and the lower side of the glass raw sheet by each heating zone, the heating temperatures of the first zone, the second zone and the third zone are respectively 548-631 ℃, the heating temperatures of the fourth zone, the fifth zone and the sixth zone are respectively 595-657 ℃, and the heating temperatures of the seventh zone, the eighth zone and the ninth zone are respectively-628 ℃.
According to a specific embodiment of the present invention, the glass raw sheet suitable for the above-mentioned forming method provided by the present invention is a low-absorption, high-transmittance glass raw sheet. The raw glass sheet to which the present invention is applied has a high iron content (for example, an iron content of 700 to 900ppm in a normal white glass, an iron content of 5000ppm in a normal green glass, and an iron content of 7000ppm in an absorbed green glass), and the iron content of the raw glass sheet to which the present invention is applied is generally 150ppm or less, more preferably 130ppm or less or 110ppm or less, still more preferably 90ppm or less. The iron content is the weight content of iron oxide. The lower the iron content the lower the absorption of the glass precursor.
The softening point temperature of the common glass raw sheet is relatively high and is 725-730 ℃, the softening point temperature of the glass raw sheet applicable to the invention is relatively low and is 707-713 ℃, and the annealing point of the glass raw sheet applicable to the invention is generally 540-550 ℃, namely, the softening point temperature is about 28-32 percent (such as 30 percent) higher than the annealing point temperature. The temperature of the softening point of the glass raw sheet to which the invention is applied is proportional to the temperature of the annealing point, and the higher the temperature of the softening point is, the higher the temperature of the corresponding annealing point is. In the above-described molding method of the present invention, the heating temperature of the first region may be higher than the temperature of the annealing point of the glass raw sheet.
In the above-mentioned molding method, the thickness of the glass raw sheet used is generally 1.6mm to 6mm. Specifically, the glass raw sheet may be a glass raw sheet having a thickness of 2.1mm (2.1C glass raw sheet, specifically, ultra-white glass) for use in the manufacture of front windshields, or a glass raw sheet having a thickness of 6mm or less for use in the manufacture of quarter glass.
In the above molding method, the glass raw sheet may have a light absorption coefficient of 0.04 to 0.2cm -1, for example, a specific value such as 0.04cm-1、0.05cm-1、0.06cm-1、0.07cm-1、0.08cm-1、0.09cm-1、0.10cm-1、0.11cm-1、0.12cm-1、0.13cm-1、0.14cm-1、0.15cm-1、0.16cm-1、0.17cm-1、0.18cm-1、0.19cm-1、0.20cm-1, and a range having any two of the specific values as the end points. Further, the light absorption coefficient may be 0.04-0.1cm -1.
In the present invention, the light absorption coefficient refers to the negative value of the natural logarithm of the internal transmittance of natural light per cm distance of the glass raw sheet. When the incident light is perpendicularly incident on the glass sheet, the light intensity is attenuated by the absorption of the glass sheet, and the light absorption coefficient value can be calculated by measuring the natural light transmittance of the glass sheet. Specifically, the following formula can be used for calculation:
K is the light absorption coefficient of the glass raw sheet, l is the thickness of the glass raw sheet in the stacking direction, n is the refractive index of the glass raw sheet for the laser light with the specific wavelength, and T is the transmittance of the glass raw sheet for the laser light with the specific wavelength.
In some embodiments, the raw glass sheet employed in the present invention may be obtained by a float glass production process, such as an electronic grade float glass production process.
The total forming temperature (namely the hot bending forming temperature, namely the heating temperature of the glass raw sheet in a heating furnace) in the forming method is approximately 550-690 ℃, is generally lower than the existing automobile glass forming temperature by more than 10 ℃, is further lower than the existing automobile glass forming temperature by more than 13 ℃, and is further lower than the existing automobile glass forming temperature by more than 15 ℃. The above-mentioned molding temperature range can be applied to the heat molding of a glass raw sheet having a thickness of 1.6 to 6 mm.
In the above molding method, each heating zone in the heating furnace is a first zone, a second zone, a third zone, a fourth zone, a fifth zone, a sixth zone, a seventh zone, an eighth zone and a ninth zone which are sequentially connected along the sheet feeding end to the sheet discharging end of the heating furnace (i.e. along the conveying direction of the glass raw sheet from the furnace feeding end to the furnace discharging end). The heating temperature gradually increases from the first zone to the ninth zone. The first region, the second region and the third region may be referred to as a first third region, the fourth region, the fifth region and the sixth region may be referred to as a middle third region, and the seventh region, the eighth region and the ninth region may be referred to as a second third region. The heating temperature gradually increases from the first zone to the ninth zone (the overall trend is upward, and the condition that the temperatures of adjacent heating zones are similar is not excluded). Specifically, the heating temperature gradually increases from the first zone to the seventh zone, the eighth zone is similar to the seventh zone in heating temperature, and the ninth zone is the same as or similar to the eighth zone in heating temperature.
According to a specific embodiment of the present invention, the heating temperatures of the first, second and third zones are generally controlled to be respectively 548-631 ℃, for example 548 ℃, 550 ℃, 553 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃, 600 ℃, 610 ℃, 620 ℃, 626 ℃, 630 ℃, 631 ℃ and the like, and ranges having any two of the above specific values as endpoints. Further, the heating temperatures of the first, second and third zones may be controlled to 550-629 ℃, and still further may be 553-626 ℃.
According to a specific embodiment of the present invention, the heating temperatures of the fourth, fifth and sixth zones are generally controlled to be 595-657 ℃, respectively, such as 595 ℃, 600 ℃, 610 ℃, 620 ℃, 630 ℃, 640 ℃, 650 ℃, 652 ℃, 655 ℃, 657 ℃ and the like, and ranges ending with any two of the above specific values. Further, the heating temperatures of the fourth, fifth and sixth zones may be controlled to 597-655 ℃, and still further may be 600-652 ℃.
According to a specific embodiment of the present invention, the heating temperatures of the seventh zone, the eighth zone and the ninth zone are generally controlled to be respectively 628-674 ℃, for example, 628 ℃, 630 ℃, 633 ℃, 640 ℃, 650 ℃, 660 ℃, 669 ℃, 670 ℃, 674 ℃ and the like, and ranges having any two of the above specific values as endpoints. Further, the heating temperatures of the seventh zone, the eighth zone, and the ninth zone may be controlled to be 630 to 672 ℃, and still further may be 633 to 669 ℃.
In the above molding method, the top heating temperature of each heating section and each heating zone is generally higher than the bottom heating temperature. In some embodiments, the heating apparatus is disposed at the top and bottom of each heating section and each heating zone in the heating furnace, so that the top heating temperature and the bottom heating temperature of each heating section and each heating zone can be controlled individually. In the invention, the distance between the heating equipment at the top of the same heating zone and the glass raw sheet is larger than the distance between the heating equipment at the bottom and the glass raw sheet, and correspondingly, the heating temperature at the top of the same heating zone is generally higher than the heating temperature at the bottom so as to ensure that the glass raw sheet is heated uniformly on the upper surface and the lower surface.
The height of each heating zone is denoted as h, the glass raw sheet is positioned on the central line of the height direction of the heating zone, the top is the region which is positioned above the glass raw sheet and has a vertical distance of more than 0 and less than or equal to 50% h from the glass raw sheet, and the bottom is the region which is positioned below the glass raw sheet and has a vertical distance of more than 0 and less than or equal to 20% h from the glass raw sheet.
According to a specific embodiment of the present invention, the top heating temperatures of the first zone, the second zone, and the third zone may be controlled to be 560 to 631 ℃, respectively, and for example, may be 560 ℃, 562 ℃, 565 ℃, 570 ℃, 580 ℃, 590 ℃, 600 ℃, 610 ℃, 620 ℃, 626 ℃, 629 ℃, 630 ℃, 631 ℃ and the like, and a range having any two of the above specific values as endpoints, further may be 562 to 629 ℃, and still further may be 565 to 626 ℃.
According to a specific embodiment of the present invention, the bottom heating temperatures of the first, second and third zones may be controlled to be 548-617 ℃, respectively, for example, 548, 550, 553, 560, 570, 580, 590, 600, 610, 612, 615, 617, etc., and ranges having any two of the above specific values as endpoints, further 550-615 ℃, still further 553-612.
According to a specific embodiment of the present invention, the top heating temperatures of the fourth zone, the fifth zone and the sixth zone may be 606 to 657 ℃, respectively, and may be, for example, specific values of 606 ℃, 610 ℃, 620 ℃, 630 ℃, 640 ℃, 650 ℃, 657 ℃ and the like, and ranges having any two of the above specific values as endpoints, further may be 608 to 655 ℃, and still further may be 611 to 652 ℃.
According to a specific embodiment of the present invention, the bottom heating temperatures of the fourth zone, the fifth zone and the sixth zone may be controlled to be 595-650 ℃, respectively, and specific values such as 595 ℃, 597 ℃, 600 ℃, 610 ℃, 620 ℃, 630 ℃, 640 ℃, 645 ℃, 648 ℃, 650 ℃ and the like, and ranges having any two of the above specific values as endpoints, further may be 597-648 ℃, and still further may be 600-645 ℃.
According to a specific embodiment of the present invention, the top heating temperatures of the seventh zone, the eighth zone, and the ninth zone may be controlled to 633 to 674 ℃, respectively, and may be, for example, 633 to 640 ℃, 650 ℃, 660 ℃, 670 ℃, 674 ℃ or the like, and may further be 635 to 672 ℃, and may further be 638 to 669 ℃ in a range having any two of the above specific values as an end point.
According to a specific embodiment of the present invention, the bottom heating temperatures of the seventh zone, the eighth zone, and the ninth zone may be controlled to 628 to 670 ℃, respectively, and may be, for example, specific values of 628 ℃, 630 ℃, 640 ℃, 650 ℃, 660 ℃, 670 ℃, etc., and ranges having any two of the above specific values as endpoints, further may be 630 to 668 ℃, and still further may be 633 to 665 ℃.
In the above molding method, the left, middle and right sides of the top and bottom of each heating zone are provided with heating apparatuses, respectively. Each heating zone has a top left side heating temperature, a top middle heating temperature, a top right side heating temperature, a bottom left side heating temperature, a bottom middle heating temperature, a bottom right side heating temperature, and the heating temperatures at the above positions can be controlled independently. Wherein, the length of one heating zone is denoted as d, the 'middle' refers to the position of a central line (a central line vertical to the transport direction of the glass raw sheet, namely, the central line in the length direction of the heating zone) of each heating zone, the 'left side' refers to a region which is positioned at the left side of the central line of the heating zone and has a horizontal distance from the central line of more than 0 and less than or equal to 30% d, and the 'right side' refers to a region which is positioned at the right side of the central line of the heating zone and has a horizontal distance from the central line of more than 0 and less than or equal to 30% d.
In some embodiments, the heating device may be a heating furnace wire. The heating furnace wires are respectively arranged at the top and the bottom of each heating zone, and further, the heating furnace wires are respectively arranged at the top left side, the top middle, the top right side, the bottom left side, the bottom middle and the bottom right side of each heating zone. The heating temperature at each location of each heating zone may be the temperature of the heating wire.
The heating furnace can ensure that all positions of the glass raw sheet are heated uniformly (including between the upper surface and the lower surface of the glass raw sheet and between the big end, the middle end and the small end of the glass) by simultaneously heating the glass raw sheet from the top, the bottom, the left side, the middle and the right side of the same heating zone. Therefore, better microscopic optical performance is realized, and microscopic optical detection is carried out by means of a refraction plate, a mole scanner and the like so as to meet the optical requirements of the automobile windshield. By adopting the heating mode and controlling the forming temperature in a proper range, the glass can have moderate viscosity, so that the glass can be formed in a flowing mode and can not be unstable in shape due to excessive flowing, and the glass raw sheet is favorably tightly attached to the female die and the male die in the subsequent press forming stage, and a better processing effect is obtained.
In the forming method provided by the invention, the heating temperatures of the front three regions, the middle three regions and the rear three regions are respectively lower than those of the front three regions, the middle three regions and the rear three regions of the existing forming method. By reducing the heating temperature, the optical properties of the shaped glass, in particular the microscopic optical properties of the shaped glass, can be significantly improved, for example, the optical distortion can be significantly reduced (the reduction range can be up to 5-10 mdpt). In addition, the invention can make the radian of glass bending just meet the requirement by controlling the average heating temperature of the front three regions, the middle three regions and the rear three regions within a certain range. In some embodiments, the glass raw sheet for side window glass can be heated to have a curvature radius of 1000mm or more, and the glass raw sheet for front windshield glass can be heated to have a curvature radius of 200-3000mm.
According to a specific embodiment of the present invention, the average heating temperature of the first three zones in the forming method of the present invention is 14 ℃ or more lower than the average heating temperature of the first three zones in the conventional automotive glass raw sheet forming method. The glass raw sheet adopted by the invention has low softening point and low corresponding forming temperature. The average heating temperature of the first three areas in the forming method is controlled in a certain range, so that the radian of glass bending just meets the requirement. For example, the average value of the top intermediate heating temperatures of the first three regions of the existing molding method for green sheet glass is 607 ℃, and the average value of the top intermediate heating temperatures of the first three regions of the molding method of the present invention is 593 ℃, which is 14 ℃ lower than the average value of the heating temperatures at the same position of the existing molding method.
Further, in the molding method of the present invention, the top heating temperature of the first three zones is 4 ℃ or higher than the bottom heating temperature.
In the above molding method, the top heating temperature of the first zone is 560 to 596 ℃, further may be 557 to 599 ℃, and further may be 565 to 591 ℃.
In the above molding method, the bottom heating temperature of the first zone may be 548 to 592 ℃, and may further be 550 to 590 ℃, and may further be 553 to 587 ℃.
In the above molding method, the top heating temperature of the second zone is 569 to 615 ℃, further may be 571 to 613 ℃, and further may be 574 to 610 ℃.
In the above molding method, the bottom heating temperature of the second zone is 561 to 602 ℃, further may be 563 to 600 ℃, and further may be 566 to 597 ℃.
In the above molding method, the top heating temperature of the third zone is 592 to 631 ℃, further may be 594 to 629 ℃, and further may be 597 to 626 ℃.
In the above molding method, the bottom heating temperature of the third zone is 571 to 617 ℃, further 573 to 615 ℃, and still further 576 to 612 ℃.
According to a specific embodiment of the present invention, the average heating temperature in the middle three zones of the inventive molding process is 18 ℃ or more lower than the average heating temperature in the middle three zones of the prior art automotive glass sheet molding process.
Further, in the molding method of the invention, the top heating temperature of the middle three zones is 7 ℃ or more higher than the bottom heating temperature.
In the above molding method, the top heating temperature of the fourth zone may be 606 to 646 ℃, further may be 608 to 644 ℃, and further may be 611 to 641 ℃.
In the above molding method, the top heating temperature of the fourth zone is 595-638 ℃, further may be 597-636 ℃, and still further may be 600-633 ℃.
In the above molding method, the top heating temperature of the fifth zone may be 616 to 656 ℃, further 618 to 654 ℃, and further 621 to 651 ℃.
In the above molding method, the bottom heating temperature of the fifth zone may be 602 to 646 ℃, further may be 604 to 644 ℃, and further may be 607 to 641 ℃.
In the above molding method, the top heating temperature of the sixth zone is 618-657 ℃, further may be 620-655 ℃, and further may be 623-652 ℃.
In the above molding method, the bottom heating temperature of the sixth zone may be 608 to 650 ℃, further may be 610 to 648 ℃, and further may be 613 to 645 ℃.
According to a specific embodiment of the present invention, the average heating temperature of the last three zones of the inventive molding process is 4 ℃ or more lower than the average heating temperature of the last three zones of the prior art automotive glass sheet molding process.
Further, in the molding method of the invention, the top heating temperature of the latter three zones is 10 ℃ or more higher than the bottom heating temperature.
In the above molding method, the top heating temperature of the seventh zone is 633 to 673 ℃, further may be 635 to 671 ℃, and further may be 638 to 668 ℃.
In the above molding method, the bottom heating temperature of the seventh zone may be 628 to 666 ℃, further 630 to 664 ℃, and still further 633 to 661 ℃.
In the above molding method, the top heating temperature of the eighth zone is 634-674 ℃, further may be 636-672 ℃, and further may be 639-669 ℃.
In the above molding method, the bottom heating temperature of the eighth zone may be 630 to 670 ℃, further may be 632 to 668 ℃, and further may be 635 to 665 ℃.
In the above molding method, the top heating temperature of the ninth zone is 633 to 674 ℃, further 635 to 672 ℃, and further 638 to 669 ℃.
In the above molding method, the bottom heating temperature of the ninth zone may be 628 to 669 ℃, further may be 630 to 667 ℃, and further may be 633 to 664 ℃.
Further, in the forming method of the present invention, the heating temperatures of the same height of each heating zone may be symmetrically distributed along the center line so as to uniformly heat the surface of the glass sheet.
According to an embodiment of the present invention, the heating furnace may include at least one of a single sheet press forming furnace, a dead weight bending forming furnace, a double sheet press forming furnace, and the like.
According to a specific embodiment of the invention, the glass raw sheet treated by the heating furnace is generally sent to a forming section outside the furnace from a sheet outlet end (a ninth zone) of the heating furnace for press forming, so as to form the low-absorption high-permeability glass.
According to a specific embodiment of the present invention, in the first to ninth zones, the length of each heating zone is generally 1500 to 4000mm. The first to eighth zones are usually used as heating zones, and the main functions are heating (first to seventh zones) and insulating (eighth zone) of the glass raw sheet, and the ninth zone is used as a heating transport zone for conveying the glass raw sheet to the shaping section in addition to maintaining the heating temperature of the glass raw sheet (close to or substantially the same as the heating temperature of the eighth zone). Accordingly, the conveying speed of the glass raw sheet in the first region to the eighth region may be 50-300mm/s, for example, 50mm/s, 100mm/s, 150mm/s, 200mm/s, 250mm/s, 300mm/s, etc., and a range having any two of the above specific values as an end point, the glass raw sheet is conveyed at a constant speed in the ninth region, the conveying speed of the ninth region is increased relative to the conveying speed of the eighth region, specifically, the conveying speed of the glass raw sheet in the ninth region may be 800-1500mm/s, for example, 800mm/s, 900mm/s, 1000mm/s, 1100mm/s, 1200mm/s, 1300mm/s, 1400mm/s, 1500mm/s, etc., and a range having any two of the above specific values as an end point. In particular embodiments, the transport speed of the glass precursor sheet in each heating zone may be adjusted according to the actual thickness of the glass precursor sheet, e.g., for larger thickness glass precursor sheets, the transport speed may be lower and the heating temperature increased to provide sufficient heating of the glass precursor sheet.
According to the specific embodiment of the invention, the press forming process comprises the steps of conveying a glass raw sheet subjected to heating treatment to a forming section provided with a female die and a male die, supporting the glass raw sheet by the female die until the upper surface of the glass raw sheet is contacted with the male die, simultaneously contacting the glass raw sheet with the female die and the male die, and pressing, after the pressing is finished, sucking the glass raw sheet by the male die, lifting the glass raw sheet, extending a conveying shuttle of the forming section to the position below the male die and the glass raw sheet, separating the male die from the glass raw sheet after the stroke of the conveying shuttle is in place, and conveying the glass raw sheet to an annealing area by the conveying shuttle for annealing to finish press forming.
In the press forming process, the female die in the forming section is positioned below the glass raw sheet, and the concave surface is of a quadrangular die frame structure. The female die is contacted with the periphery of the glass raw sheet.
In the above-mentioned molding process, the male mold in the molding section is located above the glass raw sheet, and has a circular arc-shaped surface, which can be in contact with the entire upper surface of the glass raw sheet. Further, the surface of the male die can be regularly distributed with a plurality of (more than two) small holes, and the aperture of the small holes is generally below 5 mm. Through the small holes, the male die can move the glass raw sheet by vacuum adsorption.
In the press molding process, the time for the glass sheet to be simultaneously contacted (i.e., clamped) with the female die and the male die is a press time, and the press time is generally 2sec or less.
The invention also provides low-absorption high-transmittance (SuperClear, short for SC) glass, which is formed by the forming method.
In some embodiments, the optical distortion of the low-absorption high-transmission glass and/or the laminated glass made of the low-absorption high-transmission glass is less than or equal to 150mdpt, the tensile stress of the low-absorption high-transmission glass and/or the laminated glass made of the low-absorption high-transmission glass is less than 12MPa, and the edge compressive stress of the low-absorption high-transmission glass and/or the laminated glass made of the low-absorption high-transmission glass is more than 12MPa. The laminated glass may comprise two layers of the low-absorption high-transmittance glass, and an adhesive layer such as PVB (polyvinyl butyral) is sandwiched between the two glass plates.
In some specific embodiments, parameters such as refractive index, fitness and the like of the laminated glass made of the low-absorption high-transmittance glass meet the requirements of GB9656-2003 safety glass for automobiles.
In some embodiments, the glass precursor has a transmittance of 90% or more, and further 91% or more, for light having a wavelength of 800-1600nm, and the low-absorption high-transmittance glass produced by the molding method of the present invention using the glass precursor also maintains the transmittance. The transmittance of the low-absorption high-transmittance glass for light with the wavelength of 800-1600nm can reach more than 90%, more preferably more than 91%, still more preferably more than 91.2%.
In some embodiments, the glass precursor sheet has a light absorption coefficient of 0.04-0.2cm -1, and further up to 0.04-0.1cm -1, and the low-absorption high-transmittance glass produced by the shaping method of the present invention using the glass precursor sheet also maintains low-absorption properties, and the low-absorption high-transmittance glass has a light absorption coefficient of 0.04-0.2cm -1, and further up to 0.04-0.1cm -1, for light having a wavelength of 800-1600 nm.
The invention also provides a vehicle window glass which is made of the low-absorption high-transmittance glass. In some embodiments, the glazing may be particularly a front windscreen, a rear windscreen, a side glazing, a sunroof glazing, a quarter glazing or the like. The low-absorption high-transmittance glass provided by the invention has higher optical transmittance in a near infrared band, and can meet the requirements of optical sensors such as LiDAR, infrared cameras and the like on the transmittance of the glass, so that the low-absorption high-transmittance glass can be used for manufacturing functional integrated window glass, such as functional integrated front windshield glass.
The beneficial effects of the invention include:
the low-absorption high-transmittance glass provided by the invention has the advantages of low forming temperature, low absorption, high light transmittance and higher optical transmittance especially in an 800-1600nm light wave band. The low-absorption high-transmittance glass can meet the requirement of the optical sensor on light transmittance, and can be used for functional integrated glass, such as front windshield glass of LiDAR built-in products.
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
In the following experiments, the source of the glass raw sheet used was the ultra-white glass series of Shandong gold technology Co., ltd.
Example 1
The embodiment provides a forming method of low-absorption high-transmittance glass, which comprises the following steps:
s1, conveying a glass raw sheet into a heating furnace for heating treatment;
and S2, conveying the glass raw sheet subjected to the heating treatment from the heating furnace to a forming section for press forming to obtain low-absorption high-transmittance glass, which is named as SC glass.
The glass raw sheet used in this example was a low-absorption high-transmittance glass raw sheet having an iron content of 150ppm or less (130 ppm or less, 110ppm or less, or 90ppm or less, as well) and a softening point of 710.+ -. 3 ℃ and an annealing point of 545.+ -. 5 ℃. The thickness of the glass raw sheet was 2.1mm.
The heating furnace adopted in the embodiment is a single-piece press forming furnace.
The heating furnace is provided with a preheating section, a heating section and a constant temperature gradual change section. Specifically, the heating furnace has 9 heating zones in total, and the conveying direction of the glass raw sheet is from left to right, and each heating zone is sequentially from left to right, namely a first zone, a second zone, a third zone, a fourth zone, a fifth zone, a sixth zone, a seventh zone, an eighth zone and a ninth zone. The heating temperatures of the first region to the ninth region gradually rise. Wherein the first zone to the third zone are preheating sections, the fourth zone to the seventh zone are heating sections, and the eighth zone and the ninth zone are constant temperature gradual change sections.
The top and the bottom of each heating zone are respectively provided with a heating furnace wire as a heating device, and the top heating temperature of the same heating zone is higher than the bottom heating temperature.
The left side, the middle and the right side of the same height are respectively provided with a heating furnace wire. That is, each heating zone is provided with heating wires at the left side of the top, the middle of the top, the right side of the top, the left side of the bottom, the middle of the bottom, and the right side of the bottom, respectively. The temperature of each heating furnace wire is independently controlled, and the heating furnace wires in each heating zone can heat the glass raw sheet simultaneously. At the same height of the same heating zone, the heating temperature gradually rises from left to right.
Wherein the height of each heating zone is denoted as h, the glass raw sheet is positioned on the central line of the height direction of the heating zone, the top is the region which is positioned above the glass raw sheet and has a vertical distance of more than 0 and less than or equal to 50% h from the glass raw sheet, and the bottom is the region which is positioned below the glass raw sheet and has a vertical distance of more than 0 and less than or equal to 20% h from the glass raw sheet.
The length of each heating zone is d, the ranges corresponding to the middle, left and right sides of the same height are that the middle refers to the region positioned at the central line in the length direction of the heating zone, the left refers to the region positioned at the left side of the central line in the length direction and having a horizontal distance from the central line of more than 0 and less than or equal to 30 percent d, and the right refers to the region positioned at the right side of the central line in the length direction and having a horizontal distance from the central line of more than 0 and less than or equal to 30 percent d.
The heating temperatures at the respective positions of the heating zones in S1 are shown in table 1.
And S2, the molding section for compression molding comprises a male die, a female die and a transmission shuttle.
The male die is positioned above the glass raw sheet and provided with a circular arc-shaped surface which can be contacted with the whole upper surface of the glass raw sheet. The surface of the male die can be regularly distributed with a plurality of (more than two) small holes, and the aperture of the small holes is generally below 5mm. Through the small holes, the male die can vacuum adsorb the glass raw sheet to move the glass raw sheet.
The female die is positioned below the glass raw sheet, and the concave surface is of a quadrangular die frame structure. The female die is contacted with the periphery of the glass raw sheet.
The pressing forming process of S2 specifically comprises the steps of supporting a glass raw sheet by utilizing a female die until the upper surface of the glass raw sheet is contacted with a male die, simultaneously contacting (namely clamping) the glass raw sheet with the female die and the male die, and pressing, wherein the pressing temperature is controlled to be less than the heating temperature of a fourth region to a ninth region in a heating furnace, the pressing time is controlled to be less than 2sec, the male die sucks the glass raw sheet to rise after the pressing is finished, then a conveying shuttle extends to the lower part of the male die and the glass raw sheet, the male die and the glass raw sheet are separated after the stroke of the conveying shuttle is in place, and the glass raw sheet falls on the conveying shuttle and is conveyed to an annealing region by the conveying shuttle to be annealed (the annealing temperature is 500-600 ℃ and the annealing time is 10-30 min), so that the pressing forming is completed.
Comparative example 1
The comparative example provides a method for molding green glass raw sheet, which comprises feeding green glass raw sheet into a heating furnace for heating treatment, feeding the green glass raw sheet to a molding section for press molding after being output from the heating furnace, and obtaining green glass, which is denoted as G glass.
The glass raw sheet adopted in the comparative example is a green glass raw sheet, the iron content of the glass raw sheet is 800ppm-900ppm, the softening point of the glass raw sheet is 725-730 ℃, and the annealing point is 560-620 ℃. The thickness of the glass raw sheet was 2.1mm.
The heating furnace used in this comparative example was the same as in example 1, and the distribution of each heating zone and the distribution of the heating wire were also the same as in example 1.
The heating temperatures at the respective positions of the heating zones are shown in Table 1 (numerical units:. Degree.C.). The "upper left" represents the top left side heating temperature, "upper middle" represents the top middle heating temperature, "upper right" represents the top right side heating temperature, "lower left" represents the bottom left side heating temperature, "lower middle" represents the bottom middle heating temperature, "lower right" represents the bottom right side heating temperature. The temperatures in table 1 are thermocouple temperature readings.
TABLE 1
As can be seen from Table 1, the molding temperature of the conventional green glass raw sheet molding method is 576-658 ℃, whereas the molding temperature of the present invention for the low-absorption high-transmittance glass raw sheet molding method is 553-643 ℃. The molding method provided by the invention has lower temperature.
Example 2
The embodiment provides a forming method of low-absorption high-transmittance glass, which comprises the following steps:
s1, conveying a glass raw sheet into a heating furnace for heating treatment;
and S2, conveying the glass raw sheet subjected to the heating treatment from the heating furnace to a forming section for press forming to obtain low-absorption high-transmittance glass, which is named as SC glass.
The glass raw sheet used in this example was a low-absorption high-transmittance glass raw sheet having an iron content of 150ppm or less (130 ppm or less, 110ppm or less, or 90ppm or less, as well) and a softening point of 710.+ -. 3 ℃ and an annealing point of 545.+ -. 5 ℃. The thickness of the glass raw sheet was 6mm.
The molding method of this example is similar to that of example 1, except that the temperature of the heating treatment in S1 is different. The heating temperatures at the respective positions of the heating zones in this example are shown in table 2 (SC sample).
Comparative example 2
The comparative example provides a method for molding green glass raw sheet, which comprises feeding green glass raw sheet into a heating furnace for heating treatment, feeding the green glass raw sheet to a molding section for press molding after being output from the heating furnace, and obtaining green glass, which is denoted as G glass.
The glass raw sheet adopted in the comparative example is a green glass raw sheet, the iron content of the glass raw sheet is 800ppm-900ppm, the softening point of the glass raw sheet is 725-730 ℃, and the annealing point is 560-620 ℃. The thickness of the glass raw sheet was 6mm.
The heating furnace used in this comparative example was the same as in example 2, and the distribution of each heating zone and the distribution of the heating wire were also the same as in example 2.
The heating temperatures at the respective positions of the heating zones are shown in table 2 (G sample). The numerical units in Table 2 are C. The temperatures in table 2 are thermocouple temperature readings.
TABLE 2
As can be seen from Table 2, when the thickness of the glass raw sheet is adjusted to 6mm, the molding temperature of the conventional green glass raw sheet molding method is 596-678 ℃, whereas the molding temperature of the low-absorption high-transmittance glass raw sheet molding method of the present invention is 578-669 ℃. In contrast, the molding method provided by the invention has lower heating temperature.
Test example 1
The SC glasses obtained by the molding methods of example 1 and example 2 and the G glasses obtained by the molding methods of comparative example 1 and comparative example 2 were tested for optical transmittance in the near infrared band of 800 to 1600nm by referring to the standard GB/T5137.2-2020, test method for automobile safety glass, section 2, optical property test. The laser wavelength used for the light absorption coefficient is 800-1600nm, and the calculation formula of the light absorption coefficient is as follows:
K is the light absorption coefficient of the glass raw sheet, l is the thickness of the glass raw sheet in the stacking direction, n is the refractive index of the glass raw sheet for the laser light with the specific wavelength, and T is the transmittance of the glass raw sheet for the laser light with the specific wavelength.
The low absorption high transmission glass raw sheet used in the molding method of example 1 had an iron content of 99ppm, a softening point of 710℃and an annealing point of 545℃and a light absorption coefficient of 0.09cm -1.
The green sheet used in the molding method of comparative example 1 had an iron content of 805ppm, a softening point of 728℃and an annealing point of 592℃and a light absorption coefficient of 3.76cm -1.
The transmittance of the SC glass of 2.1mm manufactured in example 1 at 800-1600nm was 91.2% (. Gtoreq.91%), and the transmittance of the green glass of 2.1mm manufactured in comparative example 1 at 800-1600nm was 61.23%.
The transmittance of the 6mm SC glass manufactured in example 2 at 800-1600nm was measured to be 90.6%, and the transmittance of the 6mm green glass manufactured in comparative example 2 at 800-1600nm was measured to be 48%.
In addition, laminated glasses made of SC glass of example 1 and example 2 were subjected to optical distortion, tensile stress, edge compressive stress, refraction, fitness, and the like. The laminated glass consisted of two SC glasses and a 0.76mm thick PVB tie layer between the two glass plates.
The laminated glass of the low absorption high transmission glass of example 1 was found to have the following properties of 129mdpt optical distortion, 10.5MPa tensile stress and 13.1MPa edge compressive stress, 148mdpt optical distortion, 11.2MPa tensile stress and 15.3MPa edge compressive stress.
The laminated glass made of the SC glass of example 1 and example 2 satisfies the requirements of GB9656-2003 safety glass for automobiles in terms of refraction, compliance and the like.
The result shows that the prior glass has lower transmittance in the near infrared band, and is difficult to meet the requirement of optical sensor elements on the optical performance of the glass, while the optical transmittance of the low-absorption high-transmittance glass manufactured by the forming method in the near infrared band can reach more than 91 percent, can meet the requirement of LiDAR and other sensors on the optical transmittance, and can be used for manufacturing the window glass of front windshield glass and the like of functional integration.
Claims (20)
1. A method of forming a low absorption, high transmission glass, the method comprising:
placing the glass raw sheet into a heating furnace for heating treatment, and then pressing and forming to obtain the low-absorption high-transmittance glass;
The heating furnace comprises a preheating section, a heating section and a constant temperature transition section which are connected in sequence;
the inlet temperature of the preheating section is 548-596 ℃, the outlet temperature of the preheating section is 571-631 ℃, and the outlet temperature of the preheating section is higher than the inlet temperature;
The inlet temperature of the heating section is 595-646 ℃, the outlet temperature of the heating section is 628-673 ℃, and the outlet temperature of the heating section is higher than the inlet temperature;
the temperature of the constant temperature transition section is 628-674 ℃;
the inlet temperature of the heating section is greater than or equal to the outlet temperature of the preheating section, and the difference value between the inlet temperature of the constant temperature gradual change section and the outlet temperature of the heating section is more than or equal to-3 ℃.
2. The molding method according to claim 1, wherein the preheating section has a temperature rising speed of 0.07 to 5.4 ℃ per second;
the heating speed of the heating section is 0.01-4.0 ℃ per second.
3. The molding method according to claim 1 or 2, wherein the heating furnace has 9 heating zones, each heating zone from a sheet inlet end to a sheet outlet end of the heating furnace is a first zone to a ninth zone in sequence, the first zone to the third zone are preheating sections, the fourth zone to the seventh zone are heating sections, and the eighth zone to the ninth zone are constant temperature gradual change sections;
heating the glass raw sheet from the upper part and the lower part of the glass raw sheet at the same time;
Wherein the heating temperatures of the first zone, the second zone and the third zone are 548-631 ℃, the heating temperatures of the fourth zone, the fifth zone and the sixth zone are 595-657 ℃, and the heating temperatures of the seventh zone, the eighth zone and the ninth zone are 628-674 ℃.
4. A forming process according to claim 3 wherein the top heating temperature is higher than the bottom heating temperature of the same heating zone;
the top heating temperatures of the first zone, the second zone and the third zone are 560-631 ℃ respectively, and the bottom heating temperatures of the first zone, the second zone and the third zone are 548-617 ℃ respectively;
The top heating temperatures of the fourth zone, the fifth zone and the sixth zone are 606-657 ℃ respectively, and the bottom heating temperatures of the fourth zone, the fifth zone and the sixth zone are 595-650 ℃ respectively;
The top heating temperatures of the seventh zone, the eighth zone and the ninth zone are 633-674 ℃ respectively, and the bottom heating temperatures of the seventh zone, the eighth zone and the ninth zone are 628-670 ℃ respectively.
5. A molding process according to claim 3, wherein the top heating temperature of the first zone is 560-596 ℃ and the bottom heating temperature of the first zone is 548-592 ℃.
6. A molding process according to claim 3, wherein the top heating temperature of the second zone is 569-615 ℃ and the bottom heating temperature of the second zone is 561-602 ℃.
7. A molding process according to claim 3, wherein the top heating temperature of the third zone is 592-631 ℃ and the bottom heating temperature of the third zone is 571-617 ℃.
8. A molding process according to claim 3, wherein the top heating temperature of the fourth zone is 606-646 ℃ and the bottom heating temperature of the fourth zone is 595-638 ℃.
9. A molding process according to claim 3, wherein the top heating temperature of the fifth zone is 616-656 ℃, and the bottom heating temperature of the fifth zone is 602-646 ℃.
10. A molding process according to claim 3, wherein the top heating temperature of the sixth zone is 618-657 ℃ and the bottom heating temperature of the sixth zone is 608-650 ℃.
11. A molding process according to claim 3, wherein the seventh zone has a top heating temperature of 633-673 ℃ and a bottom heating temperature of 628-666 ℃.
12. A molding process according to claim 3, wherein the eighth zone has a top heating temperature of 634-674 ℃ and a bottom heating temperature of 630-670 ℃.
13. A molding process according to claim 3, wherein the top heating temperature of the ninth zone is 633-674 ℃ and the bottom heating temperature of the ninth zone is 628-669 ℃.
14. A molding method according to claim 3, wherein in the first to ninth zones, the length of each heating zone is 1500 to 4000mm;
The glass raw sheet is conveyed at a constant speed in a first area to an eighth area, and the conveying speed is 50-300mm/s;
and the glass raw sheet is conveyed at a constant speed in a ninth zone, wherein the conveying speed is 800-1500mm/s.
15. The molding method according to claim 1, wherein the thickness of the glass raw sheet is 1.6-6mm;
and/or the iron content of the glass raw sheet is less than or equal to 150ppm;
And/or the light absorption coefficient of the glass raw sheet to the light with the wavelength of 800-1600nm is 0.04-0.2cm -1.
16. The molding method according to claim 1, wherein the glass raw sheet has a softening point temperature of 707 to 713 ℃ and an annealing point temperature of 540 to 550 ℃.
17. A low absorption high transmission glass molded by the molding method according to any one of claims 1 to 16.
18. The low-absorption high-transmittance glass according to claim 17, wherein the optical distortion of the low-absorption high-transmittance glass is 150 or less mdpt, the tensile stress of the low-absorption high-transmittance glass is <12MPa, and the edge compressive stress of the low-absorption high-transmittance glass is >12MPa.
19. The low-absorption high-transmittance glass according to claim 17, wherein the transmittance of the low-absorption high-transmittance glass for light having a wavelength of 800 to 1600nm is 90% or more.
20. A glazing made from the low absorption high transmission glazing of any of claims 17 to 19.
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| CN102892721A (en) * | 2010-05-12 | 2013-01-23 | 肖特公开股份有限公司 | Method for manufacturing molded glass articles, and use of the glass articles manufactured according to the method |
| KR20230153793A (en) * | 2022-04-29 | 2023-11-07 | 김근혜 | Glass panel curved part thermoforming system |
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| KR101715606B1 (en) * | 2016-09-29 | 2017-03-13 | (주)대호테크 | The Mold Device for Molding Glasses |
| CN108213314A (en) * | 2018-03-28 | 2018-06-29 | 杭州立琪燃气设备有限公司 | A kind of three-stage copper alloy valve forging thermostatic oven |
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| CN102892721A (en) * | 2010-05-12 | 2013-01-23 | 肖特公开股份有限公司 | Method for manufacturing molded glass articles, and use of the glass articles manufactured according to the method |
| KR20230153793A (en) * | 2022-04-29 | 2023-11-07 | 김근혜 | Glass panel curved part thermoforming system |
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