A wet laminating method for anti-nuclear radiation super-thick peep window laminated glass

Abstract

The present application relates to a kind of super-thick peep window anti-nuclear radiation laminated glass wet compounding method, which comprises the following steps: after washing, air-drying glass plate, static film for protection is attached to non-adhesion surface;Glass plate is placed in the glass plate perfusion device built, for glass plate glue injection;High molecular resin optical adhesive mixing: adhesive raw material is mixed using centrifugal vacuum mixing machine, then placed in adhesive cup;Adhesive is filled into glass plate perfusion device, continuous vacuum, until laminated layer is free of bubbles, then vacuum packaging;The glass plate that completes adhesive perfusion is cured, glass plate perfusion device is disassembled, after post-processing, super-thick peep window anti-nuclear radiation laminated glass wet compounding method is completed.Compared with prior art, the present application has the advantages of high qualified rate, guaranteeing glue layer free of bubbles, uniform glue layer thickness and the like.

Description

Technical Field

[0001] This invention relates to the field of nuclear industry viewing window glass plates, specifically to a wet lamination method for ultra-thick viewing window anti-nuclear radiation resistant laminated glass. Background Technology

[0002] Nuclear energy, as a clean, efficient, and high-quality energy source, has been applied in more than 30 countries worldwide. As a strategic high-tech industry, nuclear power is being developed by various countries in response to global carbon neutrality and the major shift in the world's energy landscape. Under the goal of achieving carbon peaking and carbon neutrality, China has vigorously developed nuclear power, maintaining its position as the world's largest producer of installed capacity for many consecutive years. Currently, the thickest glass plates produced by Germany's SCHOTT company reach 420 mm, while those from the US's CORNING company are 400 mm. France's LEMER PAX company, using its "Safety Laminated Lead Glass Block (SLLGB)" technology, has achieved unlimited thickness, producing glass plates as thick as 570 mm. LEMER PAX's SLLGB technology uses one or more layers of interlayer film to composite radiation-resistant glass plates of varying thicknesses into a single glass plate that meets design requirements. According to the official website of the French company LEMER PAX, laminated radiation-resistant glass panels have the following advantages: ① Excellent impact resistance: When the glass panel is impacted, the single-layer glass breaks, but because the adhesive layer prevents crack propagation, penetrating cracks along the thickness direction will not occur, thus preventing the leakage of nuclear radiation; ② No thickness limitations, allowing for greater design flexibility for viewing windows; ③ Protective layers (such as PMMA optical glass) can be laminated onto the inner and outer surfaces of the glass panel, eliminating the need for additional protective glass during viewing window assembly. This reduces optical loss, and because the protective layer and the glass panel are bonded together as a whole, there is no condensation problem. However, the technical details of the company's SLLGB technology (including adhesive layer material, optical thickness, molding process, etc.) are completely unknown, and there are no public reports on it.

[0003] China has become a manufacturing powerhouse in laminated glass for the transportation and construction sectors, with highly mature general-purpose glass lamination technology. Currently, there are two main production methods: First, the dry process, which involves sandwiching PVB, EVA, or other adhesive films between two or more layers of glass, forming them through pre-pressing with rollers and hot pressing in an autoclave; this method is suitable for mass production. Second, the wet process, which involves pouring prepared PMMA, PU, ​​or other adhesive slurries between two or more pre-molded glass sheets, polymerizing them through heating or light; this method is suitable for small-batch production. Since the demand for ultra-thick radiation-resistant glass sheets is relatively small but essential, large-scale production using the dry process would be overly expensive. Therefore, the wet process is more suitable for laminating ultra-thick radiation-resistant glass sheets. Several patents have been published regarding wet lamination processes or manufacturing methods for laminated glass, such as CN113968068A, CN106881942A, and CN110802896A. However, these processes and methods are all aimed at thin glass lamination in the transportation and construction sectors, and are applicable to adhesives such as PMMA and PU. They are not applicable to radiation-resistant glass sheets with a single layer thickness exceeding 230 mm, or to the composite of radiation-resistant special polymer resins. Compared to thin glass lamination, the wet lamination process for ultra-thick radiation-resistant glass sheets presents the following unique challenges: First, air bubbles are easily generated during the pouring of radiation-resistant special polymer resin adhesives and are difficult to eliminate; second, during the curing process after pouring, continuous and uniform pressure is required to ensure that air bubbles are expelled with the overflow adhesive and to ensure that the thickness of the laminated layer is uniform after curing, so that the product meets the thickness tolerance requirements, but this is difficult to achieve for thick and heavy glass sheets. Summary of the Invention

[0004] The purpose of this invention is to overcome at least one of the defects in the prior art and provide a wet lamination method for ultra-thick viewing windows that are resistant to nuclear radiation and have a high yield rate, ensure no bubbles in the adhesive layer, and have a uniform adhesive layer thickness.

[0005] The objective of this invention can be achieved through the following technical solutions:

[0006] A wet lamination method for ultra-thick peep window anti-nuclear radiation resistant laminated glass, the method comprising the following steps:

[0007] Glass plate pretreatment: After cleaning and air drying the glass plate, an electrostatic film for protection is attached to the non-adhesive surface;

[0008] Setup of the glass plate injection device: Place the glass plate in the assembled glass plate injection device for glass plate glue injection;

[0009] Mixing of polymer resin optical adhesives: The adhesive raw materials are mixed using a centrifugal vacuum mixer and then placed in an adhesive container;

[0010] Adhesive filling and vacuum sealing: The adhesive is poured into the glass plate filling device, and the vacuum is continuously drawn until there are no air bubbles in the interlayer, and then vacuum sealed.

[0011] Adhesive curing and post-treatment: The glass plate after adhesive infusion is cured, the glass plate infusion device is disassembled, and after post-treatment, the wet process of ultra-thick viewing window anti-nuclear radiation resistant laminated glass is completed.

[0012] Furthermore, the specific steps for cleaning the glass plate are as follows: the glass plate is cleaned in three stages. The first and second stages use tap water heated to 40-60℃, and the third stage uses deionized water or reverse osmosis water to remove salt from the tap water. The resistivity of the deionized water or reverse osmosis water is >10 MΩ or the conductivity is <10 μs.

[0013] Furthermore, the air-drying temperature is 120-150℃.

[0014] Furthermore, the construction of the glass plate infusion apparatus includes the following specific steps:

[0015] Establishment of the laminated glass injection mechanism: The protected glass plate is placed into a vacuum bag film, the side of the glass plate is covered with a smooth thin sheet, and the edge is sealed with sealing tape to form a closed chamber. The injection hole is reserved near the bottom of the side and the vacuum hole is reserved on the upper surface.

[0016] Forming of the glass plate pouring device: The adhesive cup, the laminated glass pouring mechanism, the resin collector and the vacuum pump are connected in sequence, wherein the adhesive cup is connected to the injection hole and the resin collector is connected to the vacuum hole.

[0017] Furthermore, during the construction of the glass plate infusion device, the ambient temperature is 23-25℃ and the humidity is ≤55%.

[0018] Furthermore, the adhesive mixing process employs a 5-stage mixing method, with the following specific parameters: Stage 1: Rotation 300-600 rpm, revolution 700-1000 rpm, time 90-120 s, vacuum -0.1 MPa; Stage 2: Rotation 600-800 rpm, revolution 1000-1200 rpm, time 90-120 s, vacuum -0.1 MPa; Stage 3: Rotation 600-800 rpm, revolution 1000-1200 rpm, time 90-120 s, vacuum -0.1 MPa; Stage 4: Rotation 400-600 rpm, revolution 800-1000 rpm, time 80-100 s, vacuum -0.1 MPa; Stage 5: Rotation 200-400 rpm, revolution 400-600 rpm, time 50-70 s... s, vacuum -0.1 MPa.

[0019] Furthermore, the adhesive is cured at a temperature of 60-120℃, a pressure of 0.3-1.0 MPa, and a time of 6-8 h.

[0020] Furthermore, the adhesive is cured at room temperature for no less than 24 hours.

[0021] Furthermore, the polymeric resin optical adhesive includes polyaryletherketone (PAEK), thermoplastic polyimide (TPI) resin transparent optical adhesive, or epoxy resin optical adhesive.

[0022] The glass plate includes radiation-shielding glass plate or radiation-resistant glass plate, wherein the radiation-shielding glass plate includes ZF6, ZF7 or ZF501; and the radiation-resistant glass plate includes K509 or K709.

[0023] Furthermore, the post-processing includes cutting, polishing, coating, protection, or packaging.

[0024] Compared with the prior art, the present invention has the following advantages:

[0025] (1) This invention can effectively solve the bottleneck that the thickness of current radiation-resistant glass plates cannot meet the design requirements of viewing windows in nuclear power plants or other nuclear industries. It further improves the overall localization rate of third-generation domestically produced nuclear power, reduces procurement costs and time, and solves the problem of domestic self-sufficiency and controllability of key materials;

[0026] (2) This invention requires less investment and is suitable for the lamination of ultra-thick glass for nuclear power plants or nuclear industry viewing windows because it requires less material and has many specifications;

[0027] (3) This invention solves the problem of air bubbles easily generated in wet lamination, resulting in a high pass rate. A centrifugal vacuum mixer is used to eliminate air bubbles in the adhesive body, and a vacuum injection method is used for injection. Vacuum bag sealing and pressurization or high-pressure autoclave pressurization are employed to ensure that the adhesive layer is bubble-free throughout the entire process. Furthermore, through air pressure, the lamination layer is subjected to uniform pressure, resulting in a uniform adhesive layer thickness.

[0028] (4) The glass plate of the present invention is vertical throughout, which avoids slippage and displacement when the glass plate is laid flat and the adhesive is poured, and the thickness of the cavity is uniform. Attached Figure Description

[0029] Figure 1 This is the wet composite process flow in this invention;

[0030] Figure 2 This is a schematic diagram of the laminated glass injection mechanism in the embodiment;

[0031] Figure 3 This is a schematic diagram of the glass plate injection device in the embodiment;

[0032] The numbers in the diagram indicate: 1-First glass plate, 2-Second glass plate, 3-Vacuum extraction hole, 4-Sealed laminated chamber, 5-Isolation sheet, 6-Sealing tape, 7-Injection hole, 8-Injection tube, 9-Vacuum extraction tube, 10-Vacuum pressure gauge, 11-Connecting hose, 12-Adhesive cup, 13-Laminated glass filling mechanism, 14-Resin collector, 15-Vacuum pump. Detailed Implementation

[0033] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments. These embodiments are implemented based on the technical solution of the present invention, providing detailed implementation methods and specific operating procedures. However, the scope of protection of the present invention is not limited to the following embodiments.

[0034] A wet lamination method for ultra-thick peep window anti-radiation and radiation-resistant laminated glass is disclosed. This molding method is also applicable to the lamination of three or more layers of anti-radiation and radiation-resistant glass, and is suitable for different types of glass lamination, which can be selected according to the design requirements of the peep window. The method includes the following steps:

[0035] (1) Glass Plate Cleaning: Glass plates that have passed the incoming inspection are transferred to a multi-functional cleaning and drying machine. They undergo three cleaning stages. The first and second stages use ordinary tap water heated to 40-60℃, plus water overflowing from subsequent cleaning stages. The third stage uses a deionization system or reverse osmosis system to remove salt from the tap water. The water resistivity must be >10 MΩ or the conductivity <10 µs. Radiation-resistant or nuclear-proof glass materials must meet the technical requirements stipulated by the state or nuclear power / nuclear industry design institutes. Typical domestic radiation-resistant glass materials include ZF6, ZF7, and ZF501; typical domestic nuclear-proof glass materials include K509 and K709.

[0036] (2) Transfer the cleaned glass plate to the air drying section for hot air circulation drying at a temperature of 120-150℃.

[0037] (3) Protection of non-adhesive surfaces of glass plates: Use electrostatic film of moderate strength to protect the non-adhesive surfaces of glass plates to prevent damage to the optical interface of glass plates during operation.

[0038] (4) Glass plate preparation before adhesive injection: Vertically insert the two protected glass plates 1 and 2 into a vacuum bag of appropriate size. For adhesives cured by autoclave, vacuum bag sealing is not required. Adjust the distance between the two glass plates using standard thickness spacers according to the optical design thickness of the adhesive layer. At the same time, use a horizontal template to make the four sides of the two glass plates flush. After reaching the standard, use a 1-2 mm thick non-polar material, such as polytetrafluoroethylene or polypropylene, to cover the sides of the glass plates and seal the edges with sealing tape 6 to form a closed chamber 4 between the two glass plates. Reserve the injection hole 7 near the bottom of the side and the vacuum hole 3 on the upper surface.

[0039] according to Figure 3 The interface relationships shown connect the glue injection hose 8 to the glue injection hole 7, the vacuum hose 9 to the vacuum hole 3, the resin collector 14, and the vacuum pump 15. To eliminate contamination of the adhesive film by impurities in the working environment, this process must be carried out in a cleanroom of Class 100,000 or higher, and operators must wear protective clothing and disposable silicone gloves throughout the process. The cleanroom is temperature and humidity controlled, with an ambient temperature of 23-25℃ and humidity ≤55%.

[0040] (5) Mixing of special polymer resin optical adhesives: First, calculate the amount of adhesive to be used based on the area of ​​the glass plate to be bonded and the required adhesive layer thickness. On this basis, add 20-30% as process loss and exhaust overflow loss. According to the adhesive components, add them into the material cup 12 of the centrifugal vacuum mixer. The material cup 12 needs to be cleaned and dried before use. Use a centrifugal vacuum mixer to mix the adhesive according to the specified process parameters. Remove air bubbles and moisture from the adhesive body through the dual action of centrifugal force and vacuum. The working environment of this process is the same as that of process (4). The anti-nuclear radiation optical adhesive is a transparent optical adhesive of polyaryletherketone (PAEK) or thermoplastic polyimide (TPI) resin. For application scenarios with low nuclear radiation doses, epoxy resin optical adhesives can be used.

[0041] (6) Vacuum injection of adhesive: Slowly turn on the vacuum pump, insert the injection hose into the degassed adhesive, and slowly fill the sealed chamber with adhesive. Observe whether there are air bubbles in the interlayer. Continue to evacuate the vacuum until there are no air bubbles in the interlayer. Remove the injection hose and vacuum hose, and seal the injection hole and vacuum hole with sealing strip. The working environment of this process is the same as that of process (4).

[0042] (7) Vacuum sealing of laminated glass: For room temperature curing adhesives, such as epoxy resin optical adhesives, the vacuum bag film placed at the bottom of the glass plate is lifted and smoothed, and the gas inside the bag is removed using an external vacuum pump to make the vacuum inside the bag film approximately -0.1 MPa, and then the edges are heat-sealed. Through vacuum sealing, the laminated layer is subjected to a uniform curing pressure of about 0.1 MPa.

[0043] (8) Curing of laminated glass: Depending on the curing conditions of the adhesive, the glass plate with the adhesive poured can be placed vertically in an autoclave and cured under pressure and heat. The curing temperature is 60-120℃, the curing pressure is 0.3-1.0 MPa, and the curing time is 6-8 h. After completion, it is placed in an autoclave for pressure maintenance and natural cooling to room temperature before depressurization to obtain laminated glass. The quality of the laminated layer is then checked. For epoxy resin, it can be cured at room temperature for no less than 24 hours. After curing, the vacuum bag film is removed to obtain laminated glass, and the quality of the laminated layer is checked.

[0044] (9) Post-processing of laminated glass: The laminated glass that has passed inspection is mechanically cut to meet the tolerance requirements, and then subjected to post-processing operations such as optical surface polishing, coating, protection, and packaging.

[0045] Example

[0046] In this embodiment, the radiation-shielding glass model is ZF6; glass dimensions are 300 mm × 300 mm × 200 mm; the number of glass panes is 2; the anti-nuclear radiation adhesive is epoxy resin optical adhesive; the adhesive film thickness is 0.1 ± 0.02 mm; and the adhesive dosage is 250 ± 10 g / m³. 2 ;

[0047] Composite process flow as follows Figure 1 As shown, the process parameters for the key processes are as follows:

[0048] Centrifugal vacuum mixing process parameters for adhesives:

[0049] The mixture consists of 5 stages: Stage 1: Rotation 500 rpm, revolution 900 rpm, time 120 s, vacuum -0.1 MPa; Stage 2: Rotation 700 rpm, revolution 1200 rpm, time 120 s, vacuum -0.1 MPa; Stage 3: Rotation 700 rpm, revolution 1200 rpm, time 120 s, vacuum -0.1 MPa; Stage 4: Rotation 500 rpm, revolution 900 rpm, time 90 s, vacuum -0.1 MPa; Stage 5: Rotation 300 rpm, revolution 500 rpm, time 60 s, vacuum -0.1 MPa.

[0050] Vacuum sealing process parameters for laminated glass:

[0051] 0.15 mm thick EVA vacuum bag film is used, external vacuum is applied, and the bag film sealing temperature is 120±3℃.

[0052] Laminated glass curing process parameters:

[0053] After vacuum sealing, the laminated glass is placed in a constant temperature and humidity room (temperature 24±1℃, humidity 50±5%) for natural curing, with a curing time of more than 7 days.

[0054] The products manufactured according to the above embodiments were cut and sampled, and their irradiation stability was tested according to Q / CNPE J104.65-2011 "Technical Conditions for Radiation-Proof and Radiation-Resistant Glass for Peeping Windows". The radiation source was a Co-60 gamma-ray source, and the irradiation conditions were: radiation dose rate 87.2 Gy / h, irradiation time 10h, and cumulative dose 872 Gy. The appearance quality after irradiation is shown in Table 1, and the white light transmittance before and after irradiation is shown in Table 2. The test results show that the irradiation stability of the laminated glass meets the requirements specified in Q / CNPE J104.65-2011 "Technical Conditions for Radiation-Proof and Radiation-Resistant Glass for Peeping Windows".

[0055] Table 1. Apparent quality of products sampled from the examples after irradiation

[0056]

[0057] Table 2. White light transmittance of the product samples prepared in the example before and after irradiation.

[0058]

[0059] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention in any other way. Any person skilled in the art may make changes or modifications to the above-disclosed technical content to create equivalent embodiments. However, any simple modifications, equivalent changes, and modifications made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the protection scope of the present invention.

Claims

1. A wet lamination method for ultra-thick peephole window anti-nuclear radiation resistant laminated glass, characterized in that, The method includes the following steps: Glass plate pretreatment: After cleaning and air drying the glass plate, an electrostatic film for protection is attached to the non-adhesive surface; Setup of the glass plate injection device: Place the glass plate in the assembled glass plate injection device for glass plate glue injection; Polymer resin optical adhesive mixing: The adhesive raw materials are mixed using a centrifugal vacuum mixer and then placed in an adhesive container; the polymer resin optical adhesive includes polyaryletherketone, thermoplastic polyimide resin transparent optical adhesive or epoxy resin optical adhesive. The adhesive mixing process employs a 5-stage mixing method, with the following specific parameters: Stage 1: Rotation 300-600 rpm, revolution 700-1000 rpm, time 90-120 s, vacuum -0.1 MPa; Stage 2: Rotation 600-800 rpm, revolution 1000-1200 rpm, time 90-120 s, vacuum -0.1 MPa; Stage 3: Rotation 600-800 rpm, revolution 1000-1200 rpm, time 90-120 s, vacuum -0.1 MPa; Stage 4: Rotation 400-600 rpm, revolution 800-1000 rpm, time 80-100 s, vacuum -0.1 MPa; Stage 5: Rotation 200-400 rpm, revolution 400-600 rpm, time 50-70 s... s, vacuum -0.1 MPa; Adhesive filling and vacuum sealing: The adhesive is poured into the glass plate filling device, and the vacuum is continuously drawn until there are no air bubbles in the interlayer, and then vacuum sealed. Adhesive curing and post-treatment: The glass plate after adhesive infusion is cured, the glass plate infusion device is disassembled, and after post-treatment, the wet composite method of ultra-thick viewing window anti-nuclear radiation resistant laminated glass is completed. The construction of the glass plate pouring device includes the following specific steps: Establishment of the laminated glass injection mechanism: The protected glass plate is placed into a vacuum bag film, the side of the glass plate is covered with a smooth thin sheet, and the edge is sealed with sealing tape to form a closed chamber. The injection hole is reserved near the bottom of the side and the vacuum hole is reserved on the upper surface. Forming of the glass plate pouring device: The adhesive cup, the laminated glass pouring mechanism, the resin collector and the vacuum pump are connected in sequence, wherein the adhesive cup is connected to the injection hole and the resin collector is connected to the vacuum hole. For room temperature curing adhesives, the curing temperature of the adhesive is room temperature, and the curing time is not less than 24 hours. The glass plate is vertical throughout.

2. The wet lamination method for ultra-thick peephole window anti-nuclear radiation resistant laminated glass according to claim 1, characterized in that, The air-drying temperature is 120-150℃.

3. The wet lamination method for ultra-thick peephole window anti-nuclear radiation resistant laminated glass according to claim 1, characterized in that, During the setup of the glass plate infusion device, the ambient temperature is 23-25℃ and the humidity is ≤55%.

4. The wet lamination method for ultra-thick peephole window anti-nuclear radiation resistant laminated glass according to claim 1, characterized in that, The post-processing includes cutting, polishing, coating, protection, or packaging.

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