Resin system curing process optimization method and device based on self-exothermic effect

Abstract

The invention discloses a resin system curing process optimization method and device based on a self-exothermic effect, and the method comprises the following steps: (1) designing an in-situ monitoring device based on multistage precision regulation and control, and achieving the high-precision in-situ monitoring of the resin system curing self-exothermic effect; (2) based on a Fourier heat conduction model, separating and decoupling a self-heat-release effect generated in the curing process of the resin system, and designing a self-heat-release index; and (3) preparing a sample, setting performance indexes, and screening and optimizing a curing process in combination with a self-heat release index. On the basis of the design of a high-precision in-situ monitoring device and the Fourier heat conduction theory, in-situ monitoring and evaluation are carried out on the curing self-heat-release effect of the resin system, screening optimization of a low-energy-consumption and high-performance curing process is carried out on the basis of self-heat-release and performance indexes, the optimization period of the adaptive curing process of the resin system is shortened, and the production efficiency is improved. And high-efficiency, low-energy-consumption and high-performance curing of the workpiece is realized.

Description

Technical Field

[0001] The present invention relates to a method and device for optimizing the curing process of a resin system based on the self-heating effect, belonging to the technical field of structural health monitoring, and specifically relates to a high-precision in-situ monitoring, self-heating effect analysis and curing process optimization method of the self-heating effect of a resin system curing based on multi-level precision control design and Fourier heat conduction theory. Background Art

[0002] With the further advancement of China's "dual carbon" goal process, energy conservation and emission reduction have become effective means to achieve green, environmentally friendly and low-carbon life. According to statistics, the energy consumption required for the curing process of resins and their composites accounts for more than 80% of the total energy consumption of component production. Research on optimizing the curing process of resins and their composites to reduce energy consumption has received extensive attention. The temperature field during the curing process of the resin system and its composites superimposes the heat transfer effect of the curing environment and the self-heating effect of the resin system curing reaction. The efficient utilization of the self-heating effect can significantly reduce the energy consumption during the curing process. However, affected by the curing process, excessive self-heating effect will cause local heat accumulation in the resin and composite specimens, resulting in local pyrolysis and performance loss. Therefore, it is urgent to establish a set of high-precision in-situ monitoring device and process optimization method for the self-heating effect of the resin system curing, to conduct high-precision monitoring and evaluation analysis on the self-heating effect of the resin system under the influence of the curing process, and to explore the energy consumption and performance balance relationship generated during the resin system curing process.

[0003] Currently, there have been numerous studies on the temperature field process optimization during the curing process of resin systems. The patent "An Optimization Method and Optimization System for an Epoxy Resin Curing Process, CN113807028A" established an optimization system for the epoxy resin curing process based on the EGO algorithm. Through characterization experiments such as mechanical properties and glass transition temperature, the calculated values of the optimization system were verified. The patent "A Method for Modeling the Curing Process of Composites, CN 114065578A" performed finite element simulation on the curing temperature field based on a machine learning method of a neural operator model to achieve efficient prediction from the curing process to the state information during the curing process. However, the above methods have problems such as low efficiency, large error and high calculation cost.

[0004] To solve the problems of high energy consumption, difficult monitoring of self-exothermic effect, low efficiency, and high cost in the curing process of resin systems, the present invention proposes an optimization method and device for the curing process of resin systems based on the self-exothermic effect. It designs a simple and efficient in-situ monitoring device for the self-exothermic effect of resin system curing based on multi-level precision control, realizes high-precision separation and decoupling of the curing self-exothermic effect of the resin system based on Fourier heat conduction theory, and conducts comparative screening of low-energy consumption and high-performance curing processes based on self-exothermic indicators and performance indicators. It has the characteristics of high precision and strong universality for the analysis of the curing self-exothermic effect of various resin systems under complex curing processes and the design of low-energy consumption and high-performance curing processes, reduces the sunk cost, shortens the optimization cycle of the curing process adapted to the resin system, and is conducive to the development of high-efficiency, high-performance, and low-energy consumption curing processes for resin systems. Summary of the Invention

[0005] The present invention discloses an optimization method and device for the curing process of resin systems based on the self-exothermic effect. Based on the multi-level precision control of heat conduction of each component, monitoring system error, and alignment accuracy, it realizes high-precision and low-cost in-situ monitoring of the self-exothermic effect during the curing process of the resin system. Based on the Fourier heat conduction model, it establishes a high-precision separation, decoupling, and evaluation method for the curing self-exothermic effect of the resin system, which is applicable to high-precision analysis of the self-exothermic effect of various types of resin systems under complex curing processes. Based on the comparison of self-exothermic indicators and performance indicators, it explores the influence law of high-performance resin systems adapting to low-energy consumption curing processes, shortens the optimization cycle of the curing process adapted to the resin system, and helps to realize the research and development design of high-efficiency, high-performance, and low-energy consumption curing processes for resin systems.

[0006] To achieve the above objectives, the technical solution of the present invention is as follows:

[0007] An optimization method for the curing process of resin systems based on the self-exothermic effect, characterized by comprising the following steps:

[0008] 1) Multi-level precision control design of the in-situ monitoring device: Based on heat conduction collaborative control, design the material, structural dimensions, and contact fixing method of the components to reduce the heat loss caused by component heat conduction during the curing process of the resin system; based on the system error control of temperature monitoring, select a highly adaptable temperature measurement sensor, and conduct the design of a limit-adjustable structure with multi-point layout of components to reduce the system error of temperature monitoring at each point; based on multi-level alignment precision control, conduct the design of a highly stable structure with flexible adjustment of components to improve the convenience of alignment operation and the positioning accuracy of the temperature measurement points;

[0009] 2) Separation and decoupling of the self-heating effect: In-situ monitor the curing process of the resin system. Based on the monitoring data of the resin system and the curing environment temperature, construct a Fourier heat conduction model, fit the linear interval of the model to obtain the total heat transfer coefficient, separate and decouple the heat transfer effect and the self-heating effect of the resin system curing temperature field, perform a time integral on the self-heating term in the Fourier heat conduction model, and design a self-heating index;

[0010] 3) Screening and optimization of the curing process: Design different curing processes. Based on the variance significance difference test of the total heat transfer coefficient, determine the parallelism of the in-situ monitoring device for the self-heating effect. Based on the self-heating index, evaluate the self-heating effect of the resin system under different curing processes, prepare test specimens, set performance indicators, and based on the comparison of the self-heating index and performance indicators, realize the screening and optimization of low-energy consumption and high-performance curing processes.

[0011] The process optimization method for the self-heating effect of the resin system curing is realized based on the in-situ monitoring device for the self-heating effect of the resin system curing. The device structure includes a liquid-carrying tube (1), a resin system temperature sensor (3), a curing environment temperature sensor (4), a temperature sensor fixing device (5), a telescopic carrier arm (2), a telescopic carrier arm (6), a telescopic fixing arm (7), a cross clamp 1 (8), and a cross clamp 2 (9);

[0012] The inner diameter of the liquid-carrying tube (1) is R1 and the height is H1. The liquid-carrying tube (1) is fixed on the carrier clamp (2-4) of the telescopic carrier arm (2);

[0013] The temperature sensor fixing device (5) is composed of a flexible gasket (5-1), a rigid upper jacket (5-2), a rigid lower jacket (5-3), and a positioning bolt (5-4). It is provided with a resin system temperature measurement limit hole (5-5), a curing environment temperature measurement limit hole (5-6), a resin system temperature measurement positioning hole (5-7), a curing environment temperature measurement positioning hole (5-8), and a positioning scale R2. The resin system temperature sensor (3) and the curing environment temperature sensor (4) pass through the resin system temperature measurement positioning hole (5-7) and the curing environment temperature measurement positioning hole (5-8) on the flexible gasket (5-1), embed the flexible gasket (5-1) into the carrier iron ring (6-4) of the telescopic carrier arm (6), and assemble in the order of "rigid upper jacket (5-2) - flexible gasket (5-1) - rigid lower jacket (5-3)", and tighten the positioning bolt (5-4) for fastening;

[0014] The telescopic carrier arm (2) includes a moving screw 1 (2-1), a fixed sleeve rod 1 (2-2), a rotating turbine 1 (2-3), and a carrier clamp (2-4). The moving screw 1 (2-1) is located in the fixed sleeve rod 1 (2-2), and the moving screw 1 (2-1) and the rotating turbine 1 (2-3) adjust the extension length X1 through screw drive;

[0015] The telescopic carrier arm (6) includes a moving screw rod 2 (6-1), a fixed sleeve rod 2 (6-2), a rotating turbine 2 (6-3) and a carrier iron ring (6-4). The moving screw rod 2 (6-1) is located in the fixed sleeve rod 2 (6-2), and the moving screw rod 2 (6-1) and the rotating turbine 2 (6-3) adjust the extension length X2 through screw transmission;

[0016] The telescopic fixed arm (7) includes a moving screw rod 3 (7-1), a fixed sleeve rod 3 (7-2), and a rotating turbine 3 (7-3). The moving screw rod 3 (7-1) is located in the fixed sleeve rod 3 (7-2), and the moving screw rod 3 (7-1) and the rotating turbine 3 (7-3) adjust the extension length Z1 through screw transmission.

[0017] The thermal conduction collaborative regulation refers to the collaborative design of the material, structural dimensions and contact fixing method of the liquid-carrying pipe (1) based on the thermal conductivity of the resin system; the specific steps are as follows:

[0018] ① When the thermal conductivity of the resin system ∈ [0.10 W / (m·K), 0.2 W / (m·K)], one or more of gold and silver are selected for the liquid-carrying pipe (1), the wall thickness ∈ [0.10 mm, 1.00 mm], and the contact fixing method is bonding fixation;

[0019] ② When the thermal conductivity of the resin system ∈ (0.2 W / (m·K), 0.5 W / (m·K)], one or more of aluminum and copper are selected for the liquid-carrying pipe (1), the wall thickness ∈ (0.10 mm, 2.00 mm], and the contact fixing method is one or more of bonding fixation, clamping fixation and elastic cord binding;

[0020] ③ When the thermal conductivity of the resin system ∈ (0.5 W / (m·K), 5.0 W / (m·K)], one or more of iron, stainless steel and quartz glass are selected for the liquid-carrying pipe (1), the wall thickness ∈ (0.10 mm, 5.00 mm], and the contact fixing method is one or more of bonding fixation, clamping fixation and elastic cord binding.

[0021] The highly adaptable temperature measurement sensor includes but is not limited to J-type thermocouple, K-type thermocouple, T-type thermocouple, E-type thermocouple, N-type thermocouple, and fiber optic temperature sensor. The temperature measurement range of the temperature sensor is -100°C - 800°C, the temperature measurement accuracy ∈ [0.1°C, 1.5°C], and the encapsulation diameter of the temperature measurement point ∈ [0.2 mm, 2 mm] to ensure the temperature measurement ability and monitoring accuracy.

[0022] The regulation of the systematic error of the temperature monitoring, the specific steps are as follows:

[0023] ①Based on the temperature measurement points of the resin system, set the number of temperature measurement limit holes (5-5) for the resin system, and accurately locate the position of the temperature measurement positioning hole (5-7) for the resin system in the temperature measurement limit holes (5-5) of the resin system;

[0024] ②Based on the inner diameter R1 of the carrier liquid pipe (1), set the number of temperature measurement limit holes (5-6) for the curing environment, and accurately locate the position R2 of the temperature measurement positioning hole (5-8) for the curing environment in the temperature measurement limit holes (5-6) for the curing environment. The inner diameter R1 of the carrier liquid pipe (1) and the position R2 of the temperature measurement positioning hole (5-8) for the curing environment satisfy R2 ∈ [R1 + wall thickness + 0.1mm, R1 + wall thickness + 100mm].

[0025] The resin system includes one or more of epoxy resin, phenolic resin, silicone resin, aryl acetylene resin, cyanate ester resin, vinyl resin, polyimide resin, bismaleimide resin, polyurethane, unsaturated polyester, and acrylic resin.

[0026] The curing process includes a single-step constant temperature curing process and a multi-temperature step curing process. For the single-temperature step curing process, the heating rate ∈ [0.2°C / min, 10°C / min], the constant temperature range ∈ [50°C, 600°C], and the constant temperature duration ∈ [30min, 1500min]. For the multi-temperature step curing process, the number of steps ∈ [2, 5], the heating rate ∈ [0.2°C / min, 10°C / min], the constant temperature range ∈ [50°C, 600°C], and the constant temperature duration of a single step ∈ [30min, 1500min].

[0027] The separation and decoupling of the curing self-exothermic effect are specifically carried out as follows:

[0028] ①Pre-processing of the monitored data. The resin system temperature is classified and calculated according to the position of the temperature measurement points, the curing environment temperature is averaged, the change rate of the monitored resin system temperature with time is calculated, and the difference between the resin system temperature and the curing environment temperature is calculated;

[0029] ②Construct a Fourier heat conduction model. The formula for calculating the Fourier heat conduction model is as follows:

[0030]

[0031]

[0032] is the change rate of the resin system temperature, is the difference between the resin system temperature and the curing environment temperature, Q 自放热 is the self-exothermic term of the resin system curing, is the heat transfer term of the resin system curing, K C is the total heat conduction coefficient;

[0033] ③Separation and decoupling of heat transfer effects, and the separation and decoupling of heat transfer effects satisfy Q in the Fourier heat conduction model 自放热 = 0;

[0034] ④Separation and decoupling of self-heat release effects, and the separation and decoupling of self-heat release effects satisfy the conditions in the Fourier heat conduction model

[0035] The screening and optimization of the curing process are as follows:

[0036] ①Parallelism of in-situ monitoring settings. In the variance significance difference test of the total heat transfer coefficient K C , the number of in-situ monitoring samples in each group is 3 - 6 times, the test threshold is set to 0.05, the letters or asterisk marks of each group of data are the same, and there is no significant difference between groups;

[0037] ②Comparison of self-heat release indicators. Self-heat release indicators include but are not limited to peak temperature, energy consumption, self-heat release time, and self-heat release increment. The peak temperature refers to the temperature corresponding to , refers to the first derivative of the temperature change rate of the resin system. The energy consumption refers to the integral calculation of the real-time power of the oven during the curing process time t The self-heat release time refers to the time when Q in the Fourier heat conduction model 自放热 ≠ 0. The self-heat release increment refers to the value that satisfies within the self-heat release time

[0038]

[0039] ③Comparison of performance indicators. Performance indicators include but are not limited to tensile strength and flexural strength.

[0040] Invention Effect

[0041] The present invention provides a method and device for optimizing the curing process of a resin system based on the self-heat release effect, having the following effects:

[0042] (1) Based on the multi-level precision control of the heat conduction of the device, the error of the monitoring system, and the alignment accuracy, a simple and efficient in-situ monitoring device for the self-heat release effect of resin system curing is designed to achieve high-precision and high-stability monitoring of the self-heat release effect of resin system curing;

[0043] (2) Based on the Fourier heat conduction theory, a high-precision separation and decoupling method for the self-heat release effect of resin system curing is established, which has universality for the high-precision analysis of the self-heat release effect of various types of resin systems under complex curing processes;

[0044] (3) Based on the comparison of the self-exothermic index and performance index of the resin system curing, the influence of the high-performance resin system on the adaptation of the low-energy curing process is explored, the optimization cycle of the resin system on the adaptation of the curing process is shortened, and the research and development efficiency of the resin system on the adaptation of the high-performance, low-energy curing process is improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1 Schematic diagram of a method and apparatus for optimizing a curing process of a resin system based on self-exothermic effect according to an embodiment of the present invention;

[0046] Figure 2 Schematic diagram of an in-situ monitoring device for the self-exothermic effect of curing of a resin system according to an embodiment of the present invention;

[0047] Figure 3 This is a schematic diagram of a temperature sensor fixing device according to an embodiment of the present invention;

[0048] Figure 4 A schematic diagram of a telescopic loading arm according to an embodiment of the present invention;

[0049] Figure 5 A schematic diagram of a telescopic carrier arm according to an embodiment of the present invention;

[0050] Figure 6 This is a schematic diagram of a telescopic fixed arm according to an embodiment of the present invention;

[0051] Figure 7 A monitoring graph of the resin system and curing environment temperature according to an embodiment of the present invention;

[0052] Figure 8 This is a graph showing the self-exothermic effect and heat transfer effect of the resin system during curing according to an embodiment of the present invention;

[0053] In the figure: 1. Liquid carrier tube; 2. Telescopic carrier arm; 3. Resin system temperature sensor; 4. Curing environment temperature sensor; 5. Temperature sensor fixing device; 6. Telescopic carrier arm; 7. Telescopic fixing arm; 8. Cross clamp 1; 9. Cross clamp 2; 2-1. Moving screw 1; 6-1. Moving screw 2; 7-1. Moving screw 3; 2-2. Fixed sleeve rod 1; 6-2. Fixed sleeve rod 2; 7-2. Fixed sleeve rod 3; 2-3. Rotating turbine 1; 6-3. Rotating turbine 2; 7-3. Rotating turbine 3; 2-4. Carrier clamp; 6-4. Carrier iron ring; 5-1. Flexible gasket; 5-2. Rigid upper jacket; 5-3. Rigid lower jacket; 5-4. Positioning bolt; 5-5. Resin system temperature limit hole; 5-6. Curing environment temperature limit hole; 5-7. Resin system temperature positioning hole; 5-8. Curing environment temperature sensor positioning hole. DETAILED DESCRIPTION

[0054] like Figure 1As shown, it is a schematic diagram of the process optimization method and device for curing a resin system based on the self-exothermic effect. The first step of the implementation of the present invention is to design the components at all levels of the in-situ monitoring device based on monitoring accuracy, monitoring accuracy, and monitoring stability, so as to achieve thermal conduction coordination with the resin system, control the system error of the temperature monitoring system, and alignment accuracy; the second step is to implement in-situ monitoring. Based on the temperature monitoring data of the resin system and the curing environment, a Fourier heat conduction model is constructed to perform high-precision separation and decoupling of the self-exothermic effect of the resin system curing, and a self-exothermic index is designed; the third step is the actual curing process. Based on the comparison of the self-exothermic index and the performance index, the curing process is screened and optimized.

[0055] The present invention will be further described below with reference to the accompanying drawings. It should be noted that the following description is only for explaining the present invention and does not limit its content.

[0056] Example 1

[0057] The resin system uses an epoxy resin system with a thermal conductivity of 0.3 W / (m·K).

[0058] As Figure 2 shown, it is a schematic diagram of the in-situ monitoring device for the self-exothermic effect of resin system curing. The device structure includes a carrier liquid tube (1) with low heat transfer loss prepared based on thermal conduction coordination design, a resin system temperature sensor (3) selected based on the system error regulation of temperature monitoring, a curing environment temperature sensor (4), and a designed temperature sensor fixing device (5), a telescopic carrier arm (2), a telescopic carrier arm (6), and a telescopic fixing arm (7) designed based on multi-level alignment accuracy regulation, a cross clamp 1 (8), and a cross clamp 2 (9).

[0059] The carrier liquid tube (1) is made of aluminum, with an inner diameter R1 of 28 mm, a height of 25 mm, and a wall thickness of 0.2 mm. The resin system is configured and poured into the carrier liquid tube (1). The carrier liquid tube (1) is adhesively fixed to the carrier clamp (2-4) of the telescopic carrier arm (2) to reduce the temperature loss caused by the heat conduction of the accessories to the self-exothermic effect of curing.

[0060] The resin system temperature sensor (3) and the curing environment temperature sensor (4) use fiber optic temperature sensors with a temperature measurement range of -100°C - 600°C, a grating area length of 5 mm, a temperature measurement accuracy of 0.2°C, and a temperature sensor package diameter of 0.2 mm to ensure that the temperature monitoring ability and accuracy of the temperature sensor meet the high-precision monitoring requirements for the self-exothermic effect of resin system curing.

[0061] As Figure 3As shown in the figure, it is a schematic diagram of the temperature measurement sensor fixing device. The temperature measurement sensor fixing device (5) consists of a flexible gasket (5-1), a rigid upper jacket (5-2), a rigid lower jacket (5-3), and a positioning bolt (5-4). There are a resin system temperature measurement limit hole (5-5), a curing environment temperature measurement limit hole (5-6), and a positioning scale R2. The resin system temperature measurement sensor (3) and the curing environment temperature measurement sensor (4) pass through the resin system temperature measurement positioning hole (5-7) and the curing environment temperature measurement positioning hole (5-8) on the flexible gasket (5-1). The flexible gasket (5-1) is embedded in the carrier iron ring (6-4) of the telescopic carrier arm (6). Assemble in the order of "rigid upper jacket (5-2) - flexible gasket (5-1) - rigid lower jacket (5-3)", and tighten the positioning bolt (5-4) for fastening.

[0062] As Figure 4 shown in the figure, it is a schematic diagram of the telescopic load-carrying arm. The telescopic load-carrying arm (2) includes a moving screw 1 (2-1), a fixed sleeve rod 1 (2-2), a rotating turbine 1 (2-3), and a load-carrying clamp (2-4). The moving screw 1 (2-1) is located in the fixed sleeve rod 1 (2-2). The moving screw 1 (2-1) and the rotating turbine 1 (2-3) adjust the extended length Xl through screw drive.

[0063] As Figure 5 shown in the figure, it is a schematic diagram of the telescopic carrier arm. The telescopic carrier arm (6) includes a moving screw 2 (6-1), a fixed sleeve rod 2 (6-2), a rotating turbine 2 (6-3), and a carrier iron ring (6-4). The moving screw 2 (6-1) is located in the fixed sleeve rod 2 (6-2). The moving screw 2 (6-1) and the rotating turbine 2 (6-3) adjust the extended length X2 through screw drive.

[0064] As Figure 6 shown in the figure, it is a schematic diagram of the telescopic fixed arm. The telescopic fixed arm (7) includes a moving screw 3 (7-1), a fixed sleeve rod 3 (7-2), and a rotating turbine 3 (7-3). The moving screw 3 (7-1) is located in the fixed sleeve rod 3 (7-2). The moving screw 3 (7-1) and the rotating turbine 3 (7-3) adjust the extended length Zl through screw drive.

[0065] One resin system temperature measurement limit hole (5-5) is set. The position of the resin system temperature measurement positioning hole (5-7) is the structural center of the temperature measurement sensor fixing device (5). The inner diameter R1 of the liquid-carrying pipe (1) is 28 mm. Three curing environment temperature measurement limit holes (5-6) are set, with an angular interval of 120 °C. The position R2 of the curing environment temperature measurement sensor positioning hole (5-8) is 30 mm. By increasing the number of temperature measurement sensors arranged and the fixing accuracy, the systematic error of resin system and curing environment temperature monitoring is reduced.

[0066] As Figure 2As shown in the figure, it is a schematic diagram of the in-situ monitoring device for the self-exothermic effect of resin system curing. Based on multi-level precision control, it ensures the alignment accuracy of the spatial positions of the temperature sensor (3) of the resin system, the temperature sensor (4) of the curing environment, and the carrier liquid pipe (1). The specific steps for the in-situ monitoring of the self-exothermic effect of resin system curing are as follows:

[0067] ① Rotate the cross 1 (8) and the rotary turbine 1 (2-3), precisely adjust the rotation angle U and the extended length X1 of the telescopic carrier arm (2), rotate the cross 2 (9) and the rotary turbine 2 (6-З), precisely adjust the rotation angle W and the extended length X2 of the telescopic carrier arm (6), and ensure that the temperature sensor (3) of the resin system coincides with the central vertical line of the carrier liquid pipe (1);

[0068] ② Stretch the tail fiber parts of the temperature sensor (3) of the resin system and the temperature sensor (4) of the curing environment, ensure that the extended lengths of the temperature sensor (3) of the resin system and the temperature sensor (4) of the curing environment are the same, which is H2. Rotate the rotary turbine 3 (7-3) of the telescopic fixing arm (7), precisely adjust the extended length Z1, and ensure that the depth H3 of the temperature sensor (3) of the resin system from the liquid surface of the resin system is 12.5 mm.

[0069] ③ Place the monitoring device in the curing environment, let it stand for 30 min, heat it up, and in-situ monitor the temperatures of the resin system and the curing environment.

[0070] As Figure 7 shown in the figure, it is a temperature monitoring curve graph of the resin system and the curing environment. Based on the monitoring data, a Fourier heat conduction model is constructed. The internal temperature of the resin system is classified and calculated according to the layout of the temperature measurement points, and the temperature of the curing environment is averaged. Calculate the temperature change rate of the resin system, the temperature difference between the resin system temperature and the curing environment temperature, and substitute them into the Fourier heat conduction model for calculation as follows:

[0071]

[0072] is the temperature change rate of the resin system, Q 自放热 is the self-exothermic term of resin system curing, is the heat transfer term of resin system curing, K C is the total heat conduction coefficient.

[0073] As Figure 8 shown in the figure, it is a curve graph of the self-exothermic effect and heat transfer effect of resin system curing. Separate the heat transfer and self-exothermic effects. The self-exothermic effect satisfies:

[0074]

[0075] The heat transfer effect satisfies: Q 自放热 = 0.

[0076] Under the single-temperature step curing process of 90°C / 180 min, the linear interval of the Fourier heat conduction model was fitted to obtain the total heat transfer coefficient K C was 0.00167 s -1 , in the variance significance difference test of the total heat transfer coefficient K C , the number of experimental group samples was 3 times, the test threshold was set at 0.05, and the letter mark was c. The time integral of the self-heat release term in the Fourier heat conduction model was performed, with a peak temperature of 161.70°C, an energy consumption of 30.50 kw / h, a self-heat release time of 1352 s, and a self-heat release increment of 102.68°C. Tensile and flexural test specimens of the resin system were prepared, with a tensile strength of 50 MPa and a flexural strength of 95 MPa.

[0077] Under the single-temperature step curing process of 120°C / 180 min, the linear interval of the Fourier heat conduction model was fitted to obtain the total heat transfer coefficient K C was 0.001666 s -1 , in the variance significance difference test of the total heat transfer coefficient K C , the number of experimental group samples was 3 times, the test threshold was set at 0.05, and the letter mark was c. There was no significant difference between groups, indicating that the in-situ monitoring device settings were parallel to those under the single-temperature step curing process of 90°C / 180 min. The time integral of the self-heat release term in the Fourier heat conduction model was performed, with a peak temperature of 200.50°C, an energy consumption of 40.75 kw / h, a self-heat release time of 930 s, and a self-heat release increment of 105.30°C. Tensile and flexural test specimens of the resin system were prepared, with a tensile strength of 42 MPa and a flexural strength of 83.7 MPa.

[0078] Under the single-temperature step curing process of 60°C / 180 min, the linear interval of the Fourier heat conduction model was fitted to obtain the total heat transfer coefficient K C was 0.001678 s -1 , in the variance significance difference test of the total heat transfer coefficient K C , the number of experimental group samples was 3 times, the test threshold was set at 0.05, and the letter mark was c. There was no significant difference between groups, indicating that the in-situ monitoring device settings were parallel to those under the single-temperature step curing process of 90°C / 180 min. The time integral of the self-heat release term in the Fourier heat conduction model was performed, with a peak temperature of 132°C, an energy consumption of 24.32 kw / h, a self-heat release time of 2600 s, and a self-heat release increment of 80°C. Tensile and flexural test specimens of the resin system were prepared, with a tensile strength of 45 MPa and a flexural strength of 85 MPa.

[0079] Under the two-temperature step curing process of 90°C / 180 min + 120°C / 60 min, the linear interval of the Fourier heat conduction model was fitted to obtain the total heat transfer coefficient K C is 0.001674 s -1 , in the variance significance difference test of the total heat transfer coefficient K C , the number of experimental group samples was 3 times, the test threshold was set to 0.05, and the letter mark was c. There was no significant difference between groups, indicating that the setting of the in-situ monitoring device was parallel to the setting of the in-situ monitoring device under the single-temperature step curing process of 90°C / 180 min. The time integral of the self-heat release term in the Fourier heat conduction model was performed, and the peak temperature was 160.5°C, the energy consumption was 45.20 kw / h, the self-heat release time was 1380 s, and the self-heat release increment was 101.20°C. Tensile and flexural test specimens of the resin system were prepared, with a tensile strength of 48 MPa and a flexural strength of 90 MPa

[0080] Comparative Example 2

[0081] The carrier liquid pipe (1) is made of quartz glass, and the curing process uses a single-temperature step curing process with a heating rate of 0.2°C / min, a constant temperature range of 90°C, and a constant temperature duration of 180 min. The rest is the same as in Example 1. The total heat transfer coefficient is 0.001447 s -1 , in the variance significance difference test of the total heat transfer coefficient K C , the number of experimental group samples was 3 times, the test threshold was set to 0.05, and the letter mark was d, indicating that the heat loss caused by using a low-thermal conductivity material was large, reducing the in-situ monitoring accuracy of the self-heat release effect of the resin system, resulting in a significant difference in the total heat transfer coefficient K C from Example 1, and the parallelism of the in-situ monitoring setting of the self-heat release effect was poor

[0082] Comparative Example 3

[0083] The temperature measurement sensor fixing device (5) is provided with 1 resin system temperature measurement limit hole (5-5) and 1 curing environment temperature measurement limit hole (5-6). The curing process uses a single-temperature step curing process with a heating rate of 0.2°C / min, a constant temperature range of 90°C, and a constant temperature duration of 180 min. The rest is the same as in Example 1. The total heat transfer coefficient is 0.001849 s -1 , in the variance significance difference test of the total heat transfer coefficient K C , the number of experimental group samples was 3 times, the test threshold was set to 0.05, and the letter mark was b, indicating that the reduction in the number of the curing environment temperature measurement limit holes (5-6) led to an increase in the systematic error of the curing environment temperature monitoring, reducing the monitoring accuracy, resulting in a significant difference in the total heat transfer coefficient from Example 1, and the parallelism of the in-situ monitoring setting of the self-heat release effect was poor

[0084] Comparative Example 4

[0085] The telescopic loading arm (2), telescopic carrier arm (6) and telescopic fixed arm (7) use ordinary test tube clamps without designing a positioning structure with high stability and easy adjustment for the accessories. The curing process uses a single-temperature step curing process with a heating rate of 0.2 °C / min, a constant temperature range of 90 °C, and a constant temperature duration of 180 min. Other conditions are the same as those in Example 1. The overall heat transfer coefficient is 0.001920 s -1 , in the variance significance difference test of the overall heat transfer coefficient K C , the number of experimental group samples is 3 times, the test threshold is set to 0.05, and the letter mark is a. It shows that the non-optimal design of the telescopic arm does not meet the requirements of temperature monitoring alignment accuracy, increases the systematic error of temperature monitoring and self-heat release effect analysis, resulting in a significant difference in the overall heat transfer coefficient compared with Example 1, and the parallelism of the in-situ monitoring setting of the self-heat release effect is poor.

[0086] Example 5

[0087] The resin system uses a cyanate resin system with a thermal conductivity of 0.1 W / (m·K).

[0088] The liquid-carrying tube (1) is made of silver, with an inner diameter R1 of 18 mm, a height of 25 mm, and a wall thickness of 0.1 mm.

[0089] The position R2 of the curing environment temperature measurement sensor positioning hole (5-8) is 20 mm.

[0090] The resin system temperature measurement sensor (3) and the curing environment temperature measurement sensor (4) use K-type thermocouples, with a temperature measurement range of -50 °C - 800 °C, a temperature measurement accuracy of 0.5 °C, and a packaging diameter of 1.5 mm.

[0091] Other conditions are the same as those in Example 1.

[0092] Under the two-temperature step curing process of 120 °C / 180 min + 150 °C / 120 min, the linear interval of the Fourier heat conduction model is fitted. The overall heat transfer coefficient K C is 0.001812 s -1 , in the variance significance difference test of the overall heat transfer coefficient K C , the number of experimental group samples is 3 times, the test threshold is set to 0.05, and the letter mark is b. The time integral of the self-heat release term in the Fourier heat conduction model is performed, and the peak temperature is 233.20 °C, the energy consumption is 55.80 kw / h, the self-heat release time is 3542 s, and the self-heat release increment is 116.8 °C. Tensile and bending test specimens of the resin system are prepared, with a tensile strength of 67 MPa and a bending strength of 155 MPa.

[0093] Under the two-temperature-step curing process of 90°C / 180 min + 150°C / 120 min, the linear range of the Fourier heat conduction model was fitted, and the total heat transfer coefficient K C was 0.001814 s -1 , in the variance significance difference test of the total heat transfer coefficient, the number of experimental group samples was 3 times, the test threshold was set at 0.05, and the letter mark was b. There was no significant difference between groups, indicating that the setting of the in-situ monitoring device was parallel to the setting of the in-situ monitoring device under the two-temperature-step curing process of 120°C / 180 min + 150°C / 120 min. The time integral of the self-heat release term in the Fourier heat conduction model was performed, and the peak temperature was 198.60°C, the energy consumption was 58.20 kw / h, the self-heat release time was 4500 s, and the self-heat release increment was 100.20°C. Tensile and flexural test specimens of the resin system were prepared, with a tensile strength of 62 MPa and a flexural strength of 143 MPa.

[0094] Under the single-temperature-step curing process of 150°C / 300 min, the linear range of the Fourier heat conduction model was fitted, and the total heat transfer coefficient K C was 0.001818 s -1 , in the variance significance difference test of the total heat transfer coefficient K C , the number of experimental group samples was 3 times, the test threshold was set at 0.05, and the letter mark was b. There was no significant difference between groups, indicating that the setting of the in-situ monitoring device was parallel to the setting of the in-situ monitoring device under the two-temperature-step curing process of 120°C / 180 min + 150°C / 120 min. The time integral of the self-heat release term in the Fourier heat conduction model was performed, and the peak temperature was 279.50°C, the energy consumption was 72.00 kw / h, the self-heat release time was 2700 s, and the self-heat release increment was 135.00°C. Tensile and flexural test specimens of the resin system were prepared, with a tensile strength of 58 MPa and a flexural strength of 140 MPa.

[0095] Comparative Example 6

[0096] The resin temperature sensor (3) and the curing environment temperature sensor (4) were selected as type E thermocouples, with a temperature measurement range of 0°C - 375°C, a temperature measurement accuracy of 1.0°C, a temperature measurement point encapsulation diameter of 2 mm, and the curing process was the two-temperature-step curing process of 120°C / 180 min + 150°C / 120 min, and the others were the same as in Example 5. The total heat transfer coefficient was 0.001976 s -1 , in the total heat transfer coefficient K CIn the variance significance difference test, the number of samples in the experimental group was 3 times, the test threshold was set at 0.05, and the letter marker was a, indicating that the temperature monitoring ability and accuracy of the selected temperature sensor were low, increasing the systematic error of temperature monitoring and self-exothermic effect analysis, resulting in a significant difference in the total heat transfer coefficient compared with Example 5, and poor parallelism in the in-situ monitoring setting of the self-exothermic effect.

[0097] The settings of the resin system curing process optimization method and device based on the self-exothermic effect for each example and comparative example are shown in Table 1, and the self-exothermic and performance indicators of the resin system curing are shown in Table 2. From the data of the self-exothermic and performance indicators in Table 2, it can be seen that the in-situ monitoring device and separation and decoupling method in this example have high monitoring accuracy, operation stability, and application universality for various types of resin systems under complex curing processes, greatly shortening the optimization cycle of the resin system adapting to the curing process, and improving the R & D efficiency of the resin system adapting to high-performance and low-energy-consuming curing processes.

[0098] Table 1 In-situ monitoring device and process settings for the self-exothermic effect of resin system curing

[0099]

[0100]

[0101] Table 2 Self-exothermic and performance indicators of resin system curing

[0102]

Claims

1. A method for optimizing the curing process of a resin system based on the self-exothermic effect, characterized in that, It includes the following steps: 1) Multi-level precision regulation design of in-situ monitoring device: Based on heat conduction collaborative regulation, design the materials, structural dimensions and contact fixing methods of the fittings to reduce the heat loss caused by the heat conduction of the fittings during the curing process of the resin system; Based on the regulation of the systematic error of temperature monitoring, select a highly adaptable temperature measurement sensor, and carry out the design of a limit-adjustable structure for multi-point layout of the fittings to reduce the systematic error of temperature monitoring at each point; Based on multi-level alignment precision regulation, carry out the design of a highly stable structure with flexible adjustment of the fittings to improve the convenience of alignment operation and the positioning accuracy of the temperature measurement points; 2) Separation and decoupling of self-heat release effect: Monitor the curing process of the resin system in-situ. Based on the monitoring data of the temperature of the resin system and the curing environment, construct a Fourier heat conduction model, fit the linear interval of the model to obtain the total heat transfer coefficient, separate and decouple the heat transfer effect and the self-heat release effect of the curing temperature field of the resin system, perform time integration on the self-heat release term in the Fourier heat conduction model, and design a self-heat release index; 3) Screening and optimization of curing process: Design different curing processes. Based on the variance significance difference test of the total heat transfer coefficient, determine the parallelism of the in-situ monitoring device for self-heat release effect. Based on the self-heat release index, evaluate the self-heat release effect of the resin system under different curing processes, prepare test specimens, set performance indicators, and based on the comparison of the self-heat release index and performance indicators, realize the screening and optimization of low-energy consumption and high-performance curing processes.

2. An optimization method for the curing process of a resin system based on the self-exothermic effect as shown in claim 1, characterized in that, The process optimization method for the self-heat release effect of resin system curing is realized based on the in-situ monitoring device for the self-heat release effect of resin system curing. The device structure includes a liquid-carrying tube (1), a resin system temperature measurement sensor (3), a curing environment temperature measurement sensor (4), a temperature measurement sensor fixing device (5), a telescopic carrier arm (2), a telescopic carrier arm (6), a telescopic fixing arm (7), a cross clamp 1 (8), and a cross clamp 2 (9); The inner diameter of the liquid-carrying tube (1) is R1 and the height is H1. The liquid-carrying tube (1) is fixed on the carrier clamp (2-4) of the telescopic carrier arm (2); The temperature measurement sensor fixing device (5) is composed of a flexible gasket (5-1), a rigid upper clamp sleeve (5-2), a rigid lower clamp sleeve (5-3), and a positioning bolt (5-4). It is provided with a resin system temperature measurement limit hole (5-5), a curing environment temperature measurement limit hole (5-6), a resin system temperature measurement positioning hole (5-7), a curing environment temperature measurement positioning hole (5-8), and a positioning scale R2. The resin system temperature measurement sensor (3) and the curing environment temperature measurement sensor (4) pass through the resin system temperature measurement positioning hole (5-7) and the curing environment temperature measurement positioning hole (5-8) on the flexible gasket (5-1), embed the flexible gasket (5-1) into the carrier iron ring (6-4) of the telescopic carrier arm (6), and assemble in the order of "rigid upper clamp sleeve (5-2) - flexible gasket (5-1) - rigid lower clamp sleeve (5-3)", and tighten the positioning bolt (5-4) for fastening; The telescopic load arm (2) includes a moving screw 1 (2-1), a fixed sleeve rod 1 (2-2), a rotating turbine 1 (2-3), and a load clamp (2-4). The moving screw 1 (2-1) is located in the fixed sleeve rod 1 (2-2), and the moving screw 1 (2-1) and the rotating turbine 1 (2-3) are used to adjust the extended length X1 through screw drive; The telescopic carrier arm (6) includes a moving screw 2 (6-1), a fixed sleeve rod 2 (6-2), a rotating turbine 2 (6-3), and a carrier iron ring (6-4). The moving screw 2 (6-1) is located in the fixed sleeve rod 2 (6-2), and the moving screw 2 (6-1) and the rotating turbine 2 (6-3) are used to adjust the extended length X2 through screw drive; The telescopic fixed arm (7) includes a moving screw 3 (7-1), a fixed sleeve rod 3 (7-2), and a rotating turbine 3 (7-3). The moving screw 3 (7-1) is located in the fixed sleeve rod 3 (7-2), and the moving screw 3 (7-1) and the rotating turbine 3 (7-3) are used to adjust the extended length Z1 through screw drive.

3. An optimization method for the curing process of a resin system based on the self-exothermic effect as shown in claim 1, characterized in that, The thermal conduction collaborative regulation refers to the collaborative design of the material, structural dimensions, and contact fixing method of the liquid-carrying pipe (1) based on the thermal conductivity of the resin system; the specific steps are as follows: ① When the thermal conductivity of the resin system ∈ [0.10 W / (m·K), 0.2 W / (m·K)], one or more of gold and silver are selected for the liquid-carrying pipe (1), the wall thickness ∈ [0.10 mm, 1.00 mm], and the contact fixing method is bonding fixation; ② When the thermal conductivity of the resin system ∈ (0.2 W / (m·K), 0.5 W / (m·K)], one or more of aluminum and copper are selected for the liquid-carrying pipe (1), the wall thickness ∈ (0.10 mm, 2.00 mm], and the contact fixing method is one or more of bonding fixation, clamping fixation, and elastic cord binding; ③ When the thermal conductivity of the resin system ∈ (0.5 W / (m·K), 5.0 W / (m·K)], one or more of iron, stainless steel, and quartz glass are selected for the liquid-carrying pipe (1), the wall thickness ∈ (0.10 mm, 5.00 mm], and the contact fixing method is one or more of bonding fixation, clamping fixation, and elastic cord binding.

4. An optimization method for the curing process of a resin system based on the self-exothermic effect as shown in claim 1, characterized in that, The highly adaptable temperature measurement sensor includes, but is not limited to, J-type thermocouple, K-type thermocouple, T-type thermocouple, E-type thermocouple, N-type thermocouple, and fiber optic temperature measurement sensor. The temperature measurement range of the temperature measurement sensor is -100°C - 800°C, the temperature measurement accuracy ∈ [0.1°C, 1.5°C], and the encapsulation diameter of the temperature measurement point ∈ [0.2 mm, 2 mm] to ensure the temperature measurement ability and monitoring accuracy.

5. An optimization method for the curing process of a resin system based on the self-exothermic effect as shown in claim 1, characterized in that, The system error regulation of the temperature monitoring is as follows: ① Based on the temperature measurement points of the resin system, set the number of temperature measurement limit holes (5-5) of the resin system, and accurately locate the position of the temperature measurement positioning hole (5-7) in the temperature measurement limit hole (5-5) of the resin system; ②Based on the inner diameter R1 of the liquid-carrying pipe (1), set the number of temperature measurement and limit holes (5-6) for the curing environment. Precisely locate the position R2 of the temperature measurement and positioning hole (5-8) for the curing environment in the temperature measurement and limit holes (5-6) for the curing environment. The inner diameter R1 of the liquid-carrying pipe (1) and the position R2 of the temperature measurement and positioning hole (5-8) for the curing environment satisfy R2 ∈ [R1 + wall thickness + 0.1 mm, R1 + wall thickness + 100 mm].

6. An optimization method for the curing process of a resin system based on the self-exothermic effect as shown in claim 1, characterized in that, The resin system includes one or more of epoxy resin, phenolic resin, silicone resin, aryl alkyne resin, cyanate ester resin, vinyl resin, polyimide resin, bismaleimide resin, polyurethane, unsaturated polyester, and acrylic resin.

7. An optimization method for the curing process of a resin system based on the self-exothermic effect as shown in claim 1, characterized in that, The curing process includes a single-step constant-temperature curing process and a multi-temperature-step curing process. For the single-temperature-step curing process, the heating rate ∈ [0.2 °C / min, 10 °C / min], the constant-temperature range ∈ [50 °C, 600 °C], and the constant-temperature duration ∈ [30 min, 1500 min]. For the multi-temperature-step curing process, the number of steps ∈ [2, 5], the heating rate ∈ [0.2 °C / min, 10 °C / min], the constant-temperature range ∈ [50 °C, 600 °C], and the constant-temperature duration for a single step ∈ [30 min, 1500 min].

8. An optimization method for the curing process of a resin system based on the self-exothermic effect as shown in claim 1, characterized in that, The separation and decoupling of the curing self-heat release effect are specifically as follows: ①Pre-treatment of monitoring data: The resin system temperature is classified and calculated according to the position of the temperature measurement points, the curing environment temperature is averaged, the change rate of the monitored resin system temperature over time is calculated, and the difference between the resin system temperature and the curing environment temperature is calculated. ②Construct a Fourier heat conduction model. The formula for the Fourier heat conduction model is calculated as follows: is the temperature change rate of the resin system, is the temperature difference between the resin system temperature and the curing environment temperature, Q 自放热 is the self-exothermic term of the resin system curing, is the heat transfer term of the resin system curing, K C is the total heat transfer coefficient; ③ Decoupling of the heat transfer effect, and the decoupling of the heat transfer effect satisfies Q 自放热 = 0 in the Fourier heat conduction model; ④Separation and decoupling of the self-heating effect, and the separation and decoupling of the self-heating effect satisfy the 9. An optimization method for the curing process of a resin system based on the self-exothermic effect as shown in claim 1, characterized in that, The screening and optimization of the curing process are specifically as follows: ① Parallelism of in-situ monitoring settings, in the variance significance difference test of the overall heat transfer coefficient K C In the test, the number of in-situ monitoring samples in each group is 3 to 6 times, the set test threshold is 0.05, the letters or asterisks of each group of data are marked the same, and there is no significant difference between groups; ②Comparison of self-heating indicators. The self-heating indicators include, but are not limited to, peak temperature, energy consumption, self-heating time, and self-heating increment. The peak temperature refers to the temperature that meets the corresponding temperature, refers to the first derivative of the temperature change rate of the resin system. The energy consumption refers to the integral calculation of the real-time power of the oven during the curing process time t The self-heating time refers to the time when Q 自放热 ≠0 in the Fourier heat conduction model. The self-heating increment refers to the value that meets ③Comparison of performance indicators. The performance indicators include, but are not limited to, tensile strength and flexural strength.

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