Nanometer infrared detection method and detection equipment for interface performance of epoxy resin composite material

Abstract

The invention provides a nanometer infrared detection method and detection equipment for the interface performance of an epoxy resin composite material, and the nanometer infrared detection method comprises the following steps: (1) providing an epoxy resin composite material test sample which comprises a polymer matrix and a filler; (2) carrying out characterization detection on the polymer matrix body, the filler and the interface of the polymer matrix and the filler by utilizing a nano infrared spectrum to obtain nano infrared spectrum data; and (3) analyzing and comparing the obtained nano infrared spectrum data to obtain the signal difference between the interface and the polymer matrix body and the filler, confirming the chemical bond type of the interface, and speculating the interface performance of the epoxy resin composite material test sample. The nano infrared detection method provided by the invention can be used for analyzing a chemical bond forming mechanism of a polymer matrix and a filler interface, and a test result is relatively accurate.

Description

Technical Field

[0001] The invention belongs to the technical field of interface performance testing, and relates to a nano-infrared detection method and detection equipment for the interface performance of epoxy resin composite materials. Background Art

[0002] Epoxy resin composites are multiphase materials formed by physically or chemically combining an epoxy resin polymer matrix with reinforcements (such as fibers, particles, and nanofillers). These materials combine the toughness and processability of the matrix with the high strength, high modulus, or specialized properties of the reinforcements through a synergistic effect. Due to their lightweight, high-strength, heat-resistant, and corrosion-resistant properties, they are widely used in aerospace, automotive, electronics, construction, energy, and biomedical fields.

[0003] As electronic packaging technology rapidly advances toward higher density, miniaturization, and higher performance (e.g., 2.5D / 3D packaging and chiplet technology), underfill, as a key epoxy composite material, plays an irreplaceable role in enhancing chip package reliability. Its primary function is to fill the gap between the chip and substrate (or interposer), encapsulating the solder joints and effectively alleviating thermomechanical stresses caused by material coefficient of thermal expansion (CTE) mismatch. This significantly improves solder joint fatigue resistance and the long-term reliability of the overall package structure under complex operating conditions (e.g., temperature cycling and drop shock). Modern high-performance underfills typically contain large amounts of nano- to micron-sized inorganic fillers (e.g., silica SiO2, alumina Al2O3) to modulate the CTE, improve mechanical strength, enhance thermal and electrical conductivity, and reduce cure shrinkage. Chemical bonding at the interface (e.g., covalent bonding mediated by silane coupling agents) directly determines the mechanical strength, thermal stability, and resistance to environmental aging between the materials. However, existing direct detection methods for interfacial chemical bonds still have problems such as insufficient sensitivity, destructive operations or limited analysis depth, and there is an urgent need to develop new, efficient and accurate interface characterization methods.

[0004] In organic-inorganic composite systems such as bottom fillers, the interface between the inorganic filler particles and the epoxy resin polymer matrix is ​​the core area that determines the overall performance of the material (especially mechanical properties and long-term reliability). The quality of this interface is directly related to the stress transfer efficiency, reinforcement effect, interface bonding strength and environmental stability. The bonding state of this interface is highly dependent on the surface treatment of the filler (such as silane coupling agent), the chemical compatibility of the resin and filler, and the curing process. Its key characteristics (such as the degree of coupling agent reaction, the chemical structure of the interface phase, potential defects / voids, and aging degradation behavior) are prevalent in the nanometer to submicron scale. Accurate, in-situ, and non-destructive characterization of them is a core technical challenge facing the industry. Therefore, accurately detecting the type of chemical bonds at the interface is a core requirement for optimizing process parameters and improving product reliability.

[0005] The prior art also discloses a technical solution for analyzing the interface of composite materials using spectroscopy. For example, CN105973703A discloses a detection device and method for measuring the shear strength of the interface of composite materials using Raman spectroscopy. The instrument tests the shear strength of the sample through a series of optical instruments and a supporting structure, and has the characteristics of accurate detection; CN102830132A is a fiber / polymer interface shear crystallization online detector based on stress monitoring. This method obtains the relationship between the pulling rate, interface shear stress, interface crystallization morphology and polycrystalline state by pulling the fiber in a semi-crystalline polymer melt and monitoring the interface stress and interface crystallization process online. The invention has the characteristics of high degree of integration, high displacement accuracy, and the ability to monitor interface shear stress and interface crystallization morphology in real time. However, the test methods provided by the above two prior arts are not sufficient to accurately reflect the type of chemical bonds at the interface.

[0006] Because the interface regions of epoxy composites (such as underfills) are typically nanometer-sized, the spatial resolution of common characterization methods is typically above micrometers, making it difficult to accurately measure at the nanometer scale. However, the interface regions of epoxy composites are crucial to the overall performance of the material, necessitating the development of high-resolution interface characterization methods. Summary of the Invention

[0007] In view of the shortcomings of the prior art, the object of the present invention is to provide a nano-infrared detection method and detection equipment for the interface properties of epoxy resin composite materials.

[0008] The present invention provides a method and system for directly detecting chemical bonds at the interface between a polymer matrix and a filler in epoxy resin composite materials using nano-infrared spectroscopy. Compared with existing detection methods, the detection method provided by the present invention has an ultra-high spatial resolution (10 nanometers), can accurately obtain spectral information at the interface and analyze its chemical bond composition, and can provide a new method for interface testing of epoxy resin composite materials.

[0009] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0010] In a first aspect, the present invention provides a nano-infrared detection method for the interface properties of epoxy resin composite materials, the nano-infrared detection method comprising the following steps:

[0011] (1) providing an epoxy resin composite material test sample, wherein the epoxy resin composite material test sample includes a polymer matrix and a filler;

[0012] (2) characterizing and detecting the polymer matrix, the filler, and the interface between the polymer matrix and the filler using nano-infrared spectroscopy to obtain nano-infrared spectral data;

[0013] (3) Analyze and compare the obtained nano-infrared spectrum data to obtain the signal difference between the interface and the main body of the polymer matrix and the filler, confirm the chemical bond type of the interface, and infer the interface performance of the epoxy resin composite material test sample.

[0014] The detection method provided by the present invention first performs nano-infrared spectroscopy on the polymer matrix, filler, and the interface between the two. Based on the signal differences between the interface and the polymer matrix and filler, the chemical bond type at the interface is determined, and the interfacial properties of the epoxy resin composite test sample can be inferred. Compared with conventional Fourier transform infrared spectroscopy (resolution: 10-30 microns), the present invention utilizes nano-infrared spectroscopy (combining atomic force microscopy (AFM) with Fourier transform infrared spectroscopy (FTIR) with a resolution of 10 nanometers) for testing, achieving precise detection of material interfaces and providing guidance for the analysis of their interfacial properties.

[0015] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the objectives and beneficial effects of the present invention can be better achieved and realized.

[0016] Preferably, the epoxy resin composite material test sample in step (1) has a higher flatness (ie, a lower roughness).

[0017] Preferably, the roughness of the epoxy resin composite material test sample is less than 10 microns (eg, 9 microns, 8 microns, 7 microns, 6 microns, 5 microns, 4 microns, etc.), and the interface between the resin and the filler can be observed on the surface.

[0018] Preferably, the polymer matrix comprises epoxy resin.

[0019] Preferably, the epoxy resin includes any one or a combination of at least two of bisphenol F epoxy resin, multifunctional epoxy resin, naphthalene epoxy resin and bisphenol A epoxy resin.

[0020] Preferably, the polymer matrix further comprises an auxiliary agent.

[0021] Preferably, the auxiliary agent includes any one of a curing agent, an accelerator, a coupling agent, and a catalyst, or a combination of at least two of them.

[0022] Preferably, the curing agent includes any one of an amine curing agent, an acid anhydride curing agent, and a phenolic curing agent, or a combination of at least two of them.

[0023] Preferably, the coupling agent includes any one of an organosilicon coupling agent, a silane coupling agent, and a phthalate coupling agent, or a combination of at least two of the above.

[0024] Preferably, the filler includes any one of silicon dioxide, diamond, aluminum oxide, graphene, and boron nitride, or a combination of at least two thereof.

[0025] Preferably, based on the total weight of the epoxy resin composite material test sample as 100%, the content of the epoxy resin is 5% to 60% (for example, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, etc.), the content of the auxiliary agent is 1% to 30% (for example, 1%, 2%, 3%, 5%, 10%, 15%, 20%, 25%, 30%, etc.), and the content of the filler is 40% to 70% (for example, 40%, 45%, 50%, 55%, 60%, 65%, 70%, etc.).

[0026] Preferably, when step (2) uses nano-infrared spectroscopy for characterization and detection, the cantilever beam probe of the nano-infrared spectrometer used includes at least one of the Arrow-NCPt, Arrow-NCHPt, and RTESPA series.

[0027] Preferably, when step (2) is performed using nano-infrared spectroscopy for characterization and detection, the wavelength of the nano-infrared spectroscopy is 0-800 cm -1 , 800-1800cm -1 、1800-3600cm -1 At least one of .

[0028] Preferably, when step (2) is characterized and detected using nano-infrared spectroscopy, the scanning frequency is 0.1-1 Hz, for example, 0.1 Hz, 0.2 Hz, 0.3 Hz, 0.4 Hz, 0.5 Hz, 0.6 Hz, 0.7 Hz, 0.8 Hz, 0.9 Hz, 1 Hz, etc.

[0029] The present invention controls the scanning cantilever beam probe, the test band and the scanning frequency, thereby obtaining a clear signal without causing damage to the test sample.

[0030] Preferably, when the characterization and detection is performed using nano-infrared spectroscopy in step (2), the test mode is at least one of the tapping mode, the contact mode, and the tapping AFM-IR mode.

[0031] Preferably, the signal difference in step (3) includes at least one of the appearance of a new characteristic peak, a change in the intensity of the characteristic peak, a change in displacement, a change in half-peak width, and a change in relative peak intensity. Based on these signal differences, specifically, based on the location of the new characteristic peak, the type of chemical bond at the interface can be confirmed. The new characteristic peak refers to a characteristic peak that does not appear in the bulk of the polymer matrix or the filler, but appears at the interface between the two.

[0032] The present invention does not specifically limit how to prepare the epoxy resin composite material test sample. Exemplarily, the preparation method includes the following steps:

[0033] (1) mixing epoxy resin, filler and additive to obtain a mixed glue;

[0034] (2) The mixed glue solution is cured and demolded, and the cured sample is inlaid with AB glue and then polished to obtain a test sample.

[0035] Preferably, the mixing in step (1) includes any one of vacuum high-speed mixing, solution blending, and melt blending. During mixing, the raw materials need to be mixed as evenly as possible.

[0036] Preferably, the grinding and polishing in step (2) is grinding and polishing until the roughness of the side to be tested is no more than 10 microns.

[0037] In a second aspect, the present invention provides a device for detecting the interface properties of epoxy resin composite materials, the detection device comprising a laser with adjustable wavelength, an infrared spectrometer, a cantilever arm probe, a sample stage, a memory and a processor, the memory storing a computer program, and the processor implementing the steps of the nano-infrared detection method described in the first aspect when executing the computer program.

[0038] Compared with the prior art, the present invention has the following beneficial effects:

[0039] The detection method provided by this invention first performs nano-infrared spectroscopy on the polymer matrix, filler, and the interface between them. Based on the signal differences between the interface and the polymer matrix and filler, the chemical bond type at the interface is determined, and the interfacial properties of the epoxy resin composite test sample can be inferred. Compared with conventional Fourier transform infrared spectroscopy, this invention utilizes nano-infrared spectroscopy for testing, achieving precise detection of material interfaces and providing guidance for the analysis of interfacial properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 A schematic flow chart of the nano-infrared detection method for the interface properties of epoxy resin composite materials provided in Example 1 of the present invention;

[0041] Figure 2 Schematic diagram of a device for detecting the interface properties of epoxy resin composite materials provided in Example 1 of the present invention;

[0042] Figure 3 Schematic diagram of the preparation process of the test sample provided in Example 1 of the present invention;

[0043] Figure 4 The test position marks of the test sample in step (2) of Example 1 of the present invention (the three red marks in the figure are the test positions, and the dotted arc is the interface);

[0044] Figure 5 Nano-infrared spectra of the polymer matrix body, filler, and the interface between the polymer matrix and filler provided in Example 1 of the present invention. DETAILED DESCRIPTION

[0045] The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the embodiments are merely to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0046] Example 1

[0047] In this embodiment, a nano-infrared detection method for the interface properties of epoxy resin composite materials is provided, and its flow chart is as follows: Figure 1 The schematic diagram of the detection device is shown in Figure 2 As shown, the nano-infrared detection method includes the following steps:

[0048] (1) Providing an epoxy resin composite material test sample, wherein the epoxy resin composite material test sample includes a polymer matrix and a filler.

[0049] Specifically, epoxy resin, filler, curing agent, coupling agent, and catalyst are mixed in a mass ratio of 22:65:7:5:1 to obtain a mixed glue;

[0050] Epoxy resin: naphthalene epoxy resin, purchased from DIC Corporation, brand HP7200;

[0051] Filler: epoxy-modified silica particles, purchased from Admatech Co., Ltd., brand FEB25A;

[0052] Curing agent: a mixture of methylhexahydrophthalic anhydride and methyltetrahydrophthalic anhydride, with a mass ratio of 1:1;

[0053] Coupling agent: 3-aminopropyltriethoxysilane (C,H0)SiCHNH, brand KBE903;

[0054] Catalyst: diethyltoluenediamine DETDAEthacure 100, purchased from Albemarle Japan Co., Ltd.

[0055] After the mixed glue solution is defoamed, it is cured for the first time, demoulded, and the cured sample is inlaid with AB glue, cured for the second time, and then polished to obtain a test sample with a roughness of less than 1 micron (the preparation process of the test sample is shown in the figure). Figure 3 As shown, the components other than the filler in the test sample constitute the polymer matrix);

[0056] The first curing process was to set the oven to heat up from room temperature to 125°C at a heating rate of 5°C / min, keep warm for 35 minutes, then heat up from 125°C to 165°C at a heating rate of 3°C / min, keep warm for 1.5 hours, and finally cool down from 165°C to room temperature at a cooling rate of 5°C / min.

[0057] The second curing was performed at 100°C for 3 hours.

[0058] (2) Nano-infrared spectroscopy is used to characterize and detect the polymer matrix, the filler, and the interface between the polymer matrix and the filler to obtain nano-infrared spectral data.

[0059] Specifically, the test sample is fixed on the sample stage of the nano-infrared spectrometer, and the polymer matrix, filler, and the interface between the polymer matrix and filler are characterized and detected using nano-infrared spectroscopy, such as Figure 4 As shown, this characterization technology has extremely high spatial resolution and can clearly see the interface area; the nano-infrared spectral data of the polymer matrix, filler, and the interface between the polymer matrix and filler obtained by the test are displayed in the form of images as shown below. Figure 5 As shown;

[0060] The cantilever probe of the nano-infrared spectrometer used in the test is Arrow-NCPt series, and the wavelength range of the nano-infrared spectrum is 800-1800cm -1, the scanning frequency is 0.5Hz, and the test mode is tapping mode (Tapping Mode).

[0061] (3) Analyze and compare the obtained nano-infrared spectrum data to obtain the signal difference between the interface and the main body of the polymer matrix and the filler, confirm the chemical bond type of the interface, and infer the interface performance of the epoxy resin composite material test sample.

[0062] Specifically, in this embodiment, for Figure 5 The nano-infrared spectrum data shown shows that the infrared spectrum at the interface is very close to that of the filler, at 1244 cm -1 There is an additional characteristic peak at the top, which is attributed to the epoxy group in the epoxy resin. The high intensity of this peak indicates that there is a good interface interaction between the filler and the resin.

[0063] In summary, the present invention provides a method for directly detecting chemical bonds at the interface between the polymer matrix and filler in epoxy resin composite materials using nano-infrared spectroscopy. This detection method can be used to analyze the chemical bond formation mechanism at the interface between the polymer matrix and filler, and the test results are relatively accurate, which can provide theoretical guidance for the interface performance testing of epoxy resin composite materials.

[0064] The applicant declares that while the present invention uses the aforementioned embodiments to illustrate a nano-infrared detection method and apparatus for detecting the interfacial properties of epoxy resin composite materials, the present invention is not limited to the aforementioned embodiments, nor does it necessarily rely on the aforementioned embodiments for implementation. Persons skilled in the art should understand that any improvements to the present invention, equivalent substitutions for the raw materials used, additions of auxiliary components, and selection of specific methods, etc., fall within the scope of protection and disclosure of the present invention.

Claims

1. A nano-infrared detection method for the interface properties of epoxy resin composite materials, characterized in that: The nano-infrared detection method comprises the following steps: (1) providing an epoxy resin composite material test sample, wherein the epoxy resin composite material test sample includes a polymer matrix and a filler; (2) characterizing and detecting the polymer matrix, the filler, and the interface between the polymer matrix and the filler using nano-infrared spectroscopy to obtain nano-infrared spectral data; (3) Analyze and compare the obtained nano-infrared spectrum data to obtain the signal difference between the interface and the main body of the polymer matrix and the filler, confirm the chemical bond type of the interface, and infer the interface performance of the epoxy resin composite material test sample.

2. The nano-infrared detection method according to claim 1, characterized in that: The epoxy resin composite material test sample in step (1) has high flatness; Preferably, the roughness of the epoxy resin composite material test sample is less than 10 microns; Preferably, the polymer matrix includes epoxy resin; Preferably, the epoxy resin includes any one or a combination of at least two of bisphenol F epoxy resin, multifunctional epoxy resin, naphthalene epoxy resin and bisphenol A epoxy resin.

3. The nano-infrared detection method according to claim 2, characterized in that: The polymer matrix also includes an auxiliary agent; Preferably, the auxiliary agent includes any one or a combination of at least two of a curing agent, an accelerator, a coupling agent, and a catalyst; Preferably, the curing agent includes any one of an amine curing agent, an acid anhydride curing agent, and a phenolic curing agent, or a combination of at least two thereof; Preferably, the coupling agent includes any one of an organosilicon coupling agent, a silane coupling agent, and a phthalate coupling agent, or a combination of at least two thereof.

4. The nano-infrared detection method according to any one of claims 1 to 3, characterized in that: The filler includes any one of silicon dioxide, diamond, aluminum oxide, graphene, and boron nitride, or a combination of at least two thereof; Preferably, based on the total weight of the epoxy resin composite material test sample as 100%, the content of the epoxy resin is 5% to 60%, the content of the auxiliary agent is 1% to 30%, and the content of the filler is 40% to 70%.

5. The nano-infrared detection method according to any one of claims 1 to 4, characterized in that: When the nano-infrared spectroscopy is used for characterization and detection in step (2), the cantilever beam probe of the nano-infrared spectrometer used includes at least one of the Arrow-NCPt, Arrow-NCHPt, and RTESPA series.

6. The nano-infrared detection method according to any one of claims 1 to 5, characterized in that: When step (2) is characterized and detected by nano-infrared spectroscopy, the wavelength of the nano-infrared spectroscopy is 0-800cm -1 , 800-1800cm -1 、1800-3600cm -1 At least one of .

7. The nano-infrared detection method according to any one of claims 1 to 6, characterized in that: When step (2) uses nano-infrared spectroscopy for characterization and detection, the scanning frequency is 0.1-1 Hz.

8. The nano-infrared detection method according to any one of claims 1 to 7, characterized in that: When the nano-infrared spectroscopy is used for characterization and detection in step (2), the test mode is at least one of the tapping mode, the contact mode, and the tapping AFM-IR mode.

9. The nano-infrared detection method according to any one of claims 1 to 8, characterized in that: The signal difference in step (3) includes at least one of the appearance of a new characteristic peak, a change in the intensity of the characteristic peak, a change in displacement, a change in half-peak width, and a change in relative peak intensity.

10. A device for detecting the interface properties of epoxy resin composite materials, characterized in that: The detection device includes a laser with adjustable wavelength, an infrared spectrometer, a cantilever arm probe, a sample stage, a memory and a processor. The memory stores a computer program, and when the processor executes the computer program, the steps of the nano-infrared detection method as described in any one of claims 1 to 9 are implemented.

Images