技术领域technical field
本发明涉及高分子检测技术领域，特别是一种高分子材料老化的检测方法、检测装置及检测系统。The invention relates to the technical field of polymer detection, in particular to a detection method, detection device and detection system for the aging of polymer materials.
背景技术Background technique
红外吸收光谱技术主要用于化合物鉴定及分子结构表征，亦可用于定量分析，是检测高分子材料老化的重要技术。它的基本原理是红外光谱又称分子振动转动光谱，属分子吸收光谱。样品受到频率连续变化的红外光照射时，分子吸收其中一些频率的辐射，分子振动或转动引起偶极矩的净变化，使振-转能级从基态跃迁到激发态，相应于这些区域的透射光强减弱，记录百分透过率对波数或波长的曲线，即红外光谱。红外吸收光谱可以对气态进行红外光谱测定，气体样品是在气体池中进行测定的，先把气体池中的空气抽掉，然后注入被测气体进行测谱。Infrared absorption spectroscopy is mainly used for compound identification and molecular structure characterization, and can also be used for quantitative analysis. It is an important technology for detecting the aging of polymer materials. Its basic principle is infrared spectroscopy, also known as molecular vibration rotation spectroscopy, which belongs to molecular absorption spectroscopy. When the sample is irradiated by infrared light with continuously changing frequency, the molecules absorb radiation of some of the frequencies, and the molecular vibration or rotation causes a net change in the dipole moment, causing the vibration-rotational energy level to transition from the ground state to the excited state, corresponding to the transmission of these regions When the light intensity is weakened, record the curve of percent transmittance versus wave number or wavelength, that is, infrared spectrum. Infrared absorption spectroscopy can be used to measure the gas state by infrared spectroscopy. The gas sample is measured in the gas cell. First, the air in the gas cell is pumped out, and then the gas to be measured is injected into the gas cell for spectrum measurement.
由于对气体样品的反应条件控制以及生成的气体样品容易受到影响、气密性问题、背景干扰以及测量精度等诸如因素使得其无法得到准确的检测数据。Due to factors such as the control of the reaction conditions of the gas sample and the easy influence of the generated gas sample, air tightness, background interference, and measurement accuracy, it is impossible to obtain accurate detection data.
专利文献1公开了一种在线红外原位反应系统包括加热反应器、与所述加热反应器连接的反应池、冷却装置以及抽真空装置；所述加热反应器包括一横向放置的透明反应管以及滑动套装在所述透明反应管上的加热筒，所述透明反应管内设有通过磁力装置连接可旋转的透明样品放置杆，所述加热筒通过至少一个支撑杆可滑动地安装在底座上，从而可在所述透明反应管上直线移动进行加热，所述透明反应管的末端开口并密封连接所述反应池，所述反应池上设有连接吡啶定量进样器的吡啶进样接头、抽真空接口以及色谱仪连接口，所述色谱仪连接口内设有红外窗片，所述抽真空接口通过气管连接所述冷却装置，所述冷却装置通过抽真空管连接所述抽真空装置。该专利可在连接红外表征控制系统以及色谱检测装置后进行原位红外反应表征研究，但该专利无法控制气体样品的反应条件、气密性差、背景干扰严重以及红外色谱仪和反应池之间的测量精度差，无法得到足够准确的样品随时间变化的检测数据。Patent Document 1 discloses an online infrared in-situ reaction system including a heating reactor, a reaction pool connected to the heating reactor, a cooling device and a vacuum device; the heating reactor includes a horizontally placed transparent reaction tube and The heating cartridge is slidably set on the transparent reaction tube, and the transparent reaction tube is provided with a rotatable transparent sample placement rod connected by a magnetic device, and the heating cartridge is slidably installed on the base through at least one support rod, so that It can move linearly on the transparent reaction tube for heating. The end of the transparent reaction tube is open and sealed to connect with the reaction pool. The reaction pool is provided with a pyridine sampling joint connected to a pyridine quantitative sampler and a vacuum interface. And a connection port of the chromatograph, an infrared window is arranged in the connection port of the chromatograph, the vacuum interface is connected to the cooling device through a gas pipe, and the cooling device is connected to the vacuum device through a vacuum tube. This patent can carry out in-situ infrared reaction characterization research after connecting the infrared characterization control system and chromatographic detection device, but this patent cannot control the reaction conditions of gas samples, poor air tightness, serious background interference, and the measurement between the infrared chromatograph and the reaction cell The accuracy is poor, and it is impossible to obtain sufficiently accurate detection data of samples changing over time.
专利文献2公开了一种基于泵浦探测的红外原位反应测试装置，包括原位反应池、气体缓冲混合池、底座及样品装置，底座用于支撑原位反应池；其中，原位反应池包括反应池壳体(11)，反应池壳体(11)的两端设置探测窗片(13)；反应池壳体(11)侧面设置壳体分支(121)，壳体分支(121)的末端设置泵浦窗片(12)；反应池壳体(11)上还设置样品口接头(14)和抽气口接头(15)；气体缓冲混合池包括混合池壳体(21)，混合池壳体(21)上设置卡口接头(22)、两个针阀(23)、真空装置球阀接头(24)和抽气口球阀接头(25)；其中，卡口接头(22)接堵头备用，真空装置球阀接头(24)连接真空装置球阀后与真空装置连接，抽气口球阀接头(25)连接抽气口球阀后连接三通，三通另外两个接口中的一个接口连接真空规探头，另一个接口通过波纹管与抽气口接头(15)连接；样品装置包括样品托(42)及与样品托(42)相连的顶盖(41)，顶盖(41)与样品口接头(14)可拆卸地连接，样品托(42)用于承载样品(5)，能够使样品(5)处于通过探测窗片(13)的光路与通过泵浦窗片(12)的光路的交汇处。该专利可以在真空条件、特定气体条件以及特定气体的特定压力下进行测试，有效地控制进入混合池壳体的气体的流量，但该专利无法避免反应池生成气体样品的不良影响、气密性差、背景干扰严重以及红外色谱仪和反应池之间的测量精度差，无法得到足够准确的样品随时间变化的检测数据。Patent Document 2 discloses an infrared in-situ reaction test device based on pump detection, including an in-situ reaction cell, a gas buffer mixing cell, a base and a sample device, and the base is used to support the in-situ reaction cell; wherein, the in-situ reaction cell Including the reaction tank housing (11), the two ends of the reaction tank housing (11) are provided with detection windows (13); the side of the reaction tank housing (11) is provided with a housing branch (121), and the housing branch (121) A pump window (12) is arranged at the end; a sample port connector (14) and an air inlet connector (15) are also arranged on the reaction cell housing (11); the gas buffer mixing tank includes a mixing tank housing (21), a mixing tank housing A bayonet joint (22), two needle valves (23), a vacuum device ball valve joint (24) and a suction port ball valve joint (25) are arranged on the body (21); wherein, the bayonet joint (22) is connected to a plug for standby use, The vacuum device ball valve joint (24) is connected to the vacuum device ball valve and then connected to the vacuum device. The air suction port ball valve joint (25) is connected to the air suction port ball valve and then connected to the tee. One of the other two interfaces of the tee is connected to the vacuum gauge probe, and the other The interface is connected to the air inlet connector (15) through a bellows; the sample device includes a sample holder (42) and a top cover (41) connected to the sample holder (42), and the top cover (41) and the sample port connector (14) are detachable The sample holder (42) is used to carry the sample (5), and the sample (5) can be located at the junction of the optical path passing through the detection window (13) and the optical path passing through the pumping window (12). This patent can be tested under vacuum conditions, specific gas conditions and specific pressures of specific gases, effectively controlling the flow of gas entering the mixing cell shell, but this patent cannot avoid the adverse effects of gas samples generated by the reaction cell and poor airtightness , serious background interference, and poor measurement accuracy between the infrared chromatograph and the reaction cell, it is impossible to obtain sufficiently accurate detection data of samples changing over time.
专利文献3公开了一种原位红外光谱样品池，池体包括热电偶、电热器、窗片和样品压片，设有气体进出口，通过密封圈、压紧螺母等紧固与密封，池体内设有环形预热室，流体分配器，环形预热室与物料进口管连接；另在池体外层设池外罩，池外罩由上、下法兰盘外罩组成；流体分配器上设有进气口、导气沟、出气口和中央隔板。该专利能够在样品池内模拟真实的化学反应，但该专利生成的气体样品容易受到影响、气密性差、背景干扰严重以及红外色谱仪和反应池之间的测量精度差，无法得到足够准确的样品随时间变化的检测数据。Patent Document 3 discloses an in-situ infrared spectrometer sample cell. The cell body includes a thermocouple, an electric heater, a window, and a sample pressing sheet. It is provided with a gas inlet and outlet, and is fastened and sealed by a sealing ring and a compression nut. The body is equipped with an annular preheating chamber, a fluid distributor, and the annular preheating chamber is connected to the material inlet pipe; in addition, a pool cover is provided on the outer layer of the pool, and the pool cover is composed of an upper and a lower flange cover; the fluid distributor is equipped with an inlet Air port, air channel, air outlet and central partition. This patent can simulate a real chemical reaction in the sample cell, but the gas sample generated by this patent is easily affected, has poor airtightness, serious background interference, and poor measurement accuracy between the infrared chromatograph and the reaction cell, and it is impossible to obtain a sufficiently accurate sample. Time-varying detection data.
在背景技术部分中公开的上述信息仅仅用于增强对本发明背景的理解，因此可能包含不构成在本国中本领域普通技术人员公知的现有技术的信息。The above information disclosed in this Background section is only for enhancement of understanding of the background of the invention and therefore it may contain information that does not form the prior art that is already known in this country to a person of ordinary skill in the art.
现有技术文献prior art literature
专利文献patent documents
专利文献1：中国专利公开CN204666492U号Patent Document 1: Chinese Patent Publication No. CN204666492U
专利文献2：中国专利公开CN106959283A号Patent Document 2: Chinese Patent Publication No. CN106959283A
专利文献3：中国专利公开CN1069806A号Patent Document 3: Chinese Patent Publication No. CN1069806A
发明内容Contents of the invention
发明要解决的问题The problem to be solved by the invention
如上所述，本发明需要提供一种高分子材料老化的检测方法、检测装置及检测系统，其能够对气体样品的多种反应条件进行精确控制，避免生成的气体产物受到装置的不良影响、显著提高了装置的气密性、大幅降低了背景干扰程度以及通过红外测量模块和反应模块之间的布置提高测量精度，本发明能够检测0.1-1ppm级的气态产物浓度，得到准确的气态产物的浓度变化数据，显著提高了检测的老化速率的精度。As mentioned above, the present invention needs to provide a detection method, detection device and detection system for the aging of polymer materials, which can accurately control various reaction conditions of gas samples, and avoid the adverse effects of the generated gas products on the device, significantly The airtightness of the device is improved, the degree of background interference is greatly reduced, and the measurement accuracy is improved through the arrangement between the infrared measurement module and the reaction module. The present invention can detect the concentration of gaseous products at the level of 0.1-1ppm, and obtain accurate concentration of gaseous products change data, significantly improving the accuracy of the detected aging rate.
解决问题的方案solution to the problem
本发明人等为了达成上述目的而进行了深入研究，具体而言，本发明提供一种高分子材料老化的检测方法包括下述步骤：In order to achieve the above purpose, the present inventors have conducted in-depth research. Specifically, the present invention provides a detection method for the aging of polymer materials, which includes the following steps:
高分子材料样品水平放置在原位反应模块中，所述原位反应模块放入红外光谱检测模块的检测区域，其中，原位反应模块的红外入射窗片和红外出射窗片形成的第一光路与所述红外光谱检测模块的发光端和检测端形成的第二光路同轴，且红外入射窗片和所述发光端形成密封的红外入射区域，以及所述红外出射窗片与检测端形成密封的红外出射区域；The polymer material sample is placed horizontally in the in-situ reaction module, and the in-situ reaction module is placed in the detection area of the infrared spectrum detection module, wherein the first optical path formed by the infrared incident window and the infrared exit window of the in-situ reaction module The second optical path formed by the light-emitting end and the detection end of the infrared spectrum detection module is coaxial, and the infrared incident window and the light-emitting end form a sealed infrared incident area, and the infrared emission window forms a seal with the detection end Infrared emission area;
对所述红外入射区域和红外出射区域分别充入吹扫气体进行吹扫，其中，充入的吹扫气体的流速可调节，当吹扫后所述红外入射区域和红外出射区域中背景气体含量持续小于第一预定浓度时，即可开始测量；所述背景气体指的是吹扫之前，红外入射区域和红外出射区域中的原有的气体。所述背景气体在检测时造成的干扰称为背景噪音。The infrared incident region and the infrared outgoing region are respectively filled with purge gas for purging, wherein the flow rate of the charged purge gas can be adjusted, and the background gas content in the infrared incident region and the infrared outgoing region after purging When the concentration is continuously less than the first predetermined concentration, the measurement can be started; the background gas refers to the original gas in the infrared incidence area and the infrared emission area before purging. The interference caused by the background gas during detection is called background noise.
吹扫的同时，打开第一电磁阀，所述原位反应模块充入用于与高分子材料反应的反应气体，打开第二电磁阀，抽吸所述原位反应模块内的气体，其中，充入和抽吸反应气体的流速分别可调节，当原位反应模块中反应气体含量达到不小于第二预定浓度时，关闭第一和第二电磁阀；While purging, open the first electromagnetic valve, the in-situ reaction module is filled with reaction gas for reacting with the polymer material, open the second electromagnetic valve, and suck the gas in the in-situ reaction module, wherein, The flow rates of charging and pumping the reaction gas can be adjusted separately, and when the content of the reaction gas in the in-situ reaction module reaches a second predetermined concentration, the first and second solenoid valves are closed;
光照模块发出第一预定强度的预定光经由光纤从原位反应模块的上端照射所述高分子材料样品第一预定时间，和/或，加热模块对上述高分子材料样品以预定温度加热第二预定时间，高分子材料样品生成气态产物；The illumination module emits a predetermined light of a first predetermined intensity to irradiate the polymer material sample for a first predetermined time from the upper end of the in-situ reaction module via an optical fiber, and/or, the heating module heats the above polymer material sample at a predetermined temperature for a second predetermined time. time, the polymer material sample generates gaseous products;
预定时间间隔连续检测和采集气态产物的红外光谱信号，其中，红外光谱检测模块的发光端发出第二预定强度的红外光沿着第二光路通过红外入射区域进入原位反应模块使得红外光按照第一光路穿过所述气态产物，穿过所述气态产物的红外光经由红外出射区域进入所述检测端，所述检测端检测所述气态产物的红外光谱信号；Continuously detect and collect infrared spectrum signals of gaseous products at predetermined time intervals, wherein the light-emitting end of the infrared spectrum detection module emits infrared light of a second predetermined intensity along the second optical path through the infrared incident area and enters the in-situ reaction module so that the infrared light follows the first An optical path passes through the gaseous product, the infrared light passing through the gaseous product enters the detection end through the infrared emission area, and the detection end detects the infrared spectrum signal of the gaseous product;
处理模块将预定时间间隔连续采集的红外光谱信号形成基于时间的谱图组，对比谱图组中预定波长区间内波峰随时间的变化以确定气态产物随时间的浓度变化数据，基于气态产物的浓度变化数据得出高分子材料的老化速率。The processing module forms the infrared spectrum signals collected continuously at predetermined time intervals into a time-based spectrogram group, and compares the changes of peaks in the predetermined wavelength range with time in the spectrogram group to determine the concentration change data of gaseous products over time. Based on the concentration of gaseous products The change data yields the aging rate of the polymeric material.
在所述的高分子材料老化的检测方法中，光照模块发出第一预定强度的预定光经由光纤从原位反应模块的上端照射所述高分子材料样品第一预定时间，加热模块对上述高分子材料样品以预定温度加热第二预定时间，湿度模块施加预定湿度到高分子材料样品第三预定时间，酸碱度生成模块施加预定pH值到高分子材料样品第四预定时间，按照预定条件对高分子材料样品进行若干次光照、加热、加湿和/或酸碱度以生成气态产物。In the method for detecting the aging of polymer materials, the illumination module emits a predetermined light of a first predetermined intensity to irradiate the polymer material sample for a first predetermined time from the upper end of the in-situ reaction module via an optical fiber, and the heating module The material sample is heated at a predetermined temperature for a second predetermined time, the humidity module applies predetermined humidity to the polymer material sample for a third predetermined time, and the pH generating module applies a predetermined pH value to the polymer material sample for a fourth predetermined time, and the polymer material is treated according to predetermined conditions The sample is subjected to light, heat, humidity and/or pH several times to generate gaseous products.
在所述的高分子材料老化的检测方法中，处理模块基于光照的第一预定强度和第一预定时间，和/或，加热的预定温度和第二预定时间确定高分子材料的老化速率。In the method for detecting aging of a polymer material, the processing module determines the aging rate of the polymer material based on a first predetermined intensity of light and a first predetermined time, and/or a predetermined temperature of heating and a second predetermined time.
在所述的高分子材料老化的检测方法中，所述红外入射窗片和所述发光端形成红外入射区域以及所述红外出射窗片与检测端形成红外出射区域，所述发光端设有向红外入射区域吹扫所述吹扫气体的第一吹扫口且在红外入射区域形成正压，所述检测端设有向红外出射区域吹扫所述吹扫气体的第二吹扫口且在红外出射区域形成正压，第一吹扫口和第二吹扫口持续吹扫使得背景气体含量保持小于第一预定浓度。In the method for detecting the aging of polymer materials, the infrared incident window and the light-emitting end form an infrared incident area, and the infrared output window and the detection end form an infrared emission area, and the light-emitting end is provided with a direction to The infrared incidence area purges the first purge port of the purge gas and forms a positive pressure in the infrared incidence area, and the detection end is provided with a second purge port for purging the purge gas to the infrared emission area. A positive pressure is formed in the infrared emission area, and the first purge port and the second purge port are continuously purged so that the content of the background gas remains less than the first predetermined concentration.
根据本发明的另一方面，一种实施所述高分子材料老化的检测方法的检测装置包括原位反应模块和红外光谱检测模块，原位反应模块包括，According to another aspect of the present invention, a detection device for implementing the detection method for aging of polymer materials includes an in-situ reaction module and an infrared spectrum detection module, and the in-situ reaction module includes,
红外入射端，位于十字通道的水平方向通道的一侧的红外入射端经由第一法兰紧固结构密封连接红外入射窗片，Infrared incident end, the infrared incident end located on one side of the horizontal channel of the cross channel is sealed and connected to the infrared incident window through the first flange fastening structure,
红外出射端，位于十字通道的水平方向通道的另一侧的红外出射端经由第二法兰紧固结构密封连接红外出射窗片，红外入射窗片和红外出射窗片形成水平的第一光路，Infrared output end, the infrared output end located on the other side of the horizontal channel of the cross channel is sealed and connected to the infrared output window through the second flange fastening structure, and the infrared incident window and the infrared output window form a horizontal first optical path,
其中，第一和/或第二法兰紧固结构的两个连接端面分别设有环形氟橡胶圈，Wherein, the two connection end faces of the first and/or second flange fastening structure are respectively provided with annular fluororubber rings,
红外光谱检测模块，其包括，Infrared spectrum detection module, which includes,
发光端，其用于发射红外光，light-emitting end, which is used to emit infrared light,
检测端，其用于接收和检测穿过原位反应模块的红外光，发光端和检测端形成第二光路，第二光路和所述第一光路同轴，发光端发出第二预定强度的红外光沿着第二光路通过红外入射区域进入原位反应模块使得红外光按照第一光路穿过所述气态产物，穿过所述气态产物的红外光经由红外出射区域进入所述检测端，所述检测端检测所述气态产物的红外光谱信号，The detection end is used to receive and detect infrared light passing through the in-situ reaction module, the light emitting end and the detection end form a second optical path, the second optical path is coaxial with the first optical path, and the light emitting end emits infrared light of a second predetermined intensity The light enters the in-situ reaction module through the infrared incident area along the second optical path so that the infrared light passes through the gaseous product according to the first optical path, and the infrared light passing through the gaseous product enters the detection end through the infrared output area, and the The detection end detects the infrared spectrum signal of the gaseous product,
检测区域，用于容纳所述原位反应模块的检测区域位于发光端和检测端之间，其中，红外入射窗片和所述发光端形成密封的红外入射区域，以及所述红外出射窗片与检测端形成密封的红外出射区域。The detection area, the detection area for accommodating the in-situ reaction module is located between the light-emitting end and the detection end, wherein the infrared incident window and the light-emitting end form a sealed infrared incident area, and the infrared exit window and The detection end forms a sealed infrared emission area.
根据本发明的又一方面，一种实施所述高分子材料老化的检测方法的检测系统包括：According to yet another aspect of the present invention, a detection system implementing the detection method for the aging of polymer materials includes:
原位反应模块，用于在密封环境下提供耦合反应的原位反应模块包括呈十字形通道的石英本体，所述石英本体包括，In-situ reaction module, the in-situ reaction module for providing coupled reactions in a sealed environment includes a quartz body with a cross-shaped channel, and the quartz body includes,
红外入射端，位于十字通道的水平方向通道的一侧的红外入射端经由第一法兰紧固结构密封连接红外入射窗片，Infrared incident end, the infrared incident end located on one side of the horizontal channel of the cross channel is sealed and connected to the infrared incident window through the first flange fastening structure,
红外出射端，位于十字通道的水平方向通道的另一侧的红外出射端经由第二法兰紧固结构密封连接红外出射窗片，红外入射窗片和红外出射窗片形成水平的第一光路，Infrared output end, the infrared output end located on the other side of the horizontal channel of the cross channel is sealed and connected to the infrared output window through the second flange fastening structure, and the infrared incident window and the infrared output window form a horizontal first light path,
光照端，位于十字通道的垂直方向通道的上侧的光照端经由光纤连接光照模块以垂直向下照射，光照端经由第三法兰紧固结构密封连接紫外透过窗片，The illumination end, the illumination end located on the upper side of the vertical channel of the cross channel is connected to the illumination module through an optical fiber to illuminate vertically downward, and the illumination end is sealed and connected to the ultraviolet transparent window through the third flange fastening structure,
样品通过端，位于十字通道的垂直方向通道的下侧的样品通过端开启和密封以输入样品且保持原位反应模块形成密封环境，The sample passing end, the sample passing end located on the lower side of the vertical direction channel of the cross channel is opened and sealed to input the sample and maintain the in-situ reaction module to form a sealed environment,
其中，第一、第二和/或第三法兰紧固结构的两个连接端面分别设有环形氟橡胶圈，Wherein, the two connecting end surfaces of the first, second and/or third flange fastening structures are respectively provided with annular fluororubber rings,
进气口，设在石英本体侧壁上的进气口经由第一电磁阀连接充气单元以可调节地充入反应气体到原位反应模块，The air inlet, the air inlet provided on the side wall of the quartz body is connected to the gas charging unit via the first solenoid valve to adjustably charge the reaction gas into the in-situ reaction module,
出气口，设在石英本体侧壁上的出气口经由第二电磁阀连接抽吸单元以可调节地从原位反应模块中抽出气体，Gas outlet, the gas outlet provided on the side wall of the quartz body is connected to the suction unit via the second solenoid valve to adjustably extract the gas from the in-situ reaction module,
承载平台，用于水平承载高分子材料样品的承载平台位于十字交叉口且位于第一光路下方；The carrying platform, the carrying platform for horizontally carrying the polymer material sample is located at the intersection and below the first optical path;
耦合反应发生单元，其包括设在石英本体外经由光纤连接的光照模块、用于以预定温度加热高分子材料样品的加热模块、施加湿度到高分子材料样品的湿度模块、施加预定pH值到高分子材料样品的酸碱度生成模块和/或用于氧化高分子材料样品的氧化模块，所述光照模块包括太阳光模拟器和光强传感器、所述加热模块设有加热单元和温度传感器、所述湿度模块包括喷雾器和湿度传感器、酸碱度生成模块包括酸碱度发生器和酸碱度检测单元、和/或氧化模块包括氧化单元和氧化检测单元；The coupling reaction generation unit includes an illumination module arranged outside the quartz body and connected via an optical fiber, a heating module for heating the polymer material sample at a predetermined temperature, a humidity module for applying humidity to the polymer material sample, and applying a predetermined pH value to high temperature. A pH generation module for molecular material samples and/or an oxidation module for oxidizing polymer material samples, the illumination module includes a solar simulator and a light intensity sensor, the heating module is provided with a heating unit and a temperature sensor, the humidity The module includes a nebulizer and a humidity sensor, the pH generation module includes a pH generator and a pH detection unit, and/or the oxidation module includes an oxidation unit and an oxidation detection unit;
红外光谱检测模块，其包括，Infrared spectrum detection module, which includes,
发光端，其用于发射红外光，light-emitting end, which is used to emit infrared light,
检测端，其用于接收和检测穿过原位反应模块的红外光，发光端和检测端形成第二光路，第二光路和所述第一光路同轴，发光端发出第二预定强度的红外光沿着第二光路通过红外入射区域进入原位反应模块使得红外光按照第一光路穿过所述气态产物，穿过所述气态产物的红外光经由红外出射区域进入所述检测端，所述检测端检测所述气态产物的红外光谱信号，The detection end is used to receive and detect infrared light passing through the in-situ reaction module, the light emitting end and the detection end form a second optical path, the second optical path is coaxial with the first optical path, and the light emitting end emits infrared light of a second predetermined intensity The light enters the in-situ reaction module through the infrared incident area along the second optical path so that the infrared light passes through the gaseous product according to the first optical path, and the infrared light passing through the gaseous product enters the detection end through the infrared output area, and the The detection end detects the infrared spectrum signal of the gaseous product,
检测区域，用于容纳所述原位反应模块的检测区域位于发光端和检测端之间，其中，红外入射窗片和所述发光端形成密封的红外入射区域，以及所述红外出射窗片与检测端形成密封的红外出射区域；The detection area, the detection area for accommodating the in-situ reaction module is located between the light-emitting end and the detection end, wherein the infrared incident window and the light-emitting end form a sealed infrared incident area, and the infrared exit window and The detection end forms a sealed infrared emission area;
处理模块，其一端连接所述光强传感器、温度传感器、湿度传感器、酸碱度检测单元和/或氧化检测单元，另一端连接所述第一电磁阀、第二电磁阀、红外光谱检测模块以及光照模块、加热模块、湿度模块、酸碱度发生器和氧化单元中的一个或多个，所述处理模块基于接收的数据调节所述原位反应模块和红外光谱检测模块获得气态产物且基于气态产物的浓度变化数据得出高分子材料的老化速率。A processing module, one end of which is connected to the light intensity sensor, temperature sensor, humidity sensor, pH detection unit and/or oxidation detection unit, and the other end is connected to the first solenoid valve, second solenoid valve, infrared spectrum detection module and illumination module One or more of a heating module, a humidity module, a pH generator and an oxidation unit, the processing module adjusts the in-situ reaction module and the infrared spectrum detection module based on the received data to obtain a gaseous product and based on the concentration change of the gaseous product The data yield the aging rate of the polymeric material.
在所述的检测系统中，处理模块包括：In the detection system, the processing module includes:
数据处理单元，其将预定时间间隔连续采集的红外光谱信号形成基于时间的谱图组，a data processing unit, which forms a time-based spectrogram group from infrared spectral signals collected continuously at predetermined time intervals,
计算单元，其对比谱图组中预定波长区间内波峰随时间的变化以确定气态产物随时间的浓度变化数据，a calculation unit, which compares the changes of the peaks in the spectrogram group with time in the predetermined wavelength range to determine the concentration change data of the gaseous product over time,
评价单元，其基于气态产物的浓度变化数据得出高分子材料的老化速率。An evaluation unit that derives the aging rate of the polymer material based on the concentration change data of the gaseous products.
在所述的检测系统中，In the detection system described,
所述红外入射窗片和/或红外出射窗片为CaF2窗片，所述承载平台可拆卸地连接石英本体。The infrared incident window and/or the infrared outgoing window is a CaF2 window, and the carrying platform is detachably connected to the quartz body.
在所述的检测系统中，所述充气单元经由过滤器连接空压机，所述抽吸单元包括真空泵。In the detection system, the inflation unit is connected to an air compressor through a filter, and the suction unit includes a vacuum pump.
在所述的检测系统中，所述检测系统包括控制单元，其连接所述原位反应模块、红外光谱检测模块、充气单元和抽吸单元。In the detection system, the detection system includes a control unit, which is connected to the in-situ reaction module, the infrared spectrum detection module, the gas charging unit and the suction unit.
在所述的检测系统中，处理模块包括数字信号处理器、专用集成电路ASIC或现场可编程门阵列FPGA，处理模块包括存储器，所述存储器可以包括一个或多个只读存储器ROM、随机存取存储器RAM、快闪存储器或电子可擦除可编程只读存储器EEPROM。In the detection system, the processing module includes a digital signal processor, an application specific integrated circuit ASIC or a field programmable gate array FPGA, and the processing module includes a memory, and the memory can include one or more read-only memory ROM, random access Memory RAM, flash memory or electronically erasable programmable read-only memory EEPROM.
上述说明仅是本发明技术方案的概述，为了能够使得本发明的技术手段更加清楚明白，达到本领域技术人员可依照说明书的内容予以实施的程度，并且为了能够让本发明的上述和其它目的、特征和优点能够更明显易懂，下面以本发明的具体实施方式进行举例说明。The above description is only an overview of the technical solution of the present invention. In order to make the technical means of the present invention clearer, to the extent that those skilled in the art can implement it according to the contents of the description, and to enable the above and other purposes of the present invention, The features and advantages can be more obvious and understandable, and the specific implementation manners of the present invention are illustrated below for illustration.
附图说明Description of drawings
[图1]示出了本发明一个实施例的高分子材料老化的检测方法的步骤示意图。[ Fig. 1 ] A schematic diagram showing steps of a method for detecting aging of a polymer material according to an embodiment of the present invention.
[图2]示出了本发明一个实施例的实施所述高分子材料老化的检测方法的检测系统的结构示意图。[ Fig. 2 ] A schematic structural view showing a detection system for implementing the detection method for aging of polymer materials according to an embodiment of the present invention.
[图3]示出了本发明一个实施例的实施所述高分子材料老化的检测方法的原位反应模块的分解示意图。[ Fig. 3 ] An exploded schematic diagram showing an in-situ reaction module implementing the method for detecting aging of polymer materials according to an embodiment of the present invention.
[图4]示出了本发明一个实施例的实施所述高分子材料老化的检测方法的原位反应模块的气密性对比示意图。[ Fig. 4 ] A schematic diagram showing the airtightness comparison of the in-situ reaction module implementing the detection method for aging of polymer materials according to an embodiment of the present invention.
[图5]示出了本发明又一个实施例的实施所述高分子材料老化的检测方法的吹扫1小时后背景噪音信号与现有技术的对比示意图。[ Fig. 5 ] A schematic diagram showing the comparison of the background noise signal after purging for 1 hour and the prior art in the implementation of the polymer material aging detection method according to another embodiment of the present invention.
[图6]示出了本发明又一个实施例的实施所述高分子材料老化的检测方法的吹扫1小时后背景噪音的稳定性与现有技术的对比示意图。[ Fig. 6 ] A schematic diagram showing the comparison of the stability of the background noise after purging for 1 hour and the prior art in the method for detecting the aging of polymer materials according to another embodiment of the present invention.
符号说明Symbol Description
1 原位反应模块1 in situ reaction module
2 石英本体2 Quartz body
3 红外入射端3 Infrared incident port
4 第一法兰紧固结构4 Fastening structure of the first flange
5 红外入射窗片5 Infrared entrance window
6 红外出射端6 Infrared output port
7 第二法兰紧固结构7 Second flange fastening structure
8 红外出射窗片8 Infrared exit window
9 光照端9 light end
10 光照模块10 light modules
11 第三法兰紧固结构11 Fastening structure of the third flange
12 紫外透过窗片12 UV transparent window
13 样品通过端13 Sample through port
14 环形氟橡胶圈14 Annular Viton ring
15 进气口15 air inlet
16 第一电磁阀16 First solenoid valve
17 充气单元17 Inflatable unit
18 出气口18 air outlet
19 第二电磁阀19 Second solenoid valve
20 抽吸单元20 suction unit
21 承载平台21 carrying platform
22 耦合反应发生单元22 Coupled reaction generation unit
23 加热模块23 heating block
24 湿度模块24 humidity module
25 酸碱度生成模块25 pH Generation Module
26 氧化模块26 oxidation module
27 太阳光模拟器27 Solar Simulator
28 光强传感器28 light intensity sensor
29 加热单元29 heating unit
30 温度传感器30 temperature sensor
31 喷雾器31 sprayer
32 湿度传感器32 Humidity sensor
33 酸碱度发生器33 pH Generator
34 酸碱度检测单元34 pH detection unit
35 氧化单元35 oxidation unit
36 氧化检测单元36 Oxidation detection unit
37 红外光谱检测模块37 Infrared Spectrum Detection Module
38 发光端38 light emitting end
39 检测端39 detection terminal
40 红外入射区域40 Infrared incidence area
41 红外出射区域41 Infrared emission area
42 检测区域42 detection area
43 处理模块43 processing module
44 数据处理单元44 data processing unit
45 计算单元45 computing units
46 评价单元46 Evaluation units
具体实施方式Detailed ways
下面将参照附图更详细地描述本发明的具体实施例。虽然附图中显示了本发明的具体实施例，然而应当理解，可以以各种形式实现本发明而不应被这里阐述的实施例所限制。相反，提供这些实施例是为了能够更透彻地理解本发明，并且能够将本发明的范围完整的传达给本领域的技术人员。Specific embodiments of the present invention will be described in more detail below with reference to the accompanying drawings. Although specific embodiments of the invention are shown in the drawings, it should be understood that the invention may be embodied in various forms and is not limited to the embodiments set forth herein. Rather, these embodiments are provided for more thorough understanding of the present invention and to fully convey the scope of the present invention to those skilled in the art.
需要说明的是，在说明书及权利要求当中使用了某些词汇来指称特定组件。本领域技术人员应可以理解，技术人员可能会用不同名词来称呼同一个组件。本说明书及权利要求并不以名词的差异来作为区分组件的方式，而是以组件在功能上的差异来作为区分的准则。如在通篇说明书及权利要求当中所提及的“包含”或“包括”为一开放式用语，故应解释成“包含但不限定于”。说明书后续描述为实施本发明的较佳实施方式，然所述描述乃以说明书的一般原则为目的，并非用以限定本发明的范围。本发明的保护范围当视所附权利要求所界定者为准。It should be noted that certain terms are used in the specification and claims to refer to specific components. Those skilled in the art should understand that they may use different terms to refer to the same component. The specification and claims do not use differences in nouns as a way of distinguishing components, but use differences in functions of components as a criterion for distinguishing. "Includes" or "comprises" mentioned throughout the specification and claims is an open term, so it should be interpreted as "including but not limited to". The subsequent description in the specification is a preferred implementation mode for implementing the present invention, but the description is for the purpose of the general principles of the specification, and is not intended to limit the scope of the present invention. The scope of protection of the present invention should be defined by the appended claims.
为便于对本发明实施例的理解，下面将结合附图以几个具体实施例为例做进一步的解释说明，且各个附图并不构成对本发明实施例的限定。In order to facilitate the understanding of the embodiments of the present invention, several specific embodiments will be taken as examples for further explanation below in conjunction with the accompanying drawings, and each drawing does not constitute a limitation to the embodiments of the present invention.
具体而言，如图1所示高分子材料老化的检测方法的步骤示意图。一种高分子材料老化的检测方法包括下述步骤：Specifically, a schematic diagram of the steps of the detection method for polymer material aging is shown in FIG. 1 . A detection method for the aging of polymer materials comprises the following steps:
高分子材料样品水平放置在原位反应模块1中，所述原位反应模块1放入红外光谱检测模块37的检测区域42，其中，原位反应模块1的红外入射窗片5和红外出射窗片8形成的第一光路与所述红外光谱检测模块37的发光端38和检测端39形成的第二光路同轴，且红外入射窗片5和所述发光端38形成密封的红外入射区域40，以及所述红外出射窗片8与检测端39形成密封的红外出射区域41，The polymer material sample is placed horizontally in the in-situ reaction module 1, and the in-situ reaction module 1 is put into the detection area 42 of the infrared spectrum detection module 37, wherein the infrared incident window 5 and the infrared exit window of the in-situ reaction module 1 The first optical path formed by the sheet 8 is coaxial with the second optical path formed by the light-emitting end 38 and the detection end 39 of the infrared spectrum detection module 37, and the infrared incident window 5 and the light-emitting end 38 form a sealed infrared incident area 40 , and the infrared emission window 8 and the detection end 39 form a sealed infrared emission region 41,
对所述红外入射区域40和红外出射区域41分别充入吹扫气体进行吹扫，其中，充入的吹扫气体的流速可调节，当吹扫后所述红外入射区域40和红外出射区域41中背景气体含量持续小于第一预定浓度时，即可开始测量；The infrared incidence region 40 and the infrared emission region 41 are respectively filled with purge gas for purging, wherein the flow rate of the charged purge gas can be adjusted, and after purging, the infrared incidence region 40 and the infrared emission region 41 When the background gas content in the medium is continuously less than the first predetermined concentration, the measurement can be started;
打开第一电磁阀16，所述原位反应模块1充入用于与高分子材料反应的反应气体，打开第二电磁阀19，抽吸所述原位反应模块1内的气体，其中，充入和抽吸反应气体的流速分别可调节，当原位反应模块1中反应气体含量达到不小于第二预定浓度时，关闭第一和第二电磁阀；Open the first electromagnetic valve 16, the in-situ reaction module 1 is filled with reaction gas for reacting with the polymer material, open the second electromagnetic valve 19, and suck the gas in the in-situ reaction module 1, wherein the in-situ reaction module 1 is filled with The flow rates of the inlet and suction reaction gases can be adjusted respectively, and when the content of the reaction gas in the in-situ reaction module 1 reaches not less than the second predetermined concentration, the first and second solenoid valves are closed;
光照模块10发出第一预定强度的预定光经由光纤从原位反应模块1的上端照射所述高分子材料样品第一预定时间，和/或，加热模块23对上述高分子材料样品以预定温度加热第二预定时间，高分子材料样品生成气态产物；The illumination module 10 emits predetermined light of a first predetermined intensity to irradiate the polymer material sample for a first predetermined time from the upper end of the in-situ reaction module 1 via an optical fiber, and/or, the heating module 23 heats the above polymer material sample at a predetermined temperature At the second predetermined time, the polymer material sample generates a gaseous product;
预定时间间隔连续检测和采集气态产物的红外光谱信号，其中，红外光谱检测模块37的发光端38发出第二预定强度的红外光沿着第二光路通过红外入射区域40进入原位反应模块1使得红外光按照第一光路穿过所述气态产物，穿过所述气态产物的红外光经由红外出射区域41进入所述检测端39，所述检测端39检测所述气态产物的红外光谱信号，The infrared spectrum signal of the gaseous product is continuously detected and collected at predetermined time intervals, wherein the light-emitting end 38 of the infrared spectrum detection module 37 emits infrared light of a second predetermined intensity and enters the in-situ reaction module 1 through the infrared incident area 40 along the second optical path so that Infrared light passes through the gaseous product according to the first optical path, and the infrared light passing through the gaseous product enters the detection terminal 39 through the infrared emission region 41, and the detection terminal 39 detects the infrared spectrum signal of the gaseous product,
处理模块43将预定时间间隔连续采集的红外光谱信号形成基于时间的谱图组，对比谱图组中预定波长区间内波峰随时间的变化以确定气态产物随时间的浓度变化数据，基于气态产物的浓度变化数据得出高分子材料的老化速率。The processing module 43 forms a time-based spectrogram group from the infrared spectrum signals collected continuously at predetermined time intervals, and compares the changes of peaks in the predetermined wavelength range with time in the spectrogram group to determine the concentration change data of gaseous products over time. The concentration change data yields the aging rate of the polymeric material.
和现有技术相比，本发明所述的高分子材料老化的检测方法可以将原位反应模块1放入红外光谱检测模块37中同时进行背景吹扫和反应气体注入，通过形成密封的红外入射区域40以及红外出射区域，使得进行背景吹扫仅需对所述红外入射区域40和红外出射区域41分别充入吹扫气体进行吹扫，当吹扫后所述红外入射区域40和红外出射区域41中背景气体含量持续小于第一预定浓度时，即可开始测量，显著提高了吹扫质量以及吹扫效率，显著降低了背景噪音且稳定性强，为提高气态产物检测精度奠定了坚实基础，在背景吹扫的同时，可以打开第一电磁阀16充入用于与高分子材料反应的反应气体，当原位反应模块1中反应气体含量达到不小于第二预定浓度时，关闭第一和第二电磁阀，完成反应气体精确注入，缩短了检测周期和提高了检测准确性，本方法通过光照模块10精确可控地照射和/或加热模块23精确可控的加热使得高分子材料样品生成气态产物，第二预定强度的红外光沿着第二光路通过红外入射区域40进入原位反应模块1使得红外光按照第一光路穿过所述气态产物，穿过所述气态产物的红外光经由红外出射区域41进入所述检测端39，第一光路和第二光路同轴进一步提高了检测精度，处理模块43将预定时间间隔连续采集的红外光谱信号形成基于时间的谱图组，对比谱图组中预定波长区间内峰随时间的变化以确定气态产物随时间的浓度变化数据，基于气态产物的浓度变化数据得出高分子材料的老化速率。本发明的方法能够检测0.1-1ppm级的气态产物浓度，得到准确的气态产物的浓度变化数据，显著提高了检测的老化速率的精度。Compared with the prior art, the detection method for polymer material aging described in the present invention can put the in-situ reaction module 1 into the infrared spectrum detection module 37 to perform background purging and reaction gas injection at the same time, by forming a sealed infrared incident Area 40 and the infrared emission area, so that the background purging only needs to be filled with purge gas respectively to the infrared incident area 40 and the infrared emission area 41 for purging. After purging, the infrared incident area 40 and the infrared emission area When the background gas content in 41 is continuously less than the first predetermined concentration, the measurement can be started, which significantly improves the purging quality and purging efficiency, significantly reduces the background noise and has strong stability, and lays a solid foundation for improving the detection accuracy of gaseous products. While the background is being purged, the first electromagnetic valve 16 can be opened to charge the reaction gas used to react with the polymer material, and when the content of the reaction gas in the in-situ reaction module 1 reaches not less than the second predetermined concentration, the first and second solenoid valves are closed. The second solenoid valve completes the precise injection of the reaction gas, shortens the detection period and improves the detection accuracy. In this method, the precise and controllable irradiation of the illumination module 10 and/or the precise and controllable heating of the heating module 23 make the polymer material sample generate For the gaseous product, the infrared light of the second predetermined intensity enters the in-situ reaction module 1 through the infrared incident area 40 along the second optical path so that the infrared light passes through the gaseous product according to the first optical path, and the infrared light passing through the gaseous product passes through The infrared emission area 41 enters the detection end 39, and the first optical path and the second optical path are coaxial to further improve the detection accuracy. The processing module 43 forms a time-based spectrogram group with the infrared spectral signals collected continuously at predetermined time intervals, and compares the spectrograms. The time-dependent change of the peak in the predetermined wavelength range in the group is used to determine the concentration change data of the gaseous product over time, and the aging rate of the polymer material is obtained based on the concentration change data of the gaseous product. The method of the invention can detect the concentration of the gaseous product at the level of 0.1-1ppm, obtain accurate data on the concentration change of the gaseous product, and significantly improve the accuracy of the detected aging rate.
本发明所述的高分子材料老化的检测方法的优选实施例中，光照模块10发出第一预定强度的预定光经由光纤从原位反应模块1的上端照射所述高分子材料样品第一预定时间，加热模块23对上述高分子材料样品以预定温度加热第二预定时间，湿度模块24施加预定湿度到高分子材料样品第三预定时间，酸碱度生成模块25施加预定pH值到高分子材料样品第四预定时间，按照预定条件对高分子材料样品进行若干次光照、加热、加湿和/或酸碱度以生成气态产物。本实施例的方法可以进一步提高光照、加热、加湿和/或酸碱度等耦合反应条件下反应气体和高分子材料样品的反应，提高获得的气态产物的浓度，有利于气态产物浓度的检测。In a preferred embodiment of the detection method for polymer material aging described in the present invention, the illumination module 10 emits a predetermined light of a first predetermined intensity via an optical fiber from the upper end of the in-situ reaction module 1 to irradiate the polymer material sample for a first predetermined time The heating module 23 heats the polymer material sample at a predetermined temperature for a second predetermined time, the humidity module 24 applies a predetermined humidity to the polymer material sample for a third predetermined time, and the pH generating module 25 applies a predetermined pH value to the polymer material sample for a fourth time. At a predetermined time, the polymer material sample is subjected to light, heating, humidification and/or pH several times according to predetermined conditions to generate gaseous products. The method of this embodiment can further improve the reaction between the reaction gas and the polymer material sample under coupling reaction conditions such as light, heating, humidification and/or pH, increase the concentration of the obtained gaseous product, and facilitate the detection of the concentration of the gaseous product.
本发明所述的高分子材料老化的检测方法的优选实施例中，处理模块43基于光照的第一预定强度和第一预定时间，和/或，加热的预定温度和第二预定时间确定高分子材料的老化速率。本实施例的方法进一步根据耦合反应条件进一步提高检测的老化速率的精度。In a preferred embodiment of the method for detecting the aging of polymer materials in the present invention, the processing module 43 determines the polymer material aging based on the first predetermined intensity of light and the first predetermined time, and/or the predetermined temperature of heating and the second predetermined time. The aging rate of the material. The method of this embodiment further improves the accuracy of the detected aging rate according to the coupling reaction conditions.
本发明所述的高分子材料老化的检测方法的优选实施例中，所述红外入射窗片5和所述发光端38形成红外入射区域40以及所述红外出射窗片8与检测端39形成红外出射区域41，所述发光端38设有向红外入射区域40吹扫所述吹扫气体的第一吹扫口且在红外入射区域40形成正压，所述检测端39设有向红外出射区域41吹扫所述吹扫气体的第二吹扫口且在红外出射区域41形成正压，第一吹扫口和第二吹扫口持续吹扫使得背景气体含量保持小于第一预定浓度。本实施例中，通过正压持续吹扫降低背景噪音。In a preferred embodiment of the polymer material aging detection method described in the present invention, the infrared incident window 5 and the light-emitting end 38 form an infrared incident area 40 and the infrared outgoing window 8 and the detection end 39 form an infrared In the exit area 41, the light-emitting end 38 is provided with a first purge port for purging the purge gas to the infrared incident area 40 and forms a positive pressure in the infrared incident area 40, and the detection end 39 is provided with an infrared emission area. 41 purges the second purge port of the purge gas and forms a positive pressure in the infrared emission area 41, and the first purge port and the second purge port are continuously purged so that the background gas content is kept less than the first predetermined concentration. In this embodiment, the background noise is reduced by continuous positive pressure purging.
本发明提供了一种实施所述高分子材料老化的检测方法的检测装置，所述检测装置包括原位反应模块1和红外光谱检测模块37，原位反应模块1包括，The present invention provides a detection device for implementing the detection method for the aging of polymer materials, the detection device includes an in-situ reaction module 1 and an infrared spectrum detection module 37, and the in-situ reaction module 1 includes,
红外入射端3，位于十字通道的水平方向通道的一侧的红外入射端3经由第一法兰紧固结构4密封连接红外入射窗片5，The infrared incident end 3, the infrared incident end 3 located on one side of the horizontal channel of the cross channel is sealed and connected to the infrared incident window 5 through the first flange fastening structure 4,
红外出射端6，位于十字通道的水平方向通道的另一侧的红外出射端6经由第二法兰紧固结构7密封连接红外出射窗片8，红外入射窗片5和红外出射窗片8形成水平的第一光路，Infrared emitting end 6, the infrared emitting end 6 located on the other side of the horizontal channel of the cross channel is sealed and connected to the infrared emitting window 8 through the second flange fastening structure 7, and the infrared incident window 5 and the infrared emitting window 8 are formed horizontal first light path,
其中，第一和/或第二法兰紧固结构的两个连接端面分别设有环形氟橡胶圈14，Wherein, the two connecting end faces of the first and/or second flange fastening structure are respectively provided with annular fluororubber rings 14,
红外光谱检测模块37，其包括，Infrared spectrum detection module 37, which includes,
发光端38，其用于发射红外光，A light-emitting end 38, which is used to emit infrared light,
检测端39，其用于接收和检测穿过原位反应模块1的红外光，发光端38和检测端39形成第二光路，第二光路和所述第一光路同轴，发光端38发出第二预定强度的红外光沿着第二光路通过红外入射区域40进入原位反应模块1使得红外光按照第一光路穿过所述气态产物，穿过所述气态产物的红外光经由红外出射区域41进入所述检测端39，所述检测端39检测所述气态产物的红外光谱信号，The detection end 39 is used to receive and detect the infrared light passing through the in situ reaction module 1, the light emitting end 38 and the detection end 39 form a second optical path, the second optical path is coaxial with the first optical path, and the light emitting end 38 emits the first light path Infrared light with a predetermined intensity enters the in-situ reaction module 1 through the infrared incident area 40 along the second optical path so that the infrared light passes through the gaseous product according to the first optical path, and the infrared light passing through the gaseous product passes through the infrared output area 41 Enter the detection end 39, the detection end 39 detects the infrared spectrum signal of the gaseous product,
检测区域42，用于容纳所述原位反应模块1的检测区域42位于发光端38和检测端39之间，其中，红外入射窗片5和所述发光端38形成密封的红外入射区域40，以及所述红外出射窗片8与检测端39形成密封的红外出射区域41。The detection area 42 is used to accommodate the detection area 42 of the in situ reaction module 1 and is located between the light emitting end 38 and the detection end 39, wherein the infrared incident window 5 and the light emitting end 38 form a sealed infrared incident area 40, And the infrared emission window 8 and the detection end 39 form a sealed infrared emission region 41 .
图2示出了本发明一个实施例的实施所述高分子材料老化的检测方法的检测系统的结构示意图。实施所述高分子材料老化的检测方法的检测系统包括：FIG. 2 shows a schematic structural diagram of a detection system implementing the detection method for aging of polymer materials according to an embodiment of the present invention. The detection system that implements the detection method of described macromolecular material aging comprises:
原位反应模块1，用于在密封环境下提供耦合反应的原位反应模块1包括呈十字形通道的石英本体2，所述石英本体2包括，The in-situ reaction module 1 is used to provide a coupled reaction in a sealed environment. The in-situ reaction module 1 includes a quartz body 2 in a cross-shaped channel, and the quartz body 2 includes,
红外入射端3，位于十字通道的水平方向通道的一侧的红外入射端3经由第一法兰紧固结构4密封连接红外入射窗片5，The infrared incident end 3, the infrared incident end 3 located on one side of the horizontal channel of the cross channel is sealed and connected to the infrared incident window 5 through the first flange fastening structure 4,
红外出射端6，位于十字通道的水平方向通道的另一侧的红外出射端6经由第二法兰紧固结构7密封连接红外出射窗片8，红外入射窗片5和红外出射窗片8形成水平的第一光路，Infrared emitting end 6, the infrared emitting end 6 located on the other side of the horizontal channel of the cross channel is sealed and connected to the infrared emitting window 8 through the second flange fastening structure 7, and the infrared incident window 5 and the infrared emitting window 8 are formed horizontal first light path,
光照端9，位于十字通道的垂直方向通道的上侧的光照端9经由光纤连接光照模块10以垂直向下照射，光照端9经由第三法兰紧固结构11密封连接紫外透过窗片12，Illuminating end 9, the illuminating end 9 located on the upper side of the vertical channel of the cross channel is connected to the illuminating module 10 through an optical fiber to illuminate vertically downward, and the illuminating end 9 is sealed and connected to the ultraviolet transparent window 12 through the third flange fastening structure 11 ,
样品通过端13，位于十字通道的垂直方向通道的下侧的样品通过端13开启和密封以输入样品且保持原位反应模块1形成密封环境，The sample passes through the end 13, and the sample at the lower side of the vertical direction passage of the cross channel is opened and sealed to input the sample and keep the reaction module 1 in situ to form a sealed environment,
其中，第一、第二和/或第三法兰紧固结构的两个连接端面分别设有环形氟橡胶圈14，Wherein, the two connecting end faces of the first, second and/or third flange fastening structures are respectively provided with annular fluororubber rings 14,
进气口15，设在石英本体2侧壁上的进气口15经由第一电磁阀16连接充气单元17以可调节地充入反应气体到原位反应模块1，The air inlet 15, the air inlet 15 provided on the side wall of the quartz body 2 is connected to the gas charging unit 17 via the first solenoid valve 16 to adjustably charge the reaction gas into the in-situ reaction module 1,
出气口18，设在石英本体2侧壁上的出气口18经由第二电磁阀19连接抽吸单元20以可调节地从原位反应模块1中抽出气体，The gas outlet 18, the gas outlet 18 arranged on the side wall of the quartz body 2 is connected to the suction unit 20 via the second electromagnetic valve 19 to adjustably extract the gas from the in-situ reaction module 1,
承载平台21，用于水平承载高分子材料样品的承载平台21位于十字交叉口且位于第一光路下方；The carrying platform 21, the carrying platform 21 for horizontally carrying the polymer material sample is located at the intersection and below the first optical path;
耦合反应发生单元22，其包括设在石英本体2外经由光纤连接的光照模块10、用于以预定温度加热高分子材料样品的加热模块23、施加湿度到高分子材料样品的湿度模块24、施加预定pH值到高分子材料样品的酸碱度生成模块25和/或用于氧化高分子材料样品的氧化模块26，所述光照模块10包括太阳光模拟器27和光强传感器28、所述加热模块1设有加热单元29和温度传感器30、所述湿度模块24包括喷雾器31和湿度传感器32、酸碱度生成模块25包括酸碱度发生器33和酸碱度检测单元34、和/或氧化模块26包括氧化单元35和氧化检测单元36；Coupling reaction generating unit 22, which includes an illumination module 10 arranged outside the quartz body 2 and connected via an optical fiber, a heating module 23 for heating the polymer material sample at a predetermined temperature, a humidity module 24 for applying humidity to the polymer material sample, applying Predetermining the pH value to a pH generation module 25 of a polymer material sample and/or an oxidation module 26 for oxidizing a polymer material sample, the illumination module 10 includes a solar simulator 27 and a light intensity sensor 28, the heating module 1 A heating unit 29 and a temperature sensor 30 are provided, the humidity module 24 includes a sprayer 31 and a humidity sensor 32, the pH generation module 25 includes a pH generator 33 and a pH detection unit 34, and/or the oxidation module 26 includes an oxidation unit 35 and an oxidation unit. detection unit 36;
红外光谱检测模块37，其包括，Infrared spectrum detection module 37, which includes,
发光端38，其用于发射红外光，A light-emitting end 38, which is used to emit infrared light,
检测端39，其用于接收和检测穿过原位反应模块1的红外光，发光端38和检测端39形成第二光路，第二光路和所述第一光路同轴，发光端38发出第二预定强度的红外光沿着第二光路通过红外入射区域40进入原位反应模块1使得红外光按照第一光路穿过所述气态产物，穿过所述气态产物的红外光经由红外出射区域41进入所述检测端39，所述检测端39检测所述气态产物的红外光谱信号，The detection end 39 is used to receive and detect the infrared light passing through the in situ reaction module 1, the light emitting end 38 and the detection end 39 form a second optical path, the second optical path is coaxial with the first optical path, and the light emitting end 38 emits the first light path Infrared light with a predetermined intensity enters the in-situ reaction module 1 through the infrared incident area 40 along the second optical path so that the infrared light passes through the gaseous product according to the first optical path, and the infrared light passing through the gaseous product passes through the infrared output area 41 Enter the detection end 39, the detection end 39 detects the infrared spectrum signal of the gaseous product,
检测区域42，用于容纳所述原位反应模块1的检测区域42位于发光端38和检测端39之间，其中，红外入射窗片5和所述发光端38形成密封的红外入射区域40，以及所述红外出射窗片8与检测端39形成密封的红外出射区域41；The detection area 42 is used to accommodate the detection area 42 of the in situ reaction module 1 and is located between the light emitting end 38 and the detection end 39, wherein the infrared incident window 5 and the light emitting end 38 form a sealed infrared incident area 40, And the infrared emission window 8 and the detection end 39 form a sealed infrared emission region 41;
处理模块43，其一端连接所述光强传感器28、温度传感器30、湿度传感器32、酸碱度检测单元34和/或氧化检测单元36，另一端连接所述第一电磁阀16、第二电磁阀19、红外光谱检测模块37以及光照模块10、加热模块23、湿度模块24、酸碱度发生器33和氧化单元35中的一个或多个，所述处理模块基于接收的数据调节所述原位反应模块1和红外光谱检测模块37获得气态产物且基于气态产物的浓度变化数据得出高分子材料的老化速率。Processing module 43, one end of which is connected to the light intensity sensor 28, temperature sensor 30, humidity sensor 32, pH detection unit 34 and/or oxidation detection unit 36, and the other end is connected to the first solenoid valve 16 and the second solenoid valve 19 , one or more of the infrared spectrum detection module 37 and the illumination module 10, the heating module 23, the humidity module 24, the pH generator 33 and the oxidation unit 35, and the processing module adjusts the in-situ reaction module 1 based on the received data and the infrared spectrum detection module 37 to obtain the gaseous product and obtain the aging rate of the polymer material based on the concentration change data of the gaseous product.
在一个实施例中，图3示出了本发明一个实施例的实施所述高分子材料老化的检测方法的原位反应模块的分解示意图，原位反应模块1由石英材质加工而成，总体形状呈十字形通道，池体下半部分装有可拆卸的圆柱形承载平台，承载平台上方放有直径16mm的铝制样品盘。池体上方和左右两侧端口处采用法兰结构进行密封，每个端口处均加装有石英窗片，池体上方端口处为紫外透过窗片，池体两侧端口处为红外透过窗片，每个窗片两侧均配有O形氟橡胶圈，以保证端口处的密封性能，太阳光模拟器产生的光经由池体外部架设的光纤传导，从池体上方通过窗片照射进入池体内部。红外光谱仪中的单束红外光由池体一侧经窗片入射进入池体，并从池体另一侧经窗片出射后进入检测器。池体侧壁上开设两个通道，每个通道上连接有一个电磁阀，用于控制池体与外界的气体交换。In one embodiment, Fig. 3 shows an exploded schematic view of the in-situ reaction module implementing the method for detecting the aging of polymer materials according to an embodiment of the present invention. The in-situ reaction module 1 is made of quartz material, and its overall shape is It is a cross-shaped channel, and the lower part of the cell body is equipped with a detachable cylindrical bearing platform, and an aluminum sample tray with a diameter of 16mm is placed above the bearing platform. The ports on the top of the cell body and the ports on the left and right sides are sealed with flange structures. Each port is equipped with a quartz window. The port above the cell body is an ultraviolet transparent window, and the ports on both sides of the cell body are infrared transparent. Windows, each window is equipped with O-shaped fluororubber rings on both sides to ensure the sealing performance at the port. The light generated by the solar simulator is conducted through the optical fiber erected outside the pool body, and is irradiated from the top of the pool body through the windows into the pool. A single beam of infrared light in the infrared spectrometer enters the cell from one side of the cell through the window, and exits from the other side of the cell through the window to enter the detector. Two channels are opened on the side wall of the pool body, and each channel is connected with a solenoid valve for controlling gas exchange between the pool body and the outside world.
在一个实施例中，红外光谱检测模块37包括傅里叶变换红外光谱仪，分辨率4cm-1，其采用MCT检测器。In one embodiment, the infrared spectrum detection module 37 includes a Fourier transform infrared spectrometer with a resolution of 4 cm-1, which uses an MCT detector.
在一个实施例中，处理模块43包括：In one embodiment, the processing module 43 includes:
数据处理单元44，其将预定时间间隔连续采集的红外光谱信号形成基于时间的谱图组，A data processing unit 44, which forms a time-based spectrogram group with infrared spectral signals collected continuously at predetermined time intervals,
计算单元45，其对比谱图组中预定波长区间内峰随时间的变化以确定气态产物随时间的浓度变化数据，Calculation unit 45, which compares the changes of peaks in the predetermined wavelength range in the spectrogram group with time to determine the concentration change data of gaseous products with time,
评价单元46，其基于气态产物的浓度变化数据得出高分子材料的老化速率。An evaluation unit 46, which obtains the aging rate of the polymer material based on the concentration change data of the gaseous product.
在一个实施例中，数据处理单元44通过USB数据线连接红外光谱检测模块37，数据处理单元44以固定的时间间隔连续采集数据，保存为谱图组，计算单元45通过对比谱图中某个波长区间内峰随时间的变化来反映原位反应池中某种基团或某种物质的含量随时间的变化情况。In one embodiment, the data processing unit 44 is connected to the infrared spectrum detection module 37 through a USB data cable, and the data processing unit 44 continuously collects data at fixed time intervals, and saves them as a spectrogram group. The change of the peak in the wavelength range with time reflects the change of the content of a certain group or a certain substance in the in-situ reaction cell with time.
在一个实施例中，所述红外入射窗片5和/或红外出射窗片8为CaF2窗片，所述承载平台21可拆卸地连接石英本体2。In one embodiment, the infrared incident window 5 and/or the infrared exit window 8 are CaF2 windows, and the carrying platform 21 is detachably connected to the quartz body 2 .
在一个实施例中，所述充气单元17经由过滤器连接空压机，所述抽吸单元20包括真空泵。空压机提供一定压强的气路输出，经过二氧化碳或水过滤器处理得到不含或含有痕量二氧化碳的干空气，再将干空气接入红外光谱仪后方自带的气路吹扫口，进行红外光路的背景的吹扫。In one embodiment, the inflation unit 17 is connected to an air compressor through a filter, and the suction unit 20 includes a vacuum pump. The air compressor provides a certain pressure of gas path output, and the dry air containing no or trace carbon dioxide is obtained through carbon dioxide or water filter treatment, and then the dry air is connected to the gas path purge port at the rear of the infrared spectrometer for infrared Purge of the background of the light path.
在一个实施例中，光照模块主要由氙灯和快门开关以及光纤组成。氙灯功率150W，光束经光纤传导后，在光纤末端的光强度约42～44mW/cm2。In one embodiment, the lighting module mainly consists of a xenon lamp, a shutter switch and an optical fiber. The power of the xenon lamp is 150W. After the light beam is transmitted through the optical fiber, the light intensity at the end of the optical fiber is about 42-44mW/cm2 .
在一个实施例中，所述检测系统包括控制单元，其连接所述原位反应模块1、红外光谱检测模块37、充气单元17和抽吸单元20。In one embodiment, the detection system includes a control unit, which is connected to the in-situ reaction module 1 , the infrared spectrum detection module 37 , the gas charging unit 17 and the suction unit 20 .
在一个实施例中，处理模块43包括数字信号处理器、专用集成电路ASIC或现场可编程门阵列FPGA，处理模块43包括存储器，所述存储器可以包括一个或多个只读存储器ROM、随机存取存储器RAM、快闪存储器或电子可擦除可编程只读存储器EEPROM。In one embodiment, the processing module 43 includes a digital signal processor, an application specific integrated circuit ASIC or a field programmable gate array FPGA, and the processing module 43 includes a memory, which may include one or more read-only memory ROM, random access Memory RAM, flash memory or electronically erasable programmable read-only memory EEPROM.
在一个实施例中，加热模块23主要由温控仪和加热台构成。加热台置于原位反应池中，集成了陶瓷加热片和Pt-100热电偶，加热台两侧通过打孔的方式加装了钢丝拉环，以方便从池体上方拆卸出来进行维修更换，加热台底部的电路板上焊接有接插连接器，与焊接在池体底部的连接器连接，实现加热信号和温控信号在池体内部的传输。加热台主体材料选用稳定性突出的聚四氟乙烯，以减少测试过程中加热台材料自身的老化。温控仪集成在红外光谱仪样品室外罩的操作面板上，控温精度0.1℃，加热范围为室温-240℃。In one embodiment, the heating module 23 is mainly composed of a temperature controller and a heating platform. The heating table is placed in the in-situ reaction pool, and the ceramic heating plate and Pt-100 thermocouple are integrated. Steel wire pull rings are installed on both sides of the heating table by punching holes to facilitate disassembly from the top of the pool body for maintenance and replacement. The circuit board at the bottom of the heating table is welded with a plug-in connector, which is connected to the connector welded at the bottom of the pool body to realize the transmission of heating signals and temperature control signals inside the pool body. The main material of the heating table is made of polytetrafluoroethylene with outstanding stability to reduce the aging of the heating table material itself during the test. The temperature controller is integrated on the operation panel of the sample chamber cover of the infrared spectrometer, the temperature control accuracy is 0.1°C, and the heating range is room temperature -240°C.
为了进一步理解本发明，因为加工工艺和设计难度的问题，现有技术使用不锈钢的原位反应模块，现有技术采用的不锈钢材质存在以下几个缺陷：一是不锈钢材质不透明，很难从外部观察到内部的情况，因此对于清洗和维护都造成了很大障碍；二是不锈钢材质在加工时表面留下了许多微小的加工纹路，使得原位反应池内壁十分不光滑，使得检测过程中，原位反应模块内壁容易吸附二氧化碳、水等小分子，当温度升高时，这些被吸附的小分子又会解吸附扩散到整个原位反应模块中，对于检测结果的准确性产生较大的影响；三是不锈钢材质本身具有一定的催化活性，在检测过程中加入光照及温度等条件后，极易对原位反应模块内的某些物质产生催化作用，加剧反应池内反应过程的复杂性，难以对检测结果做出有效分析。本发明采用石英材质制作原位反应模块，同时解决了清洗难、易吸附、易催化的问题。In order to further understand the present invention, due to the difficulty of processing technology and design, the prior art uses stainless steel in-situ reaction modules, and the stainless steel material used in the prior art has the following defects: First, the stainless steel material is opaque and difficult to observe from the outside The internal situation caused great obstacles to cleaning and maintenance; second, the stainless steel material left many tiny processing lines on the surface during processing, which made the inner wall of the in-situ reaction pool very rough, so that during the detection process, the original The inner wall of the in-situ reaction module is easy to adsorb small molecules such as carbon dioxide and water. When the temperature rises, these adsorbed small molecules will desorb and diffuse into the entire in-situ reaction module, which will have a greater impact on the accuracy of the test results; The third is that the stainless steel material itself has a certain catalytic activity. After adding light and temperature conditions during the detection process, it is very easy to catalyze some substances in the in-situ reaction module, which aggravates the complexity of the reaction process in the reaction pool and is difficult to detect. Effective analysis of test results. The invention adopts the quartz material to make the in-situ reaction module, and simultaneously solves the problems of difficult cleaning, easy adsorption and easy catalysis.
图4示出了本发明一个实施例的实施所述高分子材料老化的检测方法的原位反应模块的气密性对比示意图。现有技术均采用螺纹紧固的方式进行密封，由于紧固过程中螺帽沿着螺纹旋转带来较大扭矩，会使O形密封圈发生形变而影响密封效果。本申请的法兰紧固结构后由于端口连接处在紧固过程中不存在扭矩，使得O形密封圈可以完好地保持原有的形状，从而保证密封效果。从图4所示的气密性对比示意图中可以看出，在相同条件下，本发明的石英原位反应模块气密性、保压能力远远高于现有技术。本发明提高了密封性能，避免了气密性不足对于数据稳定性及准确性带来的不良影响。Fig. 4 is a schematic diagram showing the comparison of air tightness of the in-situ reaction module implementing the method for detecting aging of polymer materials according to an embodiment of the present invention. In the prior art, the thread fastening method is used for sealing. Since the nut rotates along the thread during the fastening process to bring a large torque, the O-ring will be deformed and the sealing effect will be affected. After the flange structure of the present application is fastened, since there is no torque at the port connection during the fastening process, the O-shaped sealing ring can keep its original shape intact, thereby ensuring the sealing effect. It can be seen from the airtightness comparison schematic diagram shown in FIG. 4 that under the same conditions, the airtightness and pressure holding capacity of the quartz in-situ reaction module of the present invention are much higher than those of the prior art. The invention improves the sealing performance and avoids the adverse effect of insufficient air tightness on data stability and accuracy.
现有技术需要先背景吹扫、然后原位反应模块吹扫，其对整个样品室进行吹扫，吹扫效果很差，即使吹扫一小时，背景噪音依然很强，然后还需要对原位反应模块吹扫。本发明仅需吹扫红外入射区域40和红外出射区域41，达到稳定和降低背景噪音的目的。图5示出了本发明又一个实施例的实施所述高分子材料老化的检测方法的吹扫1小时后背景噪音信号与现有技术的对比示意图，图6示出了本发明又一个实施例的实施所述高分子材料老化的检测方法的吹扫1小时后背景噪音的稳定性与现有技术的对比示意图，如图5和6所示，经过1小时吹扫后，采用本发明得到的背景噪音信号远远小于采用旧方案得到的背景噪音信号，且背景噪音的稳定性有大幅提高，说明本发明的背景吹扫更有效。The existing technology needs to purify the background first, and then purging the in-situ reaction module. It purifies the entire sample chamber, and the purging effect is very poor. Even if it is purged for one hour, the background noise is still very strong, and then the in-situ The reaction module is purged. The present invention only needs to purge the infrared incident region 40 and the infrared emitting region 41 to achieve the purpose of stabilizing and reducing background noise. Fig. 5 shows a schematic diagram of comparison between the background noise signal and the prior art after purging for 1 hour of implementing the polymer material aging detection method according to another embodiment of the present invention, and Fig. 6 shows another embodiment of the present invention The stability of the background noise of the implementation of the detection method of polymer material aging after purging for 1 hour and the contrast schematic diagram of the prior art, as shown in Figures 5 and 6, after purging for 1 hour, adopt the present invention to obtain The background noise signal is much smaller than the background noise signal obtained by adopting the old scheme, and the stability of the background noise is greatly improved, which shows that the background purging of the present invention is more effective.
现有技术中，原位光谱模块和红外光谱检测模块是独立的两部分，必须先在样品室外完成反应气体充入，之后才能将原位光谱模块放入红外光谱检测模块中进行吹扫工作，两项工作无法同时进行。本发明可以吹扫和充入反应气体同时进行且互不干扰，进一步缩短了检测周期。同时，在第一和第二电磁阀的控制下可以方便地将原位光谱模块中的气态产物导出到其他仪器中进行进一步检测，扩展了装置的使用功能。In the prior art, the in-situ spectrum module and the infrared spectrum detection module are two independent parts, and the reaction gas must be filled outside the sample room before the in-situ spectrum module can be put into the infrared spectrum detection module for purging. Two jobs cannot be done at the same time. The invention can carry out purging and charging reaction gas simultaneously without interfering with each other, further shortening the detection period. At the same time, under the control of the first and second electromagnetic valves, the gaseous products in the in-situ spectrum module can be conveniently exported to other instruments for further detection, which expands the use function of the device.
工业实用性Industrial Applicability
本发明的高分子材料老化的检测方法、检测装置及检测系统可以在高分子材料检测领域制造并使用。The polymer material aging detection method, detection device and detection system of the present invention can be manufactured and used in the field of polymer material detection.
尽管以上结合附图对本发明的实施方案进行了描述，但本发明并不局限于上述的具体实施方案和应用领域，上述的具体实施方案仅仅是示意性的、指导性的，而不是限制性的。本领域的普通技术人员在本说明书的启示下和在不脱离本发明权利要求所保护的范围的情况下，还可以做出很多种的形式，这些均属于本发明保护之列。Although the embodiments of the present invention have been described above in conjunction with the accompanying drawings, the present invention is not limited to the above-mentioned specific embodiments and application fields, and the above-mentioned specific embodiments are only illustrative, instructive, and not restrictive . Under the enlightenment of this description and without departing from the protection scope of the claims of the present invention, those skilled in the art can also make many forms, which all belong to the protection of the present invention.
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| CN201810507537.5ACN108956518B (en) | 2018-05-24 | 2018-05-24 | Detection method, detection device and detection system of polymer material aging |
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| CN201810507537.5ACN108956518B (en) | 2018-05-24 | 2018-05-24 | Detection method, detection device and detection system of polymer material aging |
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