CN105675442A - Method for measuring viscosity of substrate support polymer film - Google Patents
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N11/00—Investigating flow properties of materials, e.g. viscosity, plasticity; Analysing materials by determining flow properties
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
本发明提供了一种基底支撑聚合物薄膜黏度的测量方法，首先将基底支撑聚合物薄膜加热并维持温度恒定；然后将测试液体置于所述维持温度恒定的聚合物薄膜表面，形成液滴，并记录放置时间；将聚合物薄膜冷却，除去聚合物薄膜表面的液滴，在所述除去液滴的聚合物薄膜表面的聚合物/液滴/空气三相线处形成润湿脊，测量润湿脊的高度；当所述液滴在聚合物薄膜表面的放置时间大于聚合物薄膜松弛时间时，所述液滴放置时间与所述润湿脊的高度之间具有线性关系，依据其线性关系的斜率可以计算得到聚合物薄膜的黏度。本发明提供的测量方法能够准确的测定基底支撑聚合物薄膜黏度，操作方法简单、成本低、适应性广。
The invention provides a method for measuring the viscosity of a substrate-supported polymer film. Firstly, the substrate-supported polymer film is heated and maintained at a constant temperature; then the test liquid is placed on the surface of the polymer film maintained at a constant temperature to form droplets And record standing time; The polymer film is cooled, removes the liquid drop on the polymer film surface, forms the wetting ridge at the polymer/droplet/air triple line place of the polymer film surface that removes liquid drop, measures wettability The height of the wet ridge; when the placement time of the droplet on the surface of the polymer film is greater than the relaxation time of the polymer film, there is a linear relationship between the drop placement time and the height of the wetting ridge, according to its linear relationship The slope of can be calculated to obtain the viscosity of the polymer film. The measurement method provided by the invention can accurately measure the viscosity of the base support polymer film, and has the advantages of simple operation method, low cost and wide adaptability.
Description
技术领域technical field
本发明涉及测量技术领域，特别涉及一种基底支撑聚合物薄膜黏度的测量方法。The invention relates to the field of measurement technology, in particular to a method for measuring the viscosity of a substrate-supported polymer film.
背景技术Background technique
聚合物的流变性能是指导聚合物材料成型加工的重要基础。黏度(η)是非晶态聚合物的一个极其重要的物性参数，反映了聚合物熔体或者黏弹态高分子发生黏性流动的能力。黏度与材料的力学性能、耐热性、成型和加工性能以及使用寿命密切相关。例如，降低黏度可提高聚合物的加工流动性，充模过程聚合物熔体易于流过狭窄的管道，提高了制品质量，也减小了注塑机、挤出机运转所需能量；高黏度聚合物制品受热不易发生形变，具有较高的热稳定性。同时，黏度是高分子链运动的体现。研究聚合物黏度对于构建聚合物凝聚态体系的结构模型及其分子运动的物理图像也具有非常重要的理论意义。The rheological properties of polymers are an important basis for guiding the molding and processing of polymer materials. Viscosity (η) is an extremely important physical parameter of amorphous polymers, which reflects the viscous flow ability of polymer melt or viscoelastic polymer. Viscosity is closely related to the mechanical properties, heat resistance, molding and processing properties and service life of materials. For example, reducing the viscosity can improve the processing fluidity of the polymer, and the polymer melt can easily flow through the narrow pipe during the filling process, which improves the quality of the product and reduces the energy required for the operation of the injection molding machine and the extruder; high viscosity polymerization The product is not easy to deform when heated, and has high thermal stability. At the same time, viscosity is the embodiment of polymer chain movement. The study of polymer viscosity is also of great theoretical significance for the construction of structural models of polymer condensed matter systems and physical images of molecular motion.
聚合物薄膜被广泛应用于纳米材料领域。以聚合物薄膜作为载体，利用各种微纳米加工技术，可在聚合物薄膜表面制备各种纳米图案化结构，进而制备有机光电材料、微电子器件等纳米功能材料。另外，聚合物薄膜也可直接用作涂层材料应用于封装材料等领域，不仅可以保护底层材料免受外部环境侵蚀，亦可改变材料的耐摩擦性、疏水或疏油性、粘结性等表面性能。聚合物薄膜黏度决定了聚合物纳米材料的制备加工条件以及使用性能。Polymer thin films are widely used in the field of nanomaterials. Using polymer film as a carrier, various nano-patterned structures can be prepared on the surface of polymer film by using various micro-nano processing technologies, and then nano-functional materials such as organic optoelectronic materials and microelectronic devices can be prepared. In addition, polymer films can also be directly used as coating materials in packaging materials and other fields, which can not only protect the underlying material from external environmental erosion, but also change the surface of the material such as friction resistance, hydrophobicity or oleophobicity, and adhesion. performance. The viscosity of polymer films determines the preparation, processing conditions and performance of polymer nanomaterials.
当聚合物薄膜厚度降低至几百纳米以下时，聚合物薄膜的物理化学性质开始与其本体性质发生偏离。厚度越低，偏离的程度越大。聚合物超薄膜的黏度也随着薄膜厚度的降低而发生变化，例如，当温度为340K时，9nm聚苯乙烯薄膜黏度比本体值降低大约三个数量级。聚合物薄膜的黏度是薄膜厚度的函数，不同厚度的薄膜具有不同的黏度。另外，底层材料与聚合物薄膜之间的相互作用也将影响薄膜的黏度值。研究发现，表面钝化的硅基底(H-Si)上聚苯乙烯薄膜黏度比氧化硅基底上的聚苯乙烯薄膜的黏度增大3倍。当底层材料与聚合物薄膜具有较强相互作用时，薄膜的黏度将随膜厚降低而增大。因而，不能简单的将聚合物本体的黏度等同于聚合物薄膜的黏度。When the thickness of the polymer film decreases below a few hundred nanometers, the physicochemical properties of the polymer film begin to deviate from its bulk properties. The lower the thickness, the greater the degree of deviation. The viscosity of polymer ultra-thin film also changes with the decrease of film thickness. For example, when the temperature is 340K, the viscosity of 9nm polystyrene film is about three orders of magnitude lower than the bulk value. The viscosity of polymer films is a function of film thickness, and films of different thicknesses have different viscosities. In addition, the interaction between the underlying material and the polymer film will also affect the viscosity value of the film. It was found that the viscosity of polystyrene film on surface passivated silicon substrate (H-Si) was 3 times higher than that of polystyrene film on silicon oxide substrate. When the underlying material has a strong interaction with the polymer film, the viscosity of the film will increase as the film thickness decreases. Therefore, the viscosity of the polymer body cannot be simply equated with the viscosity of the polymer film.
由于传统的测量本体聚合物黏度及流变性质的方法(如流变仪)并不适用于纳米尺度聚合物薄膜黏度的研究，最近十多年间，研究学者一直致力于开发聚合物薄膜黏度的新测量方法，如通过研究聚合物表面形貌演变测量聚合物薄膜的黏度、通过“纳米鼓泡法(nano-bubbleinflation)”研究聚合物薄膜的黏度、通过研究漂浮在甘油表面聚苯乙烯薄膜“去润湿”动力学研究薄膜黏度的厚度依赖性。然而，目前准确测量聚合物薄膜特别是基底支撑的聚合物薄膜的黏度仍然是学界的一大挑战。Since the traditional methods for measuring the viscosity and rheological properties of bulk polymers (such as rheometers) are not suitable for the study of the viscosity of polymer films at the nanoscale, researchers have been working on developing new methods for the viscosity of polymer films in the past ten years. Measurement methods, such as measuring the viscosity of polymer films by studying the evolution of polymer surface morphology, studying the viscosity of polymer films by "nano-bubble inflation", and studying the "going away" of polystyrene films floating on the surface of glycerin "wetting" kinetics to study the thickness dependence of film viscosity. However, accurate measurement of the viscosity of polymer films, especially those supported by substrates, is still a major challenge in the academic community.
发明内容Contents of the invention
本发明的目的在于提供一种基底支撑聚合物薄膜黏度的测量方法，能够准确测定基底支撑聚合物薄膜的黏度。The purpose of the present invention is to provide a method for measuring the viscosity of a substrate-supported polymer film, which can accurately measure the viscosity of the substrate-supported polymer film.
本发明的技术方案如下：Technical scheme of the present invention is as follows:
本发明提供了一种基底支撑聚合物薄膜黏度的测量方法，包括以下步骤：The invention provides a method for measuring the viscosity of a substrate-supported polymer film, comprising the following steps:
(1)将基底支撑聚合物薄膜加热并维持温度恒定；(1) heating the substrate support polymer film and keeping the temperature constant;
(2)将测试液体置于步骤(1)所述维持温度恒定的聚合物薄膜表面，形成液滴，测定所述液滴在所述聚合物薄膜表面形成的接触角θ值，记录液滴在聚合物薄膜表面的放置时间t；(2) Place the test liquid on the surface of the polymer film that maintains a constant temperature as described in step (1), form a droplet, measure the contact angle θ value that the droplet forms on the surface of the polymer film, and record the drop at The placement time t on the surface of the polymer film;
(3)将步骤(2)中所述聚合物薄膜冷却，除去所述聚合物薄膜表面的液滴，在所述除去液滴的聚合物薄膜表面的聚合物/液滴/空气三相线处形成润湿脊，测量润湿脊的高度h；(3) cooling the polymer film described in step (2), removing the droplets on the surface of the polymer film, at the polymer/droplet/air triple line on the surface of the polymer film where the droplets are removed Form a wetting ridge, measure the height h of the wetting ridge;
(4)改变液滴在聚合物薄膜表面的放置时间t，获得润湿脊的高度h随液滴放置时间t的h～t变化关系；(4) Change the placement time t of the droplet on the surface of the polymer film to obtain the variation relationship between the height h of the wetting ridge and the droplet placement time t from h to t;
当所述液滴在聚合物薄膜表面的放置时间大于聚合物薄膜松弛时间时，所述液滴放置时间与所述润湿脊的高度之间具有式I所示的线性关系；When the placement time of the droplet on the surface of the polymer film is greater than the relaxation time of the polymer film, there is a linear relationship shown in formula I between the droplet placement time and the height of the wetting ridge;
基于式I线性关系的斜率k，根据所述式II计算得到聚合物薄膜的黏度：Based on the slope k of the linear relationship of formula I, the viscosity of the polymer film is calculated according to the formula II:
h＝kt+b式I，h=kt+b formula I,
其中，h—润湿脊的高度，Among them, h—the height of the wetting ridge,
t—液滴在聚合物薄膜表面的放置时间，t—the placement time of the droplet on the surface of the polymer film,
k—斜率，k—slope,
b—截距；b—intercept;
η＝0.37γsinθ/k式II，η=0.37γsinθ/k Formula II,
其中，η—聚合物薄膜的黏度，Among them, η—the viscosity of the polymer film,
γ—液滴的表面张力，γ—the surface tension of the droplet,
θ—液滴与聚合物薄膜表面形成的接触角，θ—the contact angle formed by the droplet on the surface of the polymer film,
k—式I中的斜率。k—the slope in Formula I.
优选的，步骤(1)中所述聚合物薄膜的厚度为10～1000nm。Preferably, the thickness of the polymer film in step (1) is 10-1000 nm.
优选的，步骤(1)中所述聚合物薄膜的厚度为50～500nm。Preferably, the thickness of the polymer film in step (1) is 50-500 nm.
优选的，步骤(1)中所述聚合物薄膜中聚合物为线性聚合物。Preferably, the polymer in the polymer film in step (1) is a linear polymer.
优选的，所述线性聚合物包括聚苯乙烯、聚苯乙烯衍生物、甲基丙烯酸酯类聚合物、聚乙烯基叔丁基醚、聚丙烯腈、聚甲基丙烯腈、聚醋酸乙烯酯、聚苯醚、聚氯乙烯、聚偏二氯乙烯、氟乙烯类聚合物、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚碳酸酯、聚乳酸、尼龙、聚丁二烯、聚异戊二烯、聚砜、聚醚中的一种或几种的共混物，或几种的共聚物。Preferably, the linear polymer includes polystyrene, polystyrene derivatives, methacrylate polymers, polyvinyl tert-butyl ether, polyacrylonitrile, polymethacrylonitrile, polyvinyl acetate, Polyphenylene ether, polyvinyl chloride, polyvinylidene chloride, vinyl fluoride polymers, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polylactic acid, nylon, poly One or more blends of butadiene, polyisoprene, polysulfone, polyether, or several copolymers.
优选的，步骤(1)中所述加热的温度高于聚合物的玻璃化温度。Preferably, the heating temperature in step (1) is higher than the glass transition temperature of the polymer.
优选的，步骤(2)中所述测试液体包括甘油、乙二醇、聚乙二醇齐聚物、聚环氧乙烷齐聚物、二甲基亚砜、N,N-二甲基甲酰胺或离子液体。Preferably, the test liquid described in step (2) includes glycerin, ethylene glycol, polyethylene glycol oligomers, polyethylene oxide oligomers, dimethylsulfoxide, N,N-dimethylmethane amides or ionic liquids.
优选的，所述离子液体包括1-乙基-3-甲基咪唑四氟硼酸盐、1-己基-3-甲基咪唑四氟硼酸盐、1-丁基-3甲基咪唑三氟甲基磺酸盐或1-丁基-3甲基咪唑甲基硫酸盐。Preferably, the ionic liquid includes 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium trifluoroborate Methanesulfonate or 1-butyl-3 methylimidazolium methosulfate.
优选的，步骤(2)中所述液滴的直径为2～7mm。Preferably, the diameter of the droplet in step (2) is 2-7mm.
优选的，步骤(3)中所述冷却是采用冷却介质将所述聚合物薄膜冷却至室温；Preferably, the cooling described in step (3) is to cool the polymer film to room temperature using a cooling medium;
所述冷却介质包括冰袋、液氮、干冰或低温金属板。The cooling medium includes ice packs, liquid nitrogen, dry ice or cryogenic metal plates.
本发明提供了一种基底支撑聚合物薄膜黏度的测量方法，首先将基底支撑聚合物薄膜加热并维持温度恒定；然后将测试液体置于所述维持温度恒定的聚合物薄膜表面，形成液滴，并记录放置时间；将聚合物薄膜冷却，除去聚合物薄膜表面的液滴，在所述除去液滴的聚合物薄膜表面的聚合物/液滴/空气三相线处形成润湿脊，测量润湿脊的高度；改变液滴放置时间，获得润湿脊高度随液滴放置时间的变化关系，当所述液滴在聚合物薄膜表面的放置时间大于聚合物薄膜松弛时间时，所述液滴放置时间与所述润湿脊高度之间具有线性关系，依据其线性关系的斜率可以计算得到聚合物薄膜的黏度。本发明提供的测量方法能够准确的测定基底支撑聚合物薄膜黏度，操作方法简单、成本低、适应性广。The invention provides a method for measuring the viscosity of a substrate-supported polymer film. Firstly, the substrate-supported polymer film is heated and maintained at a constant temperature; then the test liquid is placed on the surface of the polymer film maintained at a constant temperature to form droplets And record standing time; The polymer film is cooled, removes the liquid drop on the polymer film surface, forms the wetting ridge at the polymer/droplet/air triple line place of the polymer film surface that removes liquid drop, measures wettability The height of the wet ridge; change the droplet placement time to obtain the variation relationship of the wetting ridge height with the droplet placement time, when the placement time of the droplet on the surface of the polymer film is greater than the relaxation time of the polymer film, the droplet There is a linear relationship between the standing time and the height of the wetting ridge, and the viscosity of the polymer film can be calculated according to the slope of the linear relationship. The measurement method provided by the invention can accurately measure the viscosity of the base support polymer film, and has the advantages of simple operation method, low cost and wide adaptability.
附图说明Description of drawings
图1为本发明实施例1中PS薄膜表面润湿脊的形貌图；Fig. 1 is the morphology figure of wetting ridge on the surface of PS film in Example 1 of the present invention;
图2为本发明实施例1中PS薄膜表面润湿脊形貌的横截面图；Figure 2 is a cross-sectional view of the wetting ridge morphology on the surface of the PS film in Example 1 of the present invention;
图3为本发明实施例1中不同液滴放置时间下PS薄膜表面润湿脊形貌的横截面图；3 is a cross-sectional view of the wetting ridge morphology on the surface of the PS film under different droplet placement times in Example 1 of the present invention;
图4为本发明实施例1中PS薄膜表面润湿脊的高度与液滴放置时间的h～t关系图；Fig. 4 is the relationship diagram of h~t between the height of the wetting ridge on the surface of the PS film and the droplet placement time in Example 1 of the present invention;
图5为本发明实施例2中PS薄膜表面润湿脊的高度与液滴放置时间的h～t关系图；Fig. 5 is a h-t relationship diagram between the height of the wetting ridge on the surface of the PS film and the droplet placement time in Example 2 of the present invention;
图6为本发明实施例3中PS薄膜表面润湿脊的高度与液滴放置时间的h～t关系图；Fig. 6 is a h-t relationship diagram between the height of the wetting ridge on the surface of the PS film and the placement time of the droplet in Example 3 of the present invention;
图7为利用本发明测量方法测得本发明实施例3中PS薄膜黏度与文献值的比较图；Fig. 7 is the comparative figure of PS film viscosity and literature value in the embodiment of the present invention 3 measured by the measuring method of the present invention;
图8为本发明实施例4中PS薄膜表面润湿脊的高度与液滴放置时间的h～t关系图；Fig. 8 is a graph showing the h-t relationship between the height of the wetting ridge on the surface of the PS film and the droplet placement time in Example 4 of the present invention;
图9为本发明实施例5中PS薄膜表面润湿脊的高度与液滴放置时间的h～t关系图；Fig. 9 is a graph showing the h-t relationship between the height of the wetting ridge on the surface of the PS film and the droplet placement time in Example 5 of the present invention;
图10为本发明实施例6中PS薄膜表面润湿脊的高度与液滴放置时间的h～t关系图；Fig. 10 is a graph showing the h-t relationship between the height of the wetting ridge on the surface of the PS film and the droplet placement time in Example 6 of the present invention;
图11为本发明实施例7中不同基底的PS薄膜黏度与PS薄膜厚度的关系图。11 is a graph showing the relationship between the viscosity of PS films and the thickness of PS films on different substrates in Example 7 of the present invention.
具体实施方式detailed description
本发明提供了一种基底支撑聚合物薄膜黏度的测量方法，包括以下步骤：The invention provides a method for measuring the viscosity of a substrate-supported polymer film, comprising the following steps:
(1)将基底支撑聚合物薄膜加热并维持温度恒定；(1) heating the substrate support polymer film and keeping the temperature constant;
(2)将测试液体置于步骤(1)所述维持温度恒定的聚合物薄膜表面，形成液滴，测定所述液滴在所述聚合物薄膜表面形成的接触角θ值，记录液滴在聚合物薄膜表面放置时间t；(2) Place the test liquid on the surface of the polymer film that maintains a constant temperature as described in step (1), form a droplet, measure the contact angle θ value that the droplet forms on the surface of the polymer film, and record the drop at The time t on the surface of the polymer film;
(3)将步骤(2)中所述聚合物薄膜冷却，除去所述聚合物薄膜表面的液滴，在所述除去液滴的聚合物薄膜表面的聚合物/液滴/空气三相线处形成润湿脊，测量润湿脊的高度h；(3) cooling the polymer film described in step (2), removing the droplets on the surface of the polymer film, at the polymer/droplet/air triple line on the surface of the polymer film where the droplets are removed Form a wetting ridge, measure the height h of the wetting ridge;
(4)改变液滴在聚合物薄膜表面的放置时间t，获得润湿脊的高度h随液滴放置时间t的h～t变化关系；(4) Change the placement time t of the droplet on the surface of the polymer film to obtain the variation relationship between the height h of the wetting ridge and the droplet placement time t from h to t;
当所述液滴在聚合物薄膜表面的放置时间大于聚合物薄膜松弛时间时，所述液滴放置时间与所述润湿脊的高度之间具有式I所示的线性关系；When the placement time of the droplet on the surface of the polymer film is greater than the relaxation time of the polymer film, there is a linear relationship shown in formula I between the droplet placement time and the height of the wetting ridge;
基于式I线性关系的斜率k，根据所述式II计算得到聚合物薄膜的黏度：Based on the slope k of the linear relationship of formula I, the viscosity of the polymer film is calculated according to the formula II:
h＝kt+b式I，h=kt+b formula I,
其中，h—润湿脊的高度，Among them, h—the height of the wetting ridge,
t—液滴在聚合物薄膜表面的放置时间，t—the placement time of the droplet on the surface of the polymer film,
k—斜率，k—slope,
b—截距；b—intercept;
η＝0.37γsinθ/k式II，η=0.37γsinθ/k Formula II,
其中，η—聚合物薄膜的黏度，Among them, η—the viscosity of the polymer film,
γ—液滴的表面张力，γ—the surface tension of the droplet,
θ—液滴与聚合物薄膜表面形成的接触角，θ—the contact angle formed by the droplet on the surface of the polymer film,
k—式I中的斜率。k—the slope in Formula I.
本发明对于测定对象没有特殊的限定，采用本领域技术人员熟知的基底支撑聚合物薄膜即可。在本发明中，所述聚合物薄膜的厚度优选为10～1000nm，更优选为50～500nm。In the present invention, there is no special limitation on the measurement object, and a substrate-supporting polymer film well known to those skilled in the art can be used. In the present invention, the thickness of the polymer film is preferably 10-1000 nm, more preferably 50-500 nm.
在本发明中，所述聚合物薄膜中聚合物优选为线性聚合物。在本发明中，所述线性聚合物优选包括聚苯乙烯及其衍生物、甲基丙烯酸酯类聚合物、聚乙烯基叔丁基醚、聚丙烯腈、聚甲基丙烯腈、聚醋酸乙烯酯、聚苯醚、聚氯乙烯、聚偏二氯乙烯、氟乙烯类聚合物、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚碳酸酯、聚乳酸、尼龙、聚丁二烯、聚异戊二烯、聚砜、聚醚中的一种或几种的共混物，或几种的共聚物。In the present invention, the polymer in the polymer film is preferably a linear polymer. In the present invention, the linear polymer preferably includes polystyrene and its derivatives, methacrylate polymers, polyvinyl tert-butyl ether, polyacrylonitrile, polymethacrylonitrile, polyvinyl acetate , polyphenylene ether, polyvinyl chloride, polyvinylidene chloride, vinyl fluoride polymers, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polylactic acid, nylon, One or more blends of polybutadiene, polyisoprene, polysulfone, polyether, or several copolymers.
本发明优选在基底上制备平整的聚合物薄膜，得到基底支撑聚合物薄膜。在本发明中，所述基底不与所述聚合物发生化学反应，仅是物理结合。在本发明中，所述基底优选采用表面平整、易于传热的材料。在本发明中，所述基底的材质优选包括玻璃片、硅片、蓝宝石、云母、铁、铜或铝。The present invention preferably prepares a flat polymer film on a substrate to obtain a substrate-supported polymer film. In the present invention, the substrate does not chemically react with the polymer, but is only physically bonded. In the present invention, the substrate is preferably made of a material with a smooth surface and easy heat transfer. In the present invention, the material of the substrate preferably includes glass sheet, silicon sheet, sapphire, mica, iron, copper or aluminum.
本发明对于所述平整的聚合物薄膜的制备方法没有特殊的限定，采用本领域技术人员熟知的制备聚合物薄膜的技术方案即可。在本发明中，制备所述平整的聚合物薄膜的方法优选包括流延法、旋涂法或浸涂法。In the present invention, there is no special limitation on the preparation method of the flat polymer film, and the technical solution for preparing the polymer film well-known to those skilled in the art can be adopted. In the present invention, the method of preparing the flat polymer film preferably includes a casting method, a spin coating method or a dip coating method.
本发明对于将基底支撑聚合物薄膜加热并维持温度恒定所采用的方式没有特殊限定，采用本领域技术人员熟知的用于加热并维持温度恒定的技术方案即可。本发明优选采用精密控温热台对所述基底支撑聚合物薄膜加热并维持温度恒定。在本发明中，所述精密控温热台的控温精度优选为±1℃。在本发明中，所述加热的温度优选高于聚合物的玻璃化温度。In the present invention, there is no special limitation on the method of heating and maintaining the temperature of the substrate-supporting polymer film, and a technical solution for heating and maintaining a constant temperature known to those skilled in the art can be used. In the present invention, it is preferred to use a precise temperature-controlled heating stage to heat the substrate-supporting polymer film and keep the temperature constant. In the present invention, the temperature control accuracy of the precise temperature control hot stage is preferably ±1°C. In the present invention, the heating temperature is preferably higher than the glass transition temperature of the polymer.
完成将基底支撑聚合物薄膜加热并维持温度恒定后，本发明将测试液体置于所述维持温度恒定的聚合物薄膜表面，形成液滴，并记录放置时间t。在本发明中，所述测试液体优选满足以下三个条件：After heating the base support polymer film and keeping the temperature constant, the present invention places the test liquid on the surface of the polymer film maintained at a constant temperature to form droplets, and records the standing time t. In the present invention, the test liquid preferably satisfies the following three conditions:
(a)具有较低的挥发速率，在测量过程中由于液体挥发所导致液滴接触角减小值小于5°；(a) have a lower volatilization rate, and the droplet contact angle decrease value is less than 5° due to liquid volatilization during the measurement process;
(b)具有较高的表面张力，在所述聚合物薄膜表面形成大于30°的接触角；(b) have a higher surface tension, forming a contact angle greater than 30° on the surface of the polymer film;
(c)与所述聚合物热力学不相容，在测量过程中测试液体不会渗透入聚合物内部，不会对聚合物产生增塑效应。(c) Thermodynamically incompatible with the polymer in question, the test liquid does not penetrate into the interior of the polymer during the measurement and does not have a plasticizing effect on the polymer.
在本发明中，所述测试液体优选包括甘油、乙二醇、聚乙二醇齐聚物、聚环氧乙烷齐聚物、二甲基亚砜、N,N-二甲基甲酰胺或离子液体；所述离子液体优选包括1-乙基-3-甲基咪唑四氟硼酸盐、1-己基-3-甲基咪唑四氟硼酸盐、1-丁基-3甲基咪唑三氟甲基磺酸盐或1-丁基-3甲基咪唑甲基硫酸盐。In the present invention, the test liquid preferably includes glycerin, ethylene glycol, polyethylene glycol oligomer, polyethylene oxide oligomer, dimethylsulfoxide, N,N-dimethylformamide or Ionic liquid; said ionic liquid preferably includes 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium trifluoroborate Fluoromethylsulfonate or 1-butyl-3-methylimidazolium methosulfate.
液滴直径大小会影响测量结果的精确度，在本发明中，所述液滴的直径优选为2～7mm。在本发明的实施例中，利用德国Kruss公司生产的DSA10-MK2型接触角测试仪获得所述液滴的直径。The diameter of the droplet will affect the accuracy of the measurement result. In the present invention, the diameter of the droplet is preferably 2-7mm. In the embodiment of the present invention, the diameter of the droplet is obtained by using a DSA10-MK2 contact angle tester produced by Kruss, Germany.
本发明对于测定所述液滴与所述聚合物薄膜表面形成的接触角θ值的方法没有特殊的限定，采用本领域技术人员熟知的测定所述液滴与所述聚合物薄膜表面形成的接触角θ值的技术方案即可。本发明优选采用标准化仪器测量所述液滴与所述聚合物薄膜表面形成的接触角θ值。在本发明的实施例中，采用德国Kruss公司生产的DSA10-MK2型液滴形状分析仪测量所述液滴与所述聚合物薄膜表面形成的接触角θ值。In the present invention, there is no special limitation on the method for measuring the contact angle θ value formed between the droplet and the surface of the polymer film. The technical scheme of the angle θ value is enough. In the present invention, a standardized instrument is preferably used to measure the value of the contact angle θ formed between the droplet and the surface of the polymer film. In the embodiment of the present invention, the DSA10-MK2 droplet shape analyzer produced by Kruss Company in Germany is used to measure the contact angle θ value formed between the droplet and the surface of the polymer film.
本发明将所述液滴在所述维持温度恒定的聚合物薄膜表面放置时间t后，将所述聚合物薄膜冷却，除去所述聚合物薄膜表面的液滴，所述除去液滴的聚合物薄膜表面的聚合物/液滴/空气三相线处形成润湿脊，测量润湿脊的高度h。在本发明中，所述冷却优选采用冷却介质将所述聚合物薄膜冷却至室温；所述冷却介质优选包括冰袋、干冰、液氮或低温金属板。在本发明中，使用冷却介质能够实现快速冷却所述聚合物薄膜，以保证测量结果的准确性。In the present invention, after the liquid droplets are placed on the surface of the polymer film that maintains a constant temperature for a time t, the polymer film is cooled to remove the liquid droplets on the surface of the polymer film, and the polymer that removes the liquid droplets A wetting ridge is formed at the polymer/droplet/air triple line on the surface of the film, and the height h of the wetting ridge is measured. In the present invention, the cooling preferably uses a cooling medium to cool the polymer film to room temperature; the cooling medium preferably includes an ice pack, dry ice, liquid nitrogen or a low-temperature metal plate. In the present invention, the polymer film can be rapidly cooled by using a cooling medium to ensure the accuracy of the measurement results.
在本发明中，将所述聚合物薄膜进行冷却后，除去所述聚合物薄膜表面的液滴。本发明对于所述除去聚合物薄膜表面的液滴的方法没有特殊的限定，采用本领域技术人员熟知的除去聚合物薄膜表面的液滴的技术方案即可。本发明优选采用滤纸将聚合物薄膜表面的液滴吸净。In the present invention, after the polymer film is cooled, the liquid droplets on the surface of the polymer film are removed. In the present invention, there is no special limitation on the method for removing the liquid droplets on the surface of the polymer film, and the technical solution for removing the liquid droplets on the surface of the polymer film known to those skilled in the art can be adopted. In the present invention, filter paper is preferably used to absorb the liquid droplets on the surface of the polymer film.
在本发明中，除去所述聚合物薄膜表面的液滴后，所述除去液滴的聚合物薄膜表面的聚合物/液滴/空气三相线处形成润湿脊，测量润湿脊的高度h。由于液滴表面张力垂直分量的作用，在所述聚合物薄膜表面的聚合物/液滴/空气三相线处产生高度为数十纳米至数微米的山脊状的突起形变，所述形变称为润湿脊，英文名为wettingridge。本发明对于所述测量润湿脊的高度h的方法没有特殊的限定，采用本领域技术人员熟知的测量润湿脊的高度h的技术方案即可。本发明优选将除去液滴的聚合物薄膜放置于原子力显微镜(AFM)测试平台上，利用AFM测得所述除去液滴的聚合物薄膜表面的润湿脊的形貌图以及润湿脊形貌的横截面图，从润湿脊形貌的横截面图上得到润湿脊的高度h。In the present invention, after the droplets on the surface of the polymer film are removed, a wetting ridge is formed at the polymer/droplet/air triple line on the surface of the polymer film from which the droplets are removed, and the height of the wetting ridge is measured h. Due to the effect of the vertical component of the surface tension of the droplet, a ridge-like protrusion deformation with a height of tens of nanometers to several microns is generated at the polymer/droplet/air triple line on the surface of the polymer film, and the deformation is called Wetting ridge, the English name is wettingridge. The present invention has no special limitation on the method for measuring the height h of the wetting ridge, and a technical solution for measuring the height h of the wetting ridge well known to those skilled in the art can be used. In the present invention, the polymer film from which droplets have been removed is preferably placed on an atomic force microscope (AFM) test platform, and the topography and wetting ridge morphology of the wetting ridges on the surface of the polymer film from which droplets have been removed are measured by AFM From the cross-sectional view of the wetting ridge topography, the height h of the wetting ridge is obtained.
在本发明中，改变液滴在聚合物薄膜表面的放置时间t，获得润湿脊的高度h随液滴放置时间t的h～t变化关系；In the present invention, by changing the placement time t of the droplet on the surface of the polymer film, the relationship between the height h of the wetting ridge and the droplet placement time t from h to t is obtained;
当所述液滴在聚合物薄膜表面的放置时间大于聚合物薄膜松弛时间时，所述液滴放置时间与所述润湿脊的高度之间具有式I所示的线性关系；When the placement time of the droplet on the surface of the polymer film is greater than the relaxation time of the polymer film, there is a linear relationship shown in formula I between the droplet placement time and the height of the wetting ridge;
基于式I线性关系的斜率k，根据所述式II计算得到聚合物薄膜的黏度：Based on the slope k of the linear relationship of formula I, the viscosity of the polymer film is calculated according to the formula II:
h＝kt+b式I，h=kt+b formula I,
其中，h—润湿脊的高度，Among them, h—the height of the wetting ridge,
t—液滴在聚合物薄膜表面的放置时间，t—the placement time of the droplet on the surface of the polymer film,
k—斜率，k—slope,
b—截距；b—intercept;
η＝0.37γsinθ/k式II，η=0.37γsinθ/k Formula II,
其中，η—聚合物薄膜的黏度，Among them, η—the viscosity of the polymer film,
γ—液滴的表面张力，γ—the surface tension of the droplet,
θ—液滴与聚合物薄膜表面形成的接触角，θ—the contact angle formed by the droplet on the surface of the polymer film,
k—式I中的斜率。k—the slope in Formula I.
本发明对于测定式II中所述液滴的表面张力γ的方法没有特殊的限定，采用本领域技术人员熟知的测定液滴的表面张力γ的技术方案即可。本发明优选通过查阅文献得到液滴的表面张力γ或采用吊片法测定液滴的表面张力γ。In the present invention, there is no special limitation on the method for measuring the surface tension γ of the liquid droplet described in formula II, and the technical solution for measuring the surface tension γ of the liquid droplet well known to those skilled in the art can be used. In the present invention, it is preferred to obtain the surface tension γ of the droplet by consulting the literature or measure the surface tension γ of the droplet by using the hanging sheet method.
采用本发明提供的测量方法能够准确的测定基底支撑聚合物薄膜黏度，且操作方法简单、成本低、适应性广。The measurement method provided by the invention can accurately measure the viscosity of the substrate supporting polymer film, and has the advantages of simple operation method, low cost and wide adaptability.
下面将结合本发明中的实施例，对本发明中的技术方案进行清楚、完整地描述。显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions in the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Apparently, the described embodiments are only some of the embodiments of the present invention, but not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.
实施例1Example 1
首先，选取厚度约为600nm的聚合物薄膜，在此厚度下，聚合物薄膜的黏度与本体一致。利用本专利方案测量此聚合物薄膜的黏度，并将其与文献报道的采用其它方法获得的聚合物薄膜的黏度数值进行比较，以确定本方案的可行性。First, select a polymer film with a thickness of about 600nm. Under this thickness, the viscosity of the polymer film is consistent with that of the bulk. The viscosity of the polymer film is measured by the patented scheme, and compared with the viscosity value of the polymer film obtained by other methods reported in the literature, so as to determine the feasibility of the scheme.
(1)利用旋涂成膜方法，将聚苯乙烯(PS，重均分子量为1070kg/mol)的甲苯溶液旋涂在表面含有SiO2氧化层的硅片(SiO2-Si)基底上，制备厚度为600nm的PS薄膜；将PS薄膜置于160℃的精密控温热台上，并维持PS薄膜温度恒定。(1) Spin coating a toluene solution of polystyrene (PS, with a weight average molecular weight of 1070kg/mol) on a silicon wafer (SiO 2 -Si) substrate with an SiO 2 oxide layer on the surface to prepare A PS film with a thickness of 600nm; place the PS film on a precision temperature-controlled hot stage at 160°C, and keep the temperature of the PS film constant.
(2)将1-乙基-3-甲基咪唑四氟硼酸盐([EIm]BF4)放置于步骤(1)中所述PS薄膜表面，形成液滴，所述液滴的表面张力γ＝55mN/m，利用德国Kruss公司生产的DSA10-MK2型接触角测试仪测定所述液滴的直径为2mm以及所述液滴与所述聚合物薄膜表面形成的接触角θ＝78°。(2) 1-ethyl-3-methylimidazolium tetrafluoroborate ([EIm]BF4) is placed on the surface of the PS film described in step (1) to form a droplet, the surface tension of the droplet γ =55mN/m, using the DSA10-MK2 contact angle tester produced by German Kruss company to measure the diameter of the droplet to be 2mm and the contact angle θ=78° formed between the droplet and the surface of the polymer film.
(3)液滴在聚合物薄膜表面放置时间t后，利用5℃的不锈钢板冷却步骤(2)中所述PS薄膜至室温，利用滤纸吸净所述PS薄膜表面的液滴，所述除去液滴的PS薄膜表面的聚合物/液滴/空气三相线处形成润湿脊，利用美国Bruker生产的Multimode-8型原子力显微镜(AFM)测得所述润湿脊的形貌图(见图1)以及润湿脊形貌的横截面图(见图2)；从润湿脊形貌的横截面图上得到润湿脊的高度h。(3) After the droplet is placed on the surface of the polymer film for a time t, use a stainless steel plate at 5°C to cool the PS film described in step (2) to room temperature, and use filter paper to absorb the droplet on the surface of the PS film. Wetting ridges are formed at the polymer/droplet/air triple-phase line on the PS film surface of the droplets, and the Multimode-8 atomic force microscope (AFM) produced by U.S. Bruker is used to measure the topography of the wetting ridges (see Fig. 1) and the cross-sectional view of the wetting ridge topography (see Fig. 2); the height h of the wetting ridge is obtained from the cross-sectional view of the wetting ridge topography.
(4)改变液滴放置时间t，获得一系列润湿脊形貌的横截面图，见图3。以润湿脊的高度h对液滴放置时间t作图，从图4中可以看出，当液滴放置时间大于10000秒后，润湿脊的高度随液滴放置时间增加而线性增大。对放置时间大于10000秒的数据进行线性拟合，可得到h～t线性关系的斜率k＝2.46×10- 11m/s。(4) Change the droplet placement time t to obtain a series of cross-sectional views of the wetting ridge morphology, as shown in Fig. 3 . The height h of the wetting ridge is plotted against the droplet placement time t. It can be seen from Figure 4 that when the droplet placement time is greater than 10,000 seconds, the height of the wetting ridge increases linearly with the droplet placement time. Linear fitting is performed on the data stored for more than 10,000 seconds, and the slope k=2.46×10 - 11 m/s of the linear relationship between h and t can be obtained.
根据式II计算得到在160℃下，重均分子量为1070kg/mol的PS薄膜的黏度η＝8.1×108Pa·s。According to formula II, the viscosity of PS film with a weight average molecular weight of 1070kg/mol at 160°C is η=8.1×108Pa·s.
通过查阅文献，文献(Plazek,D.J.；O'Rourke,V.M.J.Polym.Sci,A:Polym.Phys.1971,9,209–243)记载，重均分子量为1070kg/mol的PS在160℃下的黏度值为1.84×109Pa·s。两者之间的偏差小于一个数量级，在系统误差的范围内，证实了本发明测量方法的可行性。By consulting the literature, the literature (Plazek, D.J.; O'Rourke, V.M.J. Polym.Sci, A: Polym.Phys.1971, 9, 209–243) records that the viscosity value of PS with a weight average molecular weight of 1070kg/mol at 160°C is 1.84×109Pa·s. The deviation between the two is less than an order of magnitude, within the range of systematic error, which proves the feasibility of the measurement method of the present invention.
实施例2Example 2
按照实施例1相同的方法，制备重均分子量为442kg/mol的PS薄膜，并维持所述PS薄膜的温度为170℃。将1-己基-3-甲基咪唑四氟硼酸盐([HIm]BF4)放置在PS薄膜表面形成液滴，[HIm]BF4液滴的表面张力为35mN/m，[HIm]BF4液滴与PS薄膜表面形成的接触角为51°。对PS薄膜表面润湿脊的高度随液滴放置时间增加而发生的变化的关系进行测定，从图5中可以看出，当时间大于2000秒后，润湿脊高度与液滴放置时间呈线性关系，其斜率k＝1.95×10- 10m/s。根据式II计算得到在170℃下，重均分子量为442kg/mol的PS薄膜的黏度η＝5.2×107Pa·s。Following the same method as in Example 1, a PS film with a weight average molecular weight of 442 kg/mol was prepared, and the temperature of the PS film was maintained at 170°C. Place 1-hexyl-3-methylimidazolium tetrafluoroborate ([HIm]BF4) on the surface of PS film to form droplets, the surface tension of [HIm]BF4 droplets is 35mN/m, [HIm]BF4 droplets The contact angle formed with the PS film surface is 51°. The relationship between the height of the wetting ridge on the surface of the PS film and the droplet placement time was measured. It can be seen from Figure 5 that when the time is greater than 2000 seconds, the height of the wetting ridge is linear with the droplet placement time Relationship, its slope k=1.95×10 - 10 m/s. According to formula II, the viscosity η of the PS film with a weight average molecular weight of 442kg/mol at 170°C is 5.2×107Pa·s.
通过查阅文献，文献(Plazek,D.J.；O'Rourke,V.M.J.Polym.Sci,A:Polym.Phys.1971,9,209–243)记载，重均分子量为442kg/mol的PS在170℃下的黏度值为2.4×107Pa·s。两者之间的偏差小于一个数量级，在系统误差的范围内，进一步证实了本发明测量方法的可行性。By consulting the literature, the literature (Plazek, D.J.; O'Rourke, V.M.J. Polym.Sci, A: Polym.Phys.1971, 9, 209–243) records that the viscosity value of PS with a weight average molecular weight of 442kg/mol at 170°C is 2.4×107 Pa·s. The deviation between the two is less than an order of magnitude, within the range of systematic error, further confirming the feasibility of the measurement method of the present invention.
实施例3Example 3
按照实施例1相同的方法，维持所述PS薄膜的温度为170℃、180℃以及200℃。测量不同温度下，PS薄膜表面润湿脊高度随液滴放置时间的变化，得到不同温度下的h～t关系线，见图6；并获得不同温度下h～t关系的斜率k。从图6可以看出，170℃时k＝5.9×10- 11m/s，180℃时k＝9.7×10- 11m/s，200℃时k＝4.2×10- 10m/s。根据式II计算得到在170℃、180℃以及200℃下，重均分子量为1070kg/mol的PS薄膜的黏度η分别为3.4×108Pa·s、2.0×108Pa·s以及4.7×107Pa·s。Following the same method as in Example 1, the temperature of the PS film was maintained at 170°C, 180°C and 200°C. At different temperatures, the change of the wetting ridge height on the surface of the PS film with the droplet placement time is obtained, and the h-t relationship line at different temperatures is obtained, as shown in Figure 6; and the slope k of the h-t relationship at different temperatures is obtained. It can be seen from Figure 6 that k=5.9×10-11 m / s at 170°C, k=9.7× 10-11 m / s at 180°C, and k=4.2 × 10-10 m / s at 200°C. According to formula II, the viscosity η of the PS film with a weight average molecular weight of 1070kg/mol at 170°C, 180°C and 200°C is 3.4×108Pa·s, 2.0×108Pa·s and 4.7×107Pa·s respectively.
从图7可以看出，利用本发明测量方法所测不同温度下PS薄膜的黏度与文献(Plazek,D.J.；O'Rourke,V.M.J.Polym.Sci,A:Polym.Phys.1971,9,209–243)的记载基本一致。As can be seen from Figure 7, the viscosity of the PS film under different temperatures measured by the measurement method of the present invention is consistent with that of the literature (Plazek, D.J.; O'Rourke, V.M.J.Polym.Sci, A: Polym.Phys.1971,9,209-243) The records are basically the same.
实施例4Example 4
按照实施例1相同的方法，制备重均分子量为168kg/mol的PS薄膜，并维持所述PS薄膜的温度为130℃、140℃、145℃以及150℃。测量不同温度下，PS薄膜表面润湿脊高度随液滴放置时间的变化，得到不同温度下的h～t关系线，见图8；并获得不同温度下h～t关系的斜率k。从图8可以看出，温度为130℃、140℃、145℃以及150℃时对应的斜率k分别为4.6×10- 11m/s、1.3×10- 10m/s、6.8×10- 10m/s以及1.7×10- 9m/s。根据式II计算得到在130℃、140℃、145℃以及150℃下，重均分子量为168kg/mol的PS薄膜的黏度η分别为4.3×108Pa·s、1.5×108Pa·s、2.9×107Pa·s以及1.2×107Pa·s。Following the same method as in Example 1, a PS film with a weight average molecular weight of 168 kg/mol was prepared, and the temperature of the PS film was maintained at 130°C, 140°C, 145°C and 150°C. Measure the change of the wetting ridge height on the surface of PS film with the droplet placement time at different temperatures, and obtain the h-t relationship line at different temperatures, as shown in Figure 8; and obtain the slope k of the h-t relationship at different temperatures. It can be seen from Figure 8 that the corresponding slopes k at 130°C, 140°C, 145°C and 150°C are 4.6×10 - 11 m/s, 1.3×10 - 10 m/s, 6.8×10 - 10 m/s and 1.7×10 - 9 m/s. According to formula II, at 130°C, 140°C, 145°C and 150°C, the viscosity η of the PS film with a weight average molecular weight of 168kg/mol is 4.3×108Pa·s, 1.5×108Pa·s, 2.9×107Pa·s, respectively. s and 1.2×107Pa·s.
实施例5Example 5
按照实施例1相同的方法，制备重均分子量为443kg/mol、厚度为98nm的PS薄膜。对PS薄膜表面润湿脊的高度随液滴放置时间增加而发生的变化进行测定，从图9可以看到，h～t线性区域斜率k＝4.4×10- 10m/s。根据式II计算得到在160℃下，重均分子量为443kg/mol、厚度为98nm的PS薄膜的黏度η为4.5×107Pa·s。According to the same method as in Example 1, a PS film with a weight average molecular weight of 443 kg/mol and a thickness of 98 nm was prepared. The change of the height of the wetting ridge on the surface of the PS film with the increase of the droplet placement time was measured. It can be seen from Figure 9 that the slope of the h~t linear region k=4.4×10 - 10 m/s. According to formula II, the viscosity η of the PS film with a weight average molecular weight of 443kg/mol and a thickness of 98nm at 160°C is 4.5×107Pa·s.
实施例6Example 6
按照实施例1相同的方法，以表面钝化的硅片(H-Si)为基底，制备重均分子量为443kg/mol、厚度为68nm的PS薄膜。对PS薄膜表面润湿脊的高度随液滴放置时间增加而发生的变化进行测定，从图10可以看到，h～t线性区域斜率k＝1.4×10-10m/s。根据式II计算得到在160℃下，重均分子量为443kg/mol、厚度为68nm的PS薄膜的黏度η为1.4×108Pa·s。According to the same method as in Example 1, a PS thin film with a weight-average molecular weight of 443 kg/mol and a thickness of 68 nm was prepared using a passivated silicon wafer (H-Si) as a substrate. The change of the height of the wetting ridge on the surface of the PS film with the increase of the droplet placement time was measured. It can be seen from Fig. 10 that the slope of the h~t linear region k=1.4×10 -10 m/s. According to formula II, the viscosity η of the PS film with a weight average molecular weight of 443kg/mol and a thickness of 68nm at 160°C is 1.4×108Pa·s.
实施例7Example 7
按照实施例1相同的方法，制备重均分子量为443kg/mol、厚度为100～550nm的PS薄膜，测定PS薄膜的黏度η。从图11中可以看出，当PS薄膜厚度小于220nm后，PS薄膜黏度随薄膜厚度降低而减小。According to the same method as in Example 1, a PS film with a weight average molecular weight of 443 kg/mol and a thickness of 100-550 nm was prepared, and the viscosity η of the PS film was measured. It can be seen from Figure 11 that when the thickness of the PS film is less than 220nm, the viscosity of the PS film decreases with the decrease of the film thickness.
为进一步验证结果的准确性，改变基底材料，以表面钝化的硅片(H-Si)作为基底材料，测量了PS薄膜厚度为69～700nm范围内，H-Si基底上PS薄膜的黏度随薄膜厚度的变化关系。从图11中可以看出，随着薄膜厚度的降低，PS薄膜的黏度逐渐升高。这与以表面含有SiO2氧化层的硅片为基底的PS薄膜黏度随膜厚的变化关系相反。这是由于基底与聚合物界面相互作用的差异所致。由于H-Si与PS具有相对较强的界面相互作用，导致PS薄膜的黏度随膜厚降低而升高。In order to further verify the accuracy of the results, the substrate material was changed, and the surface passivated silicon wafer (H-Si) was used as the substrate material, and the viscosity of the PS film on the H-Si substrate was measured as the thickness of the PS film was in the range of 69-700nm. Variation of film thickness. It can be seen from Figure 11 that the viscosity of the PS film increases gradually as the film thickness decreases. This is contrary to the relationship between the viscosity of the PS film based on the silicon wafer with the SiO 2 oxide layer on the surface and the film thickness. This is due to differences in the substrate-polymer interfacial interactions. Due to the relatively strong interfacial interaction between H-Si and PS, the viscosity of PS film increases with the decrease of film thickness.
由以上实施例可以看出，本发明提供的测量方法能够准确测定基底支撑聚合物薄膜的黏度，同时对基底支撑薄膜黏度变化具有很强的敏感性，能够感受到基底性质、聚合物薄膜温度以及聚合物分子量的改变对薄膜黏度的影响。As can be seen from the above examples, the measurement method provided by the present invention can accurately measure the viscosity of the substrate-supported polymer film, and has strong sensitivity to the change of the substrate-supported film viscosity, and can feel the properties of the substrate, the temperature of the polymer film and the Effect of Changes in Polymer Molecular Weight on Film Viscosity.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above is only a preferred embodiment of the present invention, and it should be pointed out that for those of ordinary skill in the art, some improvements and modifications can also be made without departing from the principles of the present invention. It should be regarded as the protection scope of the present invention.
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