CN105808933B - Method and system for judging structural stability of high-molecular surfactant - Google Patents
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Abstract
本发明提供了一种高分子表面活性剂的结构稳定性判断方法，包括：获取目标表面活性剂的分子构型、分子量及多个不同预设温度；计算得到所述目标表面活性剂的分子内相关函数的表达式；采用PY近似，建立包含所述目标表面活性剂的直接相关函数和总相关函数的闭合方程；建立包含所述目标表面活性剂的直接相关函数、总相关函数以及分子内相关函数的PRISM积分方程；计算所述闭合方程和所述PRISM积分方程，得到对应所述预设温度直接相关函数的表达式和总相关函数的表达式；计算得到所述预设温度对应的目标表面活性剂的X‑光散射强度；根据所述多个不同预设温度一一对应的所述X‑光散射强度，判断所述目标表面活性剂的结构稳定性。
The invention provides a method for judging the structural stability of a polymer surfactant, comprising: obtaining the molecular configuration, molecular weight and multiple different preset temperatures of a target surfactant; calculating the intramolecular value of the target surfactant Expression of correlation function; using PY approximation, establish a closed equation including the direct correlation function and total correlation function of the target surfactant; establish the direct correlation function, total correlation function and intramolecular correlation including the target surfactant The PRISM integral equation of the function; calculate the closed equation and the PRISM integral equation, and obtain the expression corresponding to the preset temperature direct correlation function and the expression of the total correlation function; calculate and obtain the target surface corresponding to the preset temperature X-ray scattering intensity of the active agent; according to the X-ray scattering intensity corresponding to the plurality of different preset temperatures one-to-one, determine the structural stability of the target surfactant.
Description
技术领域technical field
本发明涉及化学机械研磨工艺及测量技术领域，具体涉及一种高分子表面活性剂的结构稳定性判断方法及系统。The invention relates to the technical field of chemical mechanical grinding technology and measurement, in particular to a method and system for judging the structural stability of a polymer surfactant.
背景技术Background technique
在集成电路化学机械研磨(Chemical Mechanical Planarization,CMP)工艺过程中，表面活性剂作为研磨液的主要组分，对芯片表面的平坦化加工具有重要作用。In the chemical mechanical polishing (Chemical Mechanical Planarization, CMP) process of integrated circuits, surfactants, as the main components of the polishing liquid, play an important role in the planarization of the chip surface.
在CMP工艺过程中，表面活性剂可以降低研磨液和疏水性薄膜间的表面张力，使研磨液和疏水性薄膜更紧密贴合，减少和控制晶圆疏水性薄膜表面的残留物和研磨粒子等缺陷，改善化学机械研磨效果；并且，表面活性剂还具有较低的临界胶束浓度，容易使研磨颗粒分散，更显著地稳定研磨颗粒，提高研磨液各组分的稳定性，降低研磨表面的清洗难度等。During the CMP process, surfactants can reduce the surface tension between the slurry and the hydrophobic film, make the slurry and the hydrophobic film adhere more closely, and reduce and control the residues and abrasive particles on the surface of the hydrophobic film on the wafer. In addition, the surfactant also has a lower critical micelle concentration, which is easy to disperse the abrasive particles, stabilize the abrasive particles more significantly, improve the stability of each component of the polishing liquid, and reduce the grinding surface. Difficulty of cleaning etc.
近年来，人们致力于寻找和开发生物亲和性好且结构适宜的高分子表面活性剂，以进一步拓展CMP技术的应用范围，提升研磨表面的平坦化程度。在表面活性剂研发过程中，X-光散射强度(X-Ray Scattering Intensity，XRSI)是表征高分子表面活性剂结构的重要参数。通过X-光散射强度的聚合峰峰值，以及聚合峰和无定形峰的位置变化，即可得到判断高分子表面活性剂的结构变化。In recent years, people have devoted themselves to finding and developing polymer surfactants with good bioaffinity and suitable structure, in order to further expand the application scope of CMP technology and improve the planarization of the grinding surface. In the process of surfactant research and development, X-Ray Scattering Intensity (XRSI) is an important parameter to characterize the structure of polymer surfactants. The structural change of the polymer surfactant can be judged by the X-ray scattering intensity of the polymerization peak and the positional changes of the polymerization peak and the amorphous peak.
现有的高分子表面活性剂研发过程，通过实验合成目标表面活性剂，在不同温度下检测该目标表面活性剂的X-光散射强度，确定目标表面活性剂的结构稳定性。然而，此种方法研发周期长，成本高。In the existing research and development process of polymer surfactants, the target surfactant is synthesized through experiments, and the X-ray scattering intensity of the target surfactant is detected at different temperatures to determine the structural stability of the target surfactant. However, this method has a long development cycle and high cost.
发明内容SUMMARY OF THE INVENTION
有鉴于此，本发明提供了一种高分子表面活性剂的结构稳定性判断方法及系统，缩短了高分子表面活性剂的研发进程，降低了实验成本。In view of this, the present invention provides a method and system for judging the structural stability of a polymer surfactant, which shortens the research and development process of the polymer surfactant and reduces the experimental cost.
为实现上述目的，本发明提供如下技术方案：To achieve the above object, the present invention provides the following technical solutions:
一种高分子表面活性剂的结构稳定性判断方法，包括：A method for judging the structural stability of a polymer surfactant, comprising:
获取表面活性剂的分子构型、分子量和多个不同预设温度；Obtain the molecular configuration, molecular weight and multiple different preset temperatures of surfactants;
针对每一预设温度，分别执行以下步骤，直到获得与所述多个不同预设温度一一对应的X-光散射强度：For each preset temperature, the following steps are respectively performed until the X-ray scattering intensities corresponding to the plurality of different preset temperatures one-to-one are obtained:
根据所述表面活性剂的分子构型和分子量，计算得到所述表面活性剂的分子内相关函数的表达式；According to the molecular configuration and molecular weight of the surfactant, calculate the expression of the intramolecular correlation function of the surfactant;
采用PY近似，建立包含所述表面活性剂的直接相关函数和总相关函数的闭合方程；Using the PY approximation, establish a closed equation containing the direct correlation function and the total correlation function of the surfactant;
建立所述表面活性剂高分子参考作用点模型积分方程；establishing the integral equation of the surfactant polymer reference point model;
根据所述分子构型及预设温度，计算所述闭合方程和所述高分子参考作用点模型积分方程，得到对应所述预设温度的直接相关函数的表达式和总相关函数的表达式；According to the molecular configuration and the preset temperature, calculate the closed equation and the integral equation of the polymer reference action point model, and obtain the expression of the direct correlation function and the expression of the total correlation function corresponding to the preset temperature;
根据所述分子内相关函数的表达式、直接相关函数的表达式和总相关函数的表达式，计算得到对应所述预设温度的表面活性剂的X-光散射强度；According to the expression of the intramolecular correlation function, the expression of the direct correlation function and the expression of the total correlation function, the X-ray scattering intensity of the surfactant corresponding to the preset temperature is obtained by calculating;
根据与所述多个不同预设温度一一对应的所述X-光散射强度，判断所述表面活性剂的结构稳定性。The structural stability of the surfactant is determined according to the X-ray scattering intensities corresponding to the plurality of different preset temperatures one-to-one.
优选的，所述根据所述表面活性剂的分子构型和分子量，计算得到所述表面活性剂的分子内相关函数的表达式，包括：Preferably, the expression of the intramolecular correlation function of the surfactant is calculated according to the molecular configuration and molecular weight of the surfactant, including:
根据所述分子构型和分子量，建立所述表面活性剂的参考作用点模型；According to the molecular configuration and molecular weight, establish a reference point of action model of the surfactant;
采用生成矩阵法获得所述表面活性剂的参考作用点模型中不同作用点间的二阶矩和四阶矩 The second-order moment between different action points in the reference action point model of the surfactant is obtained by using the generative matrix method and fourth moment
计算得到所述表面活性剂的参考作用点模型的分子内相关函数的表达式：Calculate the expression of the intramolecular correlation function of the reference action point model of the surfactant:
其中， in,
优选的，所述采用PY近似，建立包含所述表面活性剂的直接相关函数和总相关函数的闭合方程，包括：Preferably, the PY approximation is used to establish a closed equation including the direct correlation function and the total correlation function of the surfactant, including:
根据所述分子构型和分子量，建立所述表面活性剂的参考作用点模型；According to the molecular configuration and molecular weight, establish a reference point of action model of the surfactant;
采用PY近似，建立包含所述参考作用点模型的直接相关函数和总相关函数的闭合方程：Using the PY approximation, a closed equation containing the direct correlation function and the total correlation function of the reference point model is established:
其中，Cαγ(r)为直接相关函数，hαγ(r)为总相关函数，kB为玻尔兹曼常数，T为绝对温度；uαγ(r)为势能函数；Among them, C αγ (r) is the direct correlation function, h αγ (r) is the total correlation function, k B is the Boltzmann constant, T is the absolute temperature; u αγ (r) is the potential energy function;
所述势能函数uαγ(r)仅包括氢键和范德华力。The potential energy function u αγ (r) includes only hydrogen bonds and van der Waals forces.
优选的，所述根据所述分子构型和分子量，建立所述表面活性剂的参考作用点模型，包括：Preferably, according to the molecular configuration and molecular weight, the reference action point model of the surfactant is established, including:
根据所述分子构型和分子量，建立所述表面活性剂的多点半自由链模型；According to the molecular configuration and molecular weight, a multi-point semi-free chain model of the surfactant is established;
根据所述表面活性剂的多点半自由链模型，将所述表面活性剂分子链上的单体简化为作用点，建立所述表面活性剂的参考作用点模型；According to the multi-point semi-free chain model of the surfactant, the monomers on the molecular chain of the surfactant are simplified as action points, and the reference action point model of the surfactant is established;
其中，所述作用点模型内作用点间的力场仅包括氢键和范德华力。Wherein, the force field between the action points in the action point model only includes hydrogen bonds and van der Waals forces.
优选的，所述建立所述表面活性剂高分子参考作用点模型积分方程，包括：Preferably, the establishing the integral equation of the surfactant polymer reference action point model includes:
利用h(r)＝∫dr'∫dr”ω(|r-r'|)C(|r'-r”|)[ω(r”)+ρh(r”)]建立所述高分子参考作用点模型积分方程，其中：ρ为活性剂的分子数密度，C(r)、h(r)和ω(r)分别为直接相关函数、总相关函数以及分子内相关函数。Use h(r)=∫dr'∫dr"ω(|r-r'|)C(|r'-r"|)[ω(r")+ρh(r")] to establish the polymer reference Point-of-action model integral equation, where: ρ is the molecular number density of the active agent, C(r), h(r) and ω(r) are the direct correlation function, total correlation function and intramolecular correlation function, respectively.
优选的，所述根据所述分子内相关函数的表达式、直接相关函数的表达式和总相关函数的表达式，计算得到对应所述预设温度的表面活性剂的X-光散射强度，包括：Preferably, according to the expression of the intramolecular correlation function, the expression of the direct correlation function and the expression of the total correlation function, the X-ray scattering intensity of the surfactant corresponding to the preset temperature is calculated and obtained, including :
根据所述分子内相关函数的表达式、直接相关函数的表达式和总相关函数的表达式，得到对应所述预设温度的表面活性剂的结构因子：According to the expression of the intramolecular correlation function, the expression of the direct correlation function and the expression of the total correlation function, the structure factor of the surfactant corresponding to the preset temperature is obtained:
其中，分别为ω(r)和C(r)的傅里叶变换形式；in, are the Fourier transform forms of ω(r) and C(r), respectively;
根据所述结构因子，计算得到对应所述预设温度的表面活性剂的X-光散射强度：According to the structure factor, the X-ray scattering intensity of the surfactant corresponding to the preset temperature is calculated:
其中，xα为α基团组分数，bα(k)为α基团散射因子，NS为单体原子基团数。Among them, x α is the number of α groups, b α (k) is the scattering factor of α groups, and N S is the number of monomer atom groups.
优选的，所述根据与所述多个不同预设温度一一对应的所述X-光散射强度，判断所述表面活性剂的结构稳定性，包括：Preferably, judging the structural stability of the surfactant according to the X-ray scattering intensities corresponding to the plurality of different preset temperatures one-to-one includes:
获取所述多个不同预设温度一一对应的所述X-光散射强度；acquiring the X-ray scattering intensities corresponding to the plurality of different preset temperatures one-to-one;
判断所述多个不同预设温度一一对应的X-光散射强度的聚合峰峰值变化最大值是否小于第一阈值，如果是，进行下一步骤；如果否，则所述表面活性剂结构不稳定；It is judged whether the maximum value of the polymerization peak-to-peak variation of the X-ray scattering intensity corresponding to the plurality of different preset temperatures is smaller than the first threshold, and if so, proceed to the next step; if not, the surfactant structure is not Stablize;
判断所述多个不同预设温度一一对应的X-光散射强度的聚合峰的位置变化最大值是否小于第二阈值，如果是，进行下一步骤；如果否，则所述表面活性剂结构不稳定；Determine whether the maximum position change of the polymerization peaks of the X-ray scattering intensities corresponding to the multiple different preset temperatures is smaller than the second threshold, if so, go to the next step; if not, then the surfactant structure unstable;
判断所述多个不同预设温度一一对应的X-光散射强度的无定形峰的位置变化最大值是否小于第三阈值，如果是，所述目标结构稳定，如果否，则所述表面活性剂结构不稳定。Judging whether the maximum position change of the amorphous peaks of the X-ray scattering intensity corresponding to the multiple different preset temperatures is smaller than a third threshold, if so, the target structure is stable, if not, the surface active The agent structure is unstable.
一种高分子表面活性剂结构稳定性判断系统，包括：A system for judging the structural stability of a polymer surfactant, comprising:
获取模块，用于获取表面活性剂分子构型、分子量及多个不同预设温度；The acquisition module is used to acquire the molecular configuration, molecular weight and multiple different preset temperatures of the surfactant;
控制模块，用于针对每一预设温度，分别控制对应模块执行计算操作，直到获得与所述多个不同预设温度一一对应的X-光散射强度：The control module is configured to, for each preset temperature, respectively control the corresponding module to perform the calculation operation, until the X-ray scattering intensities corresponding to the multiple different preset temperatures one-to-one are obtained:
第一计算模块，用于根据所述表面活性剂的分子构型和分子量，计算得到所述表面活性剂的分子内相关函数的表达式；The first calculation module is used for calculating the expression of the intramolecular correlation function of the surfactant according to the molecular configuration and molecular weight of the surfactant;
近似模块，用于采用PY近似，建立包含所述表面活性剂的直接相关函数和总相关函数的闭合方程；an approximation module for using the PY approximation to establish a closed equation including the direct correlation function and the total correlation function of the surfactant;
建模模块，用于建立所述表面活性剂高分子参考作用点模型积分方程；a modeling module for establishing the integral equation of the surfactant polymer reference point model integral equation;
第二计算模块，用于根据所述分子构型及预设温度，计算所述闭合方程和所述高分子参考作用点模型积分方程，得到对应所述预设温度的直接相关函数的表达式和总相关函数的表达式；The second calculation module is configured to calculate the closed equation and the integral equation of the polymer reference action point model according to the molecular configuration and the preset temperature, and obtain the expression of the direct correlation function corresponding to the preset temperature and the expression of the total correlation function;
第三计算模块，用于根据所述分子内相关函数的表达式、直接相关函数的表达式和总相关函数的表达式，计算得到对应所述预设温度的表面活性剂的X-光散射强度；The third calculation module is configured to calculate the X-ray scattering intensity of the surfactant corresponding to the preset temperature according to the expression of the intramolecular correlation function, the expression of the direct correlation function and the expression of the total correlation function ;
判断模块，用于与根据所述多个不同预设温度一一对应的所述X-光散射强度，判断所述表面活性剂的结构稳定性。and a judgment module for judging the structural stability of the surfactant with the X-ray scattering intensities corresponding to the plurality of different preset temperatures one-to-one.
优选的，所述第一计算模块包括：Preferably, the first calculation module includes:
第一建模单元，用于根据所述表面活性剂分子构型和分子量，建立所述表面活性剂的参考作用点模型；a first modeling unit, used for establishing a reference action point model of the surfactant according to the molecular configuration and molecular weight of the surfactant;
第一获取单元，用于采用生成矩阵法获得所述表面活性剂的参考作用点模型中不同作用点间的二阶矩和四阶矩 The first obtaining unit is used to obtain the second order moments between different action points in the reference action point model of the surfactant by using the generative matrix method and fourth moment
第一计算单元，用于计算得到所述表面活性剂的参考作用点模型的分子内相关函数的表达式：The first calculation unit is used to calculate the expression of the intramolecular correlation function of the reference action point model of the surfactant:
其中， in,
优选的，所述判断模块包括：Preferably, the judging module includes:
第二获取单元，用于获取所述多个不同预设温度一一对应的所述X-光散射强度；a second acquiring unit, configured to acquire the X-ray scattering intensities corresponding to the plurality of different preset temperatures one-to-one;
第一判断单元，用于判断所述多个不同预设温度一一对应的X-光散射强度的聚合峰峰值变化最大值是否小于第一阈值，如果是，进行下一步骤；如果否，则所述表面活性剂结构不稳定；a first judgment unit, configured to judge whether the maximum value of the aggregated peak-to-peak variation of the X-ray scattering intensities corresponding to the plurality of different preset temperatures is smaller than the first threshold, and if so, go to the next step; if not, then The surfactant structure is unstable;
第二判断单元，用于判断所述多个不同预设温度一一对应的X-光散射强度的聚合峰的位置变化最大值是否小于第二阈值，如果是，进行下一步骤；如果否，则所述表面活性剂结构不稳定；The second judgment unit is configured to judge whether the maximum position change of the polymerization peaks of the X-ray scattering intensities corresponding to the plurality of different preset temperatures one-to-one is smaller than the second threshold, and if so, go to the next step; if not, Then the surfactant structure is unstable;
第三判断单元，用于判断所述多个不同预设温度一一对应的X-光散射强度的无定形峰的位置变化最大值是否小于第三阈值，如果是，所述表面活性剂结构稳定，如果否，则所述目标结构不稳定。A third judging unit, configured to judge whether the maximum position change of the amorphous peaks of the X-ray scattering intensities corresponding to the plurality of different preset temperatures one-to-one is smaller than a third threshold, and if so, the surfactant structure is stable , if not, the target structure is unstable.
与现有技术相比，本发明具有以下优点：Compared with the prior art, the present invention has the following advantages:
采用PY近似，结合高分子参考作用点模型理论，更接近需要计算的表面活性剂的真实结构，由此得到描述预设温度下所述表面活性剂的直接相关函数、总相关函数以及分子内相关函数更加准确的表达式，从而获得准确的X-光散射强度。通过计算多个不同预设温度下表面活性剂的X-光散射强度，可以反应不同温度下表面活性剂的结构变化，从而判断所述表面活性剂的结构稳定性。相比于实验量测高分子表面活性剂的X-光散射强度，本发明不需要进行前期的实验合成和目标结构表面活性剂的X-光散射强度的测量，从而缩短研发周期，降低实验成本，提高工作效率，为实验合成新型高分子表面活性剂提供了重要工具。Using the PY approximation, combined with the polymer reference action point model theory, is closer to the real structure of the surfactant to be calculated, thereby obtaining the direct correlation function, total correlation function and intramolecular correlation describing the surfactant at the preset temperature. A more accurate expression of the function to obtain accurate X-ray scattering intensity. By calculating the X-ray scattering intensity of the surfactant at multiple different preset temperatures, the structural changes of the surfactant at different temperatures can be reflected, thereby judging the structural stability of the surfactant. Compared with the experimental measurement of the X-ray scattering intensity of the polymer surfactant, the present invention does not require preliminary experimental synthesis and measurement of the X-ray scattering intensity of the target structure surfactant, thereby shortening the research and development cycle and reducing the experimental cost. , improve work efficiency, and provide an important tool for the experimental synthesis of new polymer surfactants.
附图说明Description of drawings
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据提供的附图获得其他的附图。In order to illustrate the embodiments of the present invention or the technical solutions in the prior art more clearly, the following briefly introduces the accompanying drawings that are used in the description of the embodiments or the prior art. Obviously, the drawings in the following description are only It is an embodiment of the present invention. For those of ordinary skill in the art, other drawings can also be obtained according to the provided drawings without creative efforts.
图1为本发明实施例一的判断方法流程图；1 is a flowchart of a judgment method according to Embodiment 1 of the present invention;
图2为本发明方法中建立的参考作用点模型示意图；Fig. 2 is a schematic diagram of a reference action point model established in the method of the present invention;
图3为本发明实施例三的判断系统结构图。FIG. 3 is a structural diagram of a judgment system according to Embodiment 3 of the present invention.
具体实施方式Detailed ways
下面将结合本发明实施例中的附图，对本发明实施例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 embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, but not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.
如背景技术所述，现有的高分子表面活性剂研发过程，通过实验合成目标表面活性剂，在不同温度下检测该目标表面活性剂的X-光散射强度，确定目标表面活性剂的结构稳定性。然而，此种方法研发周期长，成本高。As described in the background art, in the existing research and development process of polymer surfactants, the target surfactant is synthesized through experiments, and the X-ray scattering intensity of the target surfactant is detected at different temperatures to determine the structural stability of the target surfactant. sex. However, this method has a long development cycle and high cost.
基于此，本发明提出一种高分子表面活性剂的结构稳定性判断方法及系统，包括：Based on this, the present invention proposes a method and system for judging the structural stability of a polymer surfactant, including:
获取表面活性剂的分子构型、分子量及多个不同预设温度；针对每一预设温度，分别执行以下步骤，直到获得与所述多个不同预设温度一一对应的X-光散射强度：根据所述表面活性剂的分子构型和分子量，计算得到所述表面活性剂的分子内相关函数的表达式；采用PY近似，建立包含所述表面活性剂的直接相关函数和总相关函数的闭合方程；建立所述表面活性剂高分子参考作用点模型积分方程；根据所述分子构型及预设温度，计算所述闭合方程和所述高分子参考作用点模型积分方程，得到对应所述预设温度的直接相关函数的表达式和总相关函数的表达式；根据所述分子内相关函数的表达式、直接相关函数的表达式和总相关函数的表达式，计算得到对应所述预设温度的表面活性剂的X-光散射强度；根据与所述多个不同预设温度一一对应的所述X-光散射强度，判断所述表面活性剂的结构稳定性。Obtain the molecular configuration, molecular weight and multiple different preset temperatures of the surfactant; for each preset temperature, perform the following steps respectively until the X-ray scattering intensity corresponding to the multiple different preset temperatures is obtained : Calculate the expression of the intramolecular correlation function of the surfactant according to the molecular configuration and molecular weight of the surfactant; use the PY approximation to establish an expression including the direct correlation function and the total correlation function of the surfactant closed equation; establish the integral equation of the surfactant polymer reference point model; according to the molecular configuration and preset temperature, calculate the closed equation and the polymer reference point model integral equation, and obtain the corresponding The expression of the direct correlation function of the preset temperature and the expression of the total correlation function; according to the expression of the intramolecular correlation function, the expression of the direct correlation function and the expression of the total correlation function, the corresponding preset temperature is calculated to obtain The X-ray scattering intensity of the surfactant at the temperature; according to the X-ray scattering intensity corresponding to the plurality of different preset temperatures one-to-one, the structural stability of the surfactant is judged.
采用PY近似，结合高分子参考作用点模型理论，更接近需要计算的表面活性剂的真实结构，由此得到描述预设温度下所述表面活性剂的直接相关函数、总相关函数以及分子内相关函数更加准确的表达式，从而获得准确的X-光散射强度。通过计算多个不同预设温度下表面活性剂的X-光散射强度，可以反应不同温度下表面活性剂的结构变化，从而判断所述表面活性剂的结构稳定性。相比于实验量测高分子表面活性剂的X-光散射强度，本发明不需要进行前期的实验合成和目标结构表面活性剂的X-光散射强度的测量，从而缩短研发周期，降低实验成本，提高工作效率，为实验合成新型高分子表面活性剂提供了重要工具。Using the PY approximation, combined with the polymer reference action point model theory, is closer to the real structure of the surfactant to be calculated, thereby obtaining the direct correlation function, total correlation function and intramolecular correlation describing the surfactant at the preset temperature. A more accurate expression of the function to obtain accurate X-ray scattering intensity. By calculating the X-ray scattering intensity of the surfactant at multiple different preset temperatures, the structural changes of the surfactant at different temperatures can be reflected, thereby judging the structural stability of the surfactant. Compared with the experimental measurement of the X-ray scattering intensity of the polymer surfactant, the present invention does not require preliminary experimental synthesis and measurement of the X-ray scattering intensity of the target structure surfactant, thereby shortening the research and development cycle and reducing the experimental cost. , improve work efficiency, and provide an important tool for the experimental synthesis of new polymer surfactants.
以上是本发明的中心思想，下面将结合本发明实施例中的附图，对本发明实施例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 above is the central idea of the present invention. The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention. not all examples. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.
实施例一Example 1
本实施例提供了一种高分子表面活性剂的结构稳定性判断方法，包括以下步骤：The present embodiment provides a method for judging the structural stability of a polymer surfactant, comprising the following steps:
步骤S0：确定表面活性剂的分子构型、分子量及多个不同预设温度。Step S0: Determine the molecular configuration, molecular weight and multiple different preset temperatures of the surfactant.
该步骤主要用于确定高分子表面活性剂的分子构型以及表面活性剂的分子量。不同分子量的表面活性剂具有不同的微观结构。并且，不同温度下，表面活性剂的结构也会有所不同This step is mainly used to determine the molecular configuration of the polymer surfactant and the molecular weight of the surfactant. Surfactants of different molecular weights have different microstructures. Moreover, the structure of surfactants will be different at different temperatures
步骤S1：针对每一预设温度，分别执行以下步骤，直到获得与所述多个不同预设温度一一对应的X-光散射强度。Step S1: For each preset temperature, the following steps are respectively performed until the X-ray scattering intensities corresponding to the plurality of different preset temperatures one-to-one are obtained.
分别计算多个不同预设温度下的X-光散射强度，可以比对不同温度下高分子表面活性剂的结构变化，从而确定高分子表面活性剂的结构稳定性。By calculating the X-ray scattering intensities at multiple different preset temperatures, the structural changes of the polymer surfactants at different temperatures can be compared, thereby determining the structural stability of the polymer surfactants.
具体的，所述步骤包括：Specifically, the steps include:
步骤S111：获取表面活性剂分子构型、分子量及预设温度。Step S111: Obtain the molecular configuration, molecular weight and preset temperature of the surfactant.
步骤S112：根据所述表面活性剂的分子构型和分子量，计算得到所述表面活性剂的分子内相关函数的表达式。Step S112: According to the molecular configuration and molecular weight of the surfactant, calculate the expression of the intramolecular correlation function of the surfactant.
具体的，本步骤包括：Specifically, this step includes:
首先，根据所述分子构型和分子量，建立所述表面活性剂的参考作用点模型。First, according to the molecular configuration and molecular weight, a reference point of action model of the surfactant is established.
在本实施例中，所述参考作用点模型的建立过程如下：In this embodiment, the establishment process of the reference action point model is as follows:
根据所述表面活性剂的分子构型和分子量，建立所述表面活性剂的多点半自由链模型；According to the molecular configuration and molecular weight of the surfactant, establish a multi-point semi-free chain model of the surfactant;
根据所述表面活性剂的多点半自由链模型，将所述表面活性剂分子链上的单体简化为作用点，建立所述表面活性剂的参考作用点模型；According to the multi-point semi-free chain model of the surfactant, the monomers on the molecular chain of the surfactant are simplified as action points, and the reference action point model of the surfactant is established;
其中，所述作用点模型内作用点间的力场仅包括氢键和范德华力。Wherein, the force field between the action points in the action point model only includes hydrogen bonds and van der Waals forces.
具体的，如图2所示，为以聚苯乙烯为例建立的参考作用点模型示意图，首先确定聚苯乙烯的分子构型及分子量，获取相关几何结构参数，将聚苯乙烯单体结构简化为8个单体，建立参考作用点模型。Specifically, as shown in Figure 2, it is a schematic diagram of the reference action point model established by taking polystyrene as an example. First, determine the molecular configuration and molecular weight of polystyrene, obtain relevant geometric structure parameters, and simplify the structure of polystyrene monomer. For 8 monomers, a reference point of action model was established.
一般地，用于CMP体系的高分子表面活性剂可以简化为链状高分子聚合物，常见的聚合物链有自由连接链、半自由链、旋转异构链等。半自由链在描述真实高分子体系过程中具有很高的模拟精度，因此，本发明主要选择半自由链模型。Generally, the polymer surfactants used in the CMP system can be simplified as chain polymers, and common polymer chains include free link chains, semi-free chains, and rotamer chains. The semi-free chain has high simulation accuracy in the process of describing the real polymer system. Therefore, the present invention mainly selects the semi-free chain model.
依据高分子构型建立PRISM理论的参考作用点。通过采用联合原子模型可以将高分子链各原子结合为原子基团，从而在不失模拟精度的前提下简化模型计算，降低模型复杂度。The reference point of PRISM theory is established according to the polymer configuration. By using the joint atom model, each atom of the polymer chain can be combined into an atomic group, thereby simplifying the model calculation and reducing the model complexity without losing the simulation accuracy.
接着，采用生成矩阵法获得所述表面活性剂的参考作用点模型中不同作用点间的二阶矩和四阶矩 Next, use the generating matrix method to obtain the second order moments between different action points in the reference action point model of the surfactant and fourth moment
计算得到所述表面活性剂的参考作用点模型的分子内相关函数的表达式：Calculate the expression of the intramolecular correlation function of the reference action point model of the surfactant:
其中， in,
步骤S113：采用PY近似，建立包含所述表面活性剂的直接相关函数和总相关函数的闭合方程。Step S113: Using the PY approximation, a closed equation including the direct correlation function and the total correlation function of the surfactant is established.
具体的，所述步骤包括：Specifically, the steps include:
根据所述分子构型和分子量，建立所述表面活性剂的参考作用点模型；According to the molecular configuration and molecular weight, establish a reference point of action model of the surfactant;
具体的，所述建立所述表面活性剂的参考作用点模型可以参考步骤112中的建模方法，在本申请其他实施例中，也可以仅进行一次建模，步骤112和步骤113均参考此模型进行相应的计算。Specifically, for establishing the reference action point model of the surfactant, reference may be made to the modeling method in step 112. In other embodiments of the present application, modeling may be performed only once, and both steps 112 and 113 refer to this The model is calculated accordingly.
采用PY近似，建立包含所述参考作用点模型的直接相关函数和总相关函数的闭合方程：Using the PY approximation, a closed equation containing the direct correlation function and the total correlation function of the reference point model is established:
其中，Cαγ(r)为直接相关函数，hαγ(r)为总相关函数，kB为玻尔兹曼常数，T为绝对温度；uαγ(r)为势能函数；Among them, C αγ (r) is the direct correlation function, h αγ (r) is the total correlation function, k B is the Boltzmann constant, T is the absolute temperature; u αγ (r) is the potential energy function;
所述势能函数uαγ(r)仅包括氢键和范德华力。The potential energy function u αγ (r) includes only hydrogen bonds and van der Waals forces.
本实施例中，本步骤主要用于引入高分子参考作用点模型(PRISM)理论计算所需的闭合方程。在求解PRISM方程过程中，需要引入相关近似，常见的如超网链近似、PY(Percus-Yevick)近似及平均球近似等。通过PY近似求解OZ(Ornstein-Zernike)积分方程，可以更接近真实的描述高分子表面活性剂的结构。In this embodiment, this step is mainly used to introduce the closed equation required for the theoretical calculation of the polymer reference action point model (PRISM). In the process of solving the PRISM equation, it is necessary to introduce relevant approximations, such as the supernet chain approximation, the PY (Percus-Yevick) approximation and the mean sphere approximation. By solving the OZ (Ornstein-Zernike) integral equation approximately by PY, the structure of the polymer surfactant can be described more closely.
步骤S114：建立所述表面活性剂的高分子参考作用点模型积分方程。Step S114 : establishing an integral equation of the polymer reference action point model of the surfactant.
具体的，利用h(r)＝∫dr'∫dr”ω(|r-r'|)C(|r'-r”|)[ω(r”)+ρh(r”)]建立所述高分子参考作用点模型积分方程，其中：ρ为活性剂的分子数密度，C(r)、h(r)和ω(r)分别为直接相关函数、总相关函数以及分子内相关函数。Specifically, using h(r)=∫dr'∫dr"ω(|r-r'|)C(|r'-r"|)[ω(r")+ρh(r")] to establish the The integral equation of the polymer reference point model, where: ρ is the molecular number density of the active agent, C(r), h(r) and ω(r) are the direct correlation function, total correlation function and intramolecular correlation function, respectively.
本步骤用于联合步骤113中的闭合方程进行PRISM理论的模拟计算。所要求解的PRISM方程，主要通过模拟高分子表面活性剂的分子内和分子间的相关函数的内在关联建立得到的。This step is used to combine the closed equation in step 113 to perform the simulation calculation of the PRISM theory. The PRISM equation to be solved is mainly established by simulating the intrinsic correlation of intramolecular and intermolecular correlation functions of polymeric surfactants.
步骤S115：根据所述分子构型及预设温度，计算所述闭合方程和所述高分子参考作用点模型积分方程，得到对应所述预设温度直接相关函数的表达式和总相关函数的表达式。Step S115: According to the molecular configuration and the preset temperature, calculate the closed equation and the integral equation of the polymer reference point model, and obtain the expression of the direct correlation function corresponding to the preset temperature and the expression of the total correlation function Mode.
具体的，对步骤113和步骤114中的方程进行联立求解，即可得到对应所述预设温度直接相关函数的表达式和总相关函数的表达式。Specifically, by simultaneously solving the equations in step 113 and step 114, the expression corresponding to the direct correlation function of the preset temperature and the expression of the total correlation function can be obtained.
步骤S116：根据所述分子内相关函数的表达式、直接相关函数的表达式和总相关函数的表达式，计算得到对应所述预设温度的表面活性剂的X-光散射强度。Step S116: Calculate the X-ray scattering intensity of the surfactant corresponding to the preset temperature according to the expression of the intramolecular correlation function, the expression of the direct correlation function and the expression of the total correlation function.
通过步骤S111-步骤S116可以计算得到预设温度下的表面活性剂的X-光散射强度。Through steps S111 to S116, the X-ray scattering intensity of the surfactant at the preset temperature can be obtained by calculation.
步骤S111-步骤S116采用高分子参考作用点模型(Polymer ReferenceInteraction Site Model，PRISM)理论计算得到了预设温度下的表面活性剂的X-光散射强度。PRISM理论是描述高分子材料结构和性质的重要理论工具，该理论从高分子内原子基团间相互作用关系出发，通过分析分子内和分子间原子(基团)相互关系，来建立自洽的理论模型，最终获得分子内和分子间不同原子(基团)间各种相关函数，进而得到体系的微观结构与宏观性质。Steps S111 to S116 adopt the Polymer Reference Interaction Site Model (PRISM) theoretical calculation to obtain the X-ray scattering intensity of the surfactant at a preset temperature. The PRISM theory is an important theoretical tool to describe the structure and properties of polymer materials. The theory starts from the interaction relationship between atomic groups in the polymer, and establishes a self-consistent relationship by analyzing the interaction between the atoms (groups) in the molecule and between the molecules. Theoretical model, and finally obtain various correlation functions between different atoms (groups) within and between molecules, and then obtain the microstructure and macroscopic properties of the system.
步骤S2：根据与所述多个不同预设温度一一对应的所述X-光散射强度，判断所述表面活性剂的结构稳定性。Step S2: Determine the structural stability of the surfactant according to the X-ray scattering intensities corresponding to the plurality of different preset temperatures one-to-one.
通过比对多个不同预设温度一一对应的所述X-光散射强度，例如聚合峰的位置以及大小，无定形峰的位置等，判断所述目标表面活性剂的结构特征。By comparing the X-ray scattering intensities corresponding to a plurality of different preset temperatures, such as the position and size of the polymerization peak, the position of the amorphous peak, etc., the structural characteristics of the target surfactant are determined.
在开发高分子表面活性剂过程中，X-光散射强度(XRSI)可以从宏观角度展示高分子表面活性剂的局部密度波动和涨落，而密度涨落直接刻画了表面活性剂的微观结构，微观结构的差异又导致宏观性质的不同，如压力、表面张力等，因此XRSI是反映高分子表面活性剂的宏观性质的重要手段之一，对于区分、检测不同表面活性剂的结构和性质具有重要意义。In the process of developing polymer surfactants, X-ray scattering intensity (XRSI) can show the local density fluctuations and fluctuations of polymer surfactants from a macroscopic perspective, and density fluctuations directly describe the microstructure of surfactants. The difference in microstructure leads to the difference in macroscopic properties, such as pressure, surface tension, etc. Therefore, XRSI is one of the important means to reflect the macroscopic properties of polymer surfactants. It is important for distinguishing and detecting the structure and properties of different surfactants. significance.
本实施例中，采用PY近似，结合PRISM理论，得到描述预设温度下所述表面活性剂的直接相关函数、总相关函数以及分子内相关函数，从而获得XRSI。通过计算多个不同预设温度下表面活性剂的XRSI，从而判断所述表面活性剂的结构稳定性。相比于实验量测高分子表面活性剂的XRSI，本发明可以降低实验成本，缩短研发周期，提高工作效率，为实验合成新型高分子表面活性剂提供了重要工具。In this embodiment, the PY approximation is used, combined with the PRISM theory, to obtain the direct correlation function, total correlation function and intramolecular correlation function describing the surfactant at a preset temperature, thereby obtaining XRSI. By calculating the XRSI of the surfactant at a plurality of different preset temperatures, the structural stability of the surfactant can be judged. Compared with the XRSI of the experimental measurement of the polymer surfactant, the present invention can reduce the experimental cost, shorten the research and development cycle, improve the work efficiency, and provide an important tool for the experimental synthesis of a new polymer surfactant.
实施例二Embodiment 2
同上一实施例相比，本实施例将步骤S112中建立表面活性剂的参考作用点模型作为一个独立的步骤，具体的所述步骤1中分为以下步骤：Compared with the previous embodiment, this embodiment takes the establishment of the reference action point model of the surfactant in step S112 as an independent step, and the specific step 1 is divided into the following steps:
步骤S120：获取表面活性剂分子构型、分子量及预设温度。Step S120: Obtain the molecular configuration, molecular weight and preset temperature of the surfactant.
步骤S121：根据所述表面活性剂的分子构型和分子量，建立表面活性剂的参考作用点模型。Step S121: According to the molecular configuration and molecular weight of the surfactant, establish a reference action point model of the surfactant.
步骤S122：计算得到所述表面活性剂的分子内相关函数的表达式。Step S122: Calculate the expression of the intramolecular correlation function of the surfactant.
在本步骤中，根据步骤121中的模型参数，直接进行计算，得到所述表面活性剂的分子内相关函数的表达式。In this step, calculation is performed directly according to the model parameters in step 121 to obtain the expression of the intramolecular correlation function of the surfactant.
步骤S123：采用PY近似，建立包含所述表面活性剂的直接相关函数和总相关函数的闭合方程。Step S123: Using the PY approximation, a closed equation including the direct correlation function and the total correlation function of the surfactant is established.
在本步骤中，由于步骤S121已经建立了相应的参考作用点模型，因此，本步骤中直接应用所述参考作用点模型中的模型参数，建立包含所述表面活性剂的直接相关函数和总相关函数的闭合方程。In this step, since the corresponding reference action point model has been established in step S121, the model parameters in the reference action point model are directly applied in this step to establish the direct correlation function and total correlation including the surfactant The closed equation of the function.
步骤S124：建立所述表面活性剂的高分子参考作用点模型积分方程。Step S124 : establishing an integral equation of the polymer reference action point model of the surfactant.
同步骤123相类似，根据步骤121中已经建立的表面活性剂的参考作用点模型，本步骤中直接应用所述参考作用点模型中的模型参数，建立包含所述表面活性剂的直接相关函数、总相关函数以及分子内相关函数的高分子参考作用点模型积分方程。Similar to step 123, according to the reference action point model of the surfactant that has been established in step 121, the model parameters in the reference action point model are directly applied in this step to establish a direct correlation function including the surfactant, Integral equations of the macromolecular reference point model for the total correlation function and the intramolecular correlation function.
步骤S125：根据所述分子构型及预设温度，计算所述闭合方程和所述高分子参考作用点模型积分方程，得到对应所述预设温度的直接相关函数的表达式和总相关函数的表达式。Step S125: According to the molecular configuration and the preset temperature, calculate the closed equation and the polymer reference point model integral equation, and obtain the expression of the direct correlation function corresponding to the preset temperature and the total correlation function. expression.
步骤S126：根据所述分子内相关函数的表达式、直接相关函数的表达式和总相关函数的表达式，计算得到对应所述预设温度的表面活性剂的X-光散射强度。Step S126: Calculate the X-ray scattering intensity of the surfactant corresponding to the preset temperature according to the expression of the intramolecular correlation function, the expression of the direct correlation function and the expression of the total correlation function.
具体的，在本实施例中，本步骤包括以下计算过程：Specifically, in this embodiment, this step includes the following calculation process:
根据所述分子内相关函数的表达式、直接相关函数的表达式和总相关函数的表达式，得到所述预设温度对应的表面活性剂的结构因子：According to the expression of the intramolecular correlation function, the expression of the direct correlation function and the expression of the total correlation function, the structure factor of the surfactant corresponding to the preset temperature is obtained:
其中，分别为ω(r)和C(r)的傅里叶变换形式；in, are the Fourier transform forms of ω(r) and C(r), respectively;
根据所述结构因子，计算得到所述预设温度对应的表面活性剂的X-光散射强度：According to the structure factor, the X-ray scattering intensity of the surfactant corresponding to the preset temperature is calculated:
其中，xα为α基团组分数，bα(k)为α基团散射因子，NS为单体原子基团数。Among them, x α is the number of α groups, b α (k) is the scattering factor of α groups, and N S is the number of monomer atom groups.
另外，在本发明的其他实施例中，根据所述PRISM模拟所获得的总相关函数还可以得到分子间相关函数：g(r)＝h(r)+1，该函数能描述高分子表面活性剂的局部堆积效应和微观结构，是统计力学理论研究流体和材料结构和性质的重要手段和方法。In addition, in other embodiments of the present invention, according to the total correlation function obtained by the PRISM simulation, an intermolecular correlation function can also be obtained: g(r)=h(r)+1, which can describe the surface activity of polymers It is an important means and method for studying the structure and properties of fluids and materials by statistical mechanics theory.
另外，本实施例中步骤2包括：In addition, step 2 in this embodiment includes:
步骤21：获取所述多个不同预设温度一一对应的所述X-光散射强度；Step 21: Obtain the X-ray scattering intensities corresponding to the plurality of different preset temperatures one-to-one;
步骤22：判断所述多个不同预设温度一一对应的X-光散射强度的聚合峰峰值变化最大值是否小于第一阈值，如果是，进行下一步骤；如果否，则所述表面活性剂结构不稳定；Step 22: Determine whether the maximum value of the peak-to-peak variation of the X-ray scattering intensity corresponding to the plurality of different preset temperatures is smaller than the first threshold, and if so, go to the next step; if not, the surface active The agent structure is unstable;
步骤23：判断所述多个不同预设温度一一对应的X-光散射强度的聚合峰的位置变化最大值是否小于第二阈值，如果是，进行下一步骤；如果否，则所述表面活性剂结构不稳定；Step 23: Determine whether the maximum position change of the aggregation peaks of the X-ray scattering intensities corresponding to the multiple different preset temperatures is smaller than the second threshold, if so, go to the next step; if not, then the surface The active agent is structurally unstable;
步骤24：判断所述多个不同预设温度一一对应的X-光散射强度的无定形峰的位置变化最大值是否小于第三阈值，如果是，所述表面活性剂结构稳定，如果否，则所述表面活性剂结构不稳定。Step 24: judging whether the maximum position change of the amorphous peaks of the X-ray scattering intensities corresponding to the multiple different preset temperatures is smaller than a third threshold, if so, the surfactant structure is stable, if not, Then the surfactant structure is unstable.
通过对不同温度下的X-光散射强度的聚合峰和无定形峰的比对，间接的对表面活性剂的结构进行微观比对，从而判断表面活性剂结构在不同温度下的稳定性。By comparing the polymerization peaks and amorphous peaks of the X-ray scattering intensity at different temperatures, the structure of the surfactant is indirectly compared microscopically to determine the stability of the surfactant structure at different temperatures.
同上一实施例相比，本实施例先建立起参考作用点模型，从而不需要多次建模。Compared with the previous embodiment, this embodiment first establishes the reference action point model, so that multiple modeling is not required.
同样的，本实施例中，采用PY近似，结合PRISM理论，得到描述预设温度下所述表面活性剂的直接相关函数、总相关函数以及分子内相关函数，从而获得XRSI。通过计算多个不同预设温度下表面活性剂的XRSI，从而判断所述表面活性剂的稳定性。相比于实验量测高分子表面活性剂的XRSI，本发明可以降低实验成本，缩短研发周期，提高工作效率，为实验合成新型高分子表面活性剂提供了重要工具。Similarly, in this embodiment, the PY approximation is used, combined with the PRISM theory, to obtain the direct correlation function, total correlation function and intramolecular correlation function describing the surfactant at a preset temperature, thereby obtaining XRSI. By calculating the XRSI of the surfactant at a plurality of different preset temperatures, the stability of the surfactant is judged. Compared with the XRSI of the experimental measurement of the polymer surfactant, the present invention can reduce the experimental cost, shorten the research and development cycle, improve the work efficiency, and provide an important tool for the experimental synthesis of a new polymer surfactant.
实施例三Embodiment 3
对应上述实施例，本实施例提供了一种高分子表面活性剂结构稳定性判断系统，结合图3可以看出，本实施例所述系统具体包括：Corresponding to the above embodiment, this embodiment provides a system for judging the structural stability of polymer surfactants. It can be seen from FIG. 3 that the system in this embodiment specifically includes:
获取模块，用于获取表面活性剂分子构型、分子量及多个不同预设温度；The acquisition module is used to acquire the molecular configuration, molecular weight and multiple different preset temperatures of the surfactant;
具体的，所述获取模块包括：Specifically, the acquisition module includes:
结构获取单元，用于确定表面活性剂的分子构型、分子量；The structure acquisition unit is used to determine the molecular configuration and molecular weight of the surfactant;
通过获取所述分子构型、分子量，从而确定表面活性剂的分子链结构。By obtaining the molecular configuration and molecular weight, the molecular chain structure of the surfactant can be determined.
温度获取单元，用于确定表面活性剂的预设温度。The temperature acquisition unit is used to determine the preset temperature of the surfactant.
控制模块，用于针对每一预设温度，分别控制对应模块执行计算操作，直到获得与所述多个不同预设温度一一对应的X-光散射强度：The control module is configured to, for each preset temperature, respectively control the corresponding module to perform the calculation operation, until the X-ray scattering intensities corresponding to the multiple different preset temperatures one-to-one are obtained:
第一计算模块，用于根据所述表面活性剂的分子构型和分子量，计算得到所述表面活性剂的分子内相关函数的表达式；The first calculation module is used for calculating the expression of the intramolecular correlation function of the surfactant according to the molecular configuration and molecular weight of the surfactant;
具体的，所述第一计算模块包括：Specifically, the first computing module includes:
第一建模单元，用于根据所述表面活性剂分子构型和分子量，建立所述表面活性剂的参考作用点模型；a first modeling unit, used for establishing a reference action point model of the surfactant according to the molecular configuration and molecular weight of the surfactant;
具体的，所述第一建模单元根据所述表面活性剂分子构型和分子量，建立所述表面活性剂的多点半自由链模型；并根据所述表面活性剂的多点半自由链模型，将所述表面活性剂分子链上的单体简化为作用点，建立所述表面活性剂的参考作用点模型；Specifically, the first modeling unit establishes a multi-point semi-free chain model of the surfactant according to the molecular configuration and molecular weight of the surfactant; and according to the multi-point semi-free chain model of the surfactant , the monomer on the molecular chain of the surfactant is simplified as the action point, and the reference action point model of the surfactant is established;
其中，所述作用点模型内作用点间的力场仅包括氢键和范德华力。Wherein, the force field between the action points in the action point model only includes hydrogen bonds and van der Waals forces.
第一获取单元，用于采用生成矩阵法获得所述表面活性剂的参考作用点模型中不同作用点间的二阶矩和四阶矩 The first obtaining unit is used to obtain the second order moments between different action points in the reference action point model of the surfactant by using the generative matrix method and fourth moment
第一计算单元，用于计算得到所述表面活性剂的参考作用点模型的分子内相关函数的表达式：The first calculation unit is used to calculate the expression of the intramolecular correlation function of the reference action point model of the surfactant:
其中， in,
近似模块，用于采用PY近似，建立包含所述表面活性剂的直接相关函数和总相关函数的闭合方程；an approximation module for using the PY approximation to establish a closed equation including the direct correlation function and the total correlation function of the surfactant;
具体的，所述近似模块包括：Specifically, the approximation module includes:
第二建模单元，用于根据所述表面活性剂分子构型和分子量，建立所述表面活性剂的参考作用点模型；a second modeling unit, configured to establish a reference action point model of the surfactant according to the molecular configuration and molecular weight of the surfactant;
近似单元，用于采用PY近似，建立包含所述参考作用点模型的直接相关函数和总相关函数的闭合方程：An approximation unit for establishing a closed equation containing the direct correlation function and the total correlation function of the reference point model using the PY approximation:
其中，Cαγ(r)为直接相关函数，hαγ(r)为总相关函数，kB为玻尔兹曼常数，T为绝对温度；uαγ(r)为势能函数；Among them, C αγ (r) is the direct correlation function, h αγ (r) is the total correlation function, k B is the Boltzmann constant, T is the absolute temperature; u αγ (r) is the potential energy function;
所述势能函数uαγ(r)仅包括氢键和范德华力。The potential energy function u αγ (r) includes only hydrogen bonds and van der Waals forces.
建模模块，用于建立所述表面活性剂高分子参考作用点模型积分方程；a modeling module for establishing the integral equation of the surfactant polymer reference point model integral equation;
具体的，所述建模模块利用h(r)＝∫dr'∫dr”ω(|r-r'|)C(|r'-r”|)[ω(r”)+ρh(r”)]建立所述高分子参考作用点模型积分方程，其中：ρ为活性剂的分子数密度，C(r)、h(r)和ω(r)分别为直接相关函数、总相关函数以及分子内相关函数。Specifically, the modeling module uses h(r)=∫dr'∫dr"ω(|r-r'|)C(|r'-r"|)[ω(r")+ρh(r" )] to establish the integral equation of the polymer reference point model, wherein: ρ is the molecular number density of the active agent, C(r), h(r) and ω(r) are the direct correlation function, total correlation function and molecular Internal correlation function.
第二计算模块，用于根据所述表面活性剂分子构型及预设温度，计算所述闭合方程和所述高分子参考作用点模型积分方程，得到对应所述预设温度的直接相关函数的表达式和总相关函数的表达式；The second calculation module is configured to calculate the closed equation and the integral equation of the polymer reference action point model according to the molecular configuration of the surfactant and the preset temperature, and obtain the direct correlation function corresponding to the preset temperature. expressions and expressions of the total correlation function;
第三计算模块，用于根据所述分子内相关函数的表达式、直接相关函数的表达式和总相关函数的表达式，计算得到所述预设温度对应的表面活性剂的X-光散射强度；The third calculation module is configured to calculate the X-ray scattering intensity of the surfactant corresponding to the preset temperature according to the expression of the intramolecular correlation function, the expression of the direct correlation function and the expression of the total correlation function ;
具体的，所述第三计算模块包括：Specifically, the third computing module includes:
第二计算单元，用于根据所述分子内相关函数的表达式、直接相关函数的表达式和总相关函数的表达式，得到所述预设温度对应的表面活性剂的结构因子：The second calculation unit is configured to obtain the structure factor of the surfactant corresponding to the preset temperature according to the expression of the intramolecular correlation function, the expression of the direct correlation function and the expression of the total correlation function:
其中，分别为ω(r)和C(r)的傅里叶变换形式；in, are the Fourier transform forms of ω(r) and C(r), respectively;
第三计算单元，用于根据所述结构因子，计算得到所述预设温度对应的表面活性剂的X-光散射强度：The third calculation unit is configured to calculate the X-ray scattering intensity of the surfactant corresponding to the preset temperature according to the structure factor:
其中，xα为α基团组分数，bα(k)为α基团散射因子，NS为单体原子基团数。Among them, x α is the number of α groups, b α (k) is the scattering factor of α groups, and N S is the number of monomer atom groups.
判断模块，用于根据所述多个不同预设温度一一对应的所述X-光散射强度，判断所述表面活性剂的结构稳定性。A judgment module, configured to judge the structural stability of the surfactant according to the X-ray scattering intensities corresponding to the plurality of different preset temperatures one-to-one.
其中，所述判断模块包括：Wherein, the judging module includes:
第二获取单元，用于获取所述多个不同预设温度一一对应的所述X-光散射强度；a second acquiring unit, configured to acquire the X-ray scattering intensities corresponding to the plurality of different preset temperatures one-to-one;
第一判断单元，用于判断所述多个不同预设温度一一对应的X-光散射强度的聚合峰峰值变化最大值是否小于第一阈值，如果是，进行下一步骤；如果否，则所述表面活性剂结构不稳定；a first judgment unit, configured to judge whether the maximum value of the aggregated peak-to-peak variation of the X-ray scattering intensities corresponding to the plurality of different preset temperatures is smaller than the first threshold, and if so, go to the next step; if not, then The surfactant structure is unstable;
第二判断单元，用于判断所述多个不同预设温度一一对应的X-光散射强度的聚合峰的位置变化最大值是否小于第二阈值，如果是，进行下一步骤；如果否，则所述表面活性剂结构不稳定；The second judgment unit is configured to judge whether the maximum position change of the polymerization peaks of the X-ray scattering intensities corresponding to the plurality of different preset temperatures one-to-one is smaller than the second threshold, and if so, go to the next step; if not, Then the surfactant structure is unstable;
第三判断单元，用于判断所述多个不同预设温度一一对应的X-光散射强度的无定形峰的位置变化最大值是否小于第三阈值，如果是，所述表面活性剂结构稳定，如果否，则所述表面活性剂结构不稳定。A third judging unit, configured to judge whether the maximum position change of the amorphous peaks of the X-ray scattering intensities corresponding to the plurality of different preset temperatures one-to-one is smaller than a third threshold, and if so, the surfactant structure is stable , if not, the surfactant structure is unstable.
本实施例中高分子表面活性剂结构稳定性判断系统，采用PY近似，结合PRISM理论，得到描述预设温度下所述表面活性剂的直接相关函数、总相关函数以及分子内相关函数，从而获得XRSI。通过计算多个不同预设温度下表面活性剂的XRSI，从而判断所述表面活性剂的结构稳定性。相比于实验量测高分子表面活性剂的XRSI，本发明可以降低实验成本，缩短研发周期，提高工作效率，为实验合成新型高分子表面活性剂提供了重要工具。In this example, the system for judging the structural stability of the polymer surfactant adopts the PY approximation and combines the PRISM theory to obtain the direct correlation function, total correlation function and intramolecular correlation function describing the surfactant at the preset temperature, thereby obtaining XRSI . By calculating the XRSI of the surfactant at a plurality of different preset temperatures, the structural stability of the surfactant can be judged. Compared with the XRSI of the experimental measurement of the polymer surfactant, the present invention can reduce the experimental cost, shorten the research and development cycle, improve the work efficiency, and provide an important tool for the experimental synthesis of a new polymer surfactant.
需要说明的是，在本发明申请文件中，所述直接相关函数的表达式、总相关函数的表达式以及分子内相关函数的表达式，根据计算结果的不同，可以为矩阵形式的表达式，也可以为已知参数的函数表达式，从而表达其所代表的意义。It should be noted that, in the application documents of the present invention, the expression of the direct correlation function, the expression of the total correlation function and the expression of the intramolecular correlation function may be expressions in matrix form according to different calculation results, It can also be a function expression with known parameters to express the meaning it represents.
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下，在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。The above description of the disclosed embodiments enables any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
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