WO2022100391A1 - 一种高压交流电缆绝缘用预交联料存储寿命检测方法 - Google Patents

一种高压交流电缆绝缘用预交联料存储寿命检测方法 Download PDF

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WO2022100391A1
WO2022100391A1 PCT/CN2021/125231 CN2021125231W WO2022100391A1 WO 2022100391 A1 WO2022100391 A1 WO 2022100391A1 CN 2021125231 W CN2021125231 W CN 2021125231W WO 2022100391 A1 WO2022100391 A1 WO 2022100391A1
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linking
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黎小林
傅明利
侯帅
惠宝军
朱闻博
伍国兴
谢宏
陈潇
徐曙
冯宾
张逸凡
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CSG Electric Power Research Institute
Shenzhen Power Supply Bureau Co Ltd
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CSG Electric Power Research Institute
Shenzhen Power Supply Bureau Co Ltd
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Priority to US17/912,541 priority patent/US12553843B2/en
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N25/00—Investigating or analyzing materials by the use of thermal means
    • G01N25/02—Investigating or analyzing materials by the use of thermal means by investigating changes of state or changes of phase; by investigating sintering
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N17/00—Investigating resistance of materials to the weather, to corrosion, or to light
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N25/00—Investigating or analyzing materials by the use of thermal means
    • G01N25/20—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/44—Resins; Plastics; Rubber; Leather
    • G01N33/442—Resins; Plastics

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  • the invention relates to the field of performance testing of high-voltage AC cable insulation materials, in particular to a storage life detection method of a pre-crosslinked material for high-voltage AC cable insulation.
  • the insulating layer of the high-voltage AC cable is made of cross-linked polyethylene as the main insulating material.
  • the most widely used method to realize the cross-linking of polyethylene is the chemical cross-linking method.
  • the principle is the free radicals generated by the thermal decomposition of the peroxide cross-linking agent.
  • the linear structure polyethylene is cross-linked into a cross-linked polyethylene with a network structure, and the cross-linked extruded material is a cross-linked polyethylene pre-cross-linking material.
  • the production process of the pre-crosslinked material is to add 0.2% antioxidant to the polyethylene at the mixing temperature of 130-250 °C, and then mix it uniformly in the screw mixer and then heat it at 110-120 °C.
  • DCP Dicumyl Peroxide
  • the cross-linking agent DCP is a strong oxidant. During the storage process before the pre-cross-linked pellets are put into the cable manufacturing process, a certain amount of DCP will be spontaneously decomposed, resulting in a decrease in the DCP content in the pre-cross-linked material.
  • DCP is the initiator of the cross-linking reaction, which has a significant impact on the efficiency of the cross-linking reaction and the cross-linking density of the final product, so the pre-cross-linking material with different storage time will be due to There are differences in the activity of different DCP content, which directly affects the performance of the finished cable insulation layer.
  • the activity and shelf life of the pre-crosslinkers are crucial to the performance of the cable insulation.
  • the embodiment of the present invention provides a method for detecting the storage life of a pre-cross-linked material for high-voltage AC cable insulation, which can determine the aging time and temperature required for an accelerated aging test of the pre-cross-linked material, and the pre-cross-linked material for high-voltage AC cable insulation. The storage life is tested.
  • An embodiment of the present invention provides a method for detecting the storage life of a pre-crosslinked material for high-voltage AC cable insulation, including:
  • the pre-cross-linked material is taken and pressed into a tablet to obtain a reference cross-linked polyethylene, wherein the pre-cross-linked material is a new pre-cross-linked material without aging;
  • the preset heating time is extended according to the preset step size, and the result obtained by re-testing
  • the cross-linking degree test data and the mechanical property test data are compared with the cross-linking degree reference data and the cross-linking degree test data, until the first comparison result does not fall within the first error tolerance range, or the second comparison result does not fall within the second error tolerance range;
  • the cross-linking material is an expired pre-cross-linking material
  • ⁇ is the half-life of the cross-linking agent at the temperature T
  • t is the time that the cross-linking agent is stored at the temperature T
  • the heating time of the expired pre-cross-linking material is deducted from the step size and converted into normal temperature time to obtain the storage life of the pre-cross-linking material.
  • measure the dielectric properties of the reference cross-linked polyethylene to obtain dielectric property reference data measure the dielectric properties of the cross-linked polyethylene prepared from the expired pre-cross-linked material, and obtain the dielectric property testing data , compare the dielectric property reference data and the dielectric property test data, and verify the deterioration of the expired pre-crosslinking material.
  • cross-linking degree of the reference cross-linked polyethylene and the cross-linking degree of the cross-linked polyethylene prepared from the accelerated aging pre-cross-linked material are measured by DSC test and thermal extension test.
  • the mechanical properties include: tensile strength, elastic modulus, and elongation at break; and the dielectric properties include: DC conductivity, AC breakdown field strength, relative permittivity, and dielectric loss tangent.
  • the embodiment of the present invention provides a method for detecting the storage life of a pre-cross-linked material for high-voltage AC cable insulation. Its cross-linking degree, mechanical properties and dielectric properties are measured as reference values; the pre-cross-linked material is accelerated and aged by heating, and the cross-linking degree of the cross-linked polyethylene obtained by pressing the pre-cross-linked material after accelerated aging is measured.
  • the decomposition rate calculation formula and the calculation formula of the half-life change with temperature are converted into normal temperature time after the heating time is deducted from the step size, and the storage life of the pre-crosslinked material is obtained.
  • the accelerated aging is carried out by heating, which shortens the test period and reduces the consumption of materials.
  • the cross-linking degree and mechanical properties of polyethylene are compared, and the aging time required for the accelerated aging test of the pre-cross-linking material is determined by combining the decomposition rate of the cross-linking agent in the pre-cross-linking material and the law of the change of half-life with temperature changes. and temperature to realize the detection of the storage life of pre-crosslinked materials.
  • FIG. 1 is a schematic flowchart of a method for detecting the storage life of a pre-crosslinked material for insulation of a high-voltage AC cable according to an embodiment of the present invention.
  • v is the reaction rate
  • C is the DCP concentration
  • K is the reaction rate constant.
  • C 0 is the initial concentration of DCP in the pre-crosslinking material.
  • Formula (3) shows that the decomposition rate of DCP increases with the prolongation of storage time, so it will affect the activity of the pre-crosslinking material.
  • the formula for calculating the reaction rate constant K can be obtained from the Arrhenius formula:
  • R is the gas constant
  • E is the apparent activation energy
  • A is the frequency factor. Therefore, at different temperatures, the ratio of the reaction rate constants is:
  • the DCP decomposition half-life ⁇ is defined as the time required for the DCP concentration to drop to half of the initial concentration at a certain ambient temperature. Substituting ⁇ into the calculation formula of the DCP decomposition rate can be solved:
  • ⁇ 0 is the half-life of DCP at a known temperature T 0 .
  • the decomposition half-life of DCP at room temperature (30°C) can be calculated to be 490 years, and the half-life at other temperatures can also be calculated.
  • the complete calculation results are shown in Table 1 below.
  • the content of DCP in the pre-crosslinked material after being stored at room temperature for a certain period of time can be calculated.
  • the stability of the pre-crosslinking material mixed system and the rationality of the aging test duration should also be considered. The problem.
  • 70 °C is the test temperature for the accelerated aging test.
  • Table 1 the decomposition half-life of DCP is 157 days.
  • formula (7) that accelerated aging for 3.8 hours can equivalently achieve the effect of storage at 30 °C for half a year, while aging for 77 hours (approximately 77 hours) 3 days) can be equivalent to 10 years of storage at room temperature.
  • 70 °C is far less than the crosslinking process temperature, so this aging temperature takes into account the stability of the pre-crosslinking material system and the rationality of the test time.
  • FIG. 1 it is a schematic flowchart of a method for detecting the storage life of a pre-crosslinked material for insulation of a high-voltage AC cable according to an embodiment of the present invention.
  • the method includes:
  • steps S10 to S12 may specifically be:
  • cross-link the new pre-crosslinked material at 180 °C use a flat vulcanizer to mold into thin sheets with a thickness of 0.2 mm and 1.0 mm, and then use a cutter to cut into round or dumbbell-shaped samples.
  • the 0.2mm thick circular sample is used for the measurement of dielectric properties
  • the 1.0mm thick dumbbell-shaped sample is used for the measurement of thermal extension and mechanical properties.
  • the cross-linking degree of the cross-linked polyethylene samples prepared from the new pre-cross-linking materials, and the measurement results are used as the standard for the subsequent evaluation of the activity and life of the pre-cross-linking materials.
  • the degree of crosslinking can be measured by DSC test and thermal extension test; mechanical properties include tensile strength, elastic modulus and elongation at break; dielectric properties include DC conductivity, AC breakdown field strength, relative permittivity and Dielectric loss tangent.
  • steps S13 to S16 may specifically be:
  • steps S19 to S20 may specifically be as follows: if the performance measurement results of the aged pre-cross-linked material and the sample remain basically unchanged compared with the new-factory pre-cross-linked material and the sample, it indicates that the pre-cross-linked material is stored at room temperature. It still maintains good activity after half a year, and the storage life at room temperature is more than half a year.
  • aging at 70°C for 3.8 hours is the step size, that is, it is equivalent to be stored at 30°C for half a year.
  • the aging time of the accelerated aging test is gradually extended to obtain an aging pre-crosslinking material with an equivalent normal temperature and a longer storage time. After completing the aging test of prolonging the aging time, press the corresponding material and test the cross-linking degree and mechanical properties of the sample until the sample with obvious changes in performance is obtained.
  • this test method also includes measuring the dielectric properties of the reference cross-linked polyethylene, obtaining reference data of dielectric properties, measuring the dielectric properties of the cross-linked polyethylene prepared from the expired pre-cross-linked material, and obtaining Dielectric property test data, compare the dielectric property reference data and the dielectric property test data, and verify the deterioration of the expired pre-crosslinking material.
  • ⁇ is the half-life of the cross-linking agent at the temperature T
  • t is the time that the cross-linking agent is stored at the temperature T
  • step S22 may specifically be:
  • the accelerated aging time of the samples with obvious changes in crosslinking degree and mechanical properties was subtracted by an aging time extension step, and the storage time at 70 °C and 30 °C was converted to obtain the pre-crosslinked material at 30 °C. storage life.
  • the embodiment of the present invention provides a method for detecting the storage life of a pre-cross-linked material for high-voltage AC cable insulation.
  • a new pre-cross-linked material is taken for tableting to obtain cross-linked polyethylene, and its cross-linking degree, mechanical properties and dielectric properties are measured.
  • Take the measurement result as a reference value; accelerate the aging of the pre-cross-linked material by heating, and measure the cross-linking degree, mechanical properties and dielectric properties of the cross-linked polyethylene obtained by pressing the pre-cross-linked material after accelerated aging.
  • the invention can shorten the test period and reduce the material consumption by adopting the heating method to accelerate the aging.
  • the cross-linking degree and mechanical properties of the pre-cross-linking materials are compared, and the aging time and temperature required for the accelerated aging test of the pre-cross-linking materials are determined by combining the decomposition rate and half-life of the cross-linking agent in the pre-cross-linking materials. , to realize the detection of the storage life of pre-crosslinked materials.

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Abstract

一种高压交流电缆绝缘用预交联料存储寿命检测方法，包括：取新预交联料压片得交联聚乙烯，测量其交联度、力学特性及介电性能，将测量结果作为参考值；通过加热加速老化预交联料，并测量加速老化后的预交联料压片得的交联聚乙烯的交联度、力学特性及介电性能，将该测量结果与参考值对比，当结果落在误差允许范围内时，根据预设步长加长加热时间，直到结果不全落在误差允许范围内；根据交联剂分解率计算公式与半衰期随温度变化计算公式，将加热时间减去步长后转化为常温时间，得到预交联料存储寿命，通过加热加速老化预交联料，取交联度、力学特性及介电性能作为活性标准，根据交联剂分解率和半衰期计算得预交联料存储寿命。

Description

一种高压交流电缆绝缘用预交联料存储寿命检测方法 技术领域
本发明涉及高压交流电缆绝缘料性能测试领域，尤其涉及一种高压交流电缆绝缘用预交联料存储寿命检测方法。
背景技术
高压交流电缆的绝缘层是以交联聚乙烯作为主绝缘材料，实现聚乙烯交联使用最广泛的方法为化学交联法，其原理为借助过氧化物交联剂受热分解产生的游离自由基将线性结构的聚乙烯交联为具有网状结构的交联聚乙烯，交联挤出的材料是交联聚乙烯预交联料。预交联料的生产工艺为在130-250℃的混炼温度下向聚乙烯中加入质量分数为0.2％的抗氧剂，在螺杆混炼机内混炼均匀后再在110-120℃下的混炼温度下加入质量分数为2％的交联剂，通常为过氧化二异丙苯(Dicumyl Peroxide,DCP)，混炼均匀后再经螺杆挤出机挤出并切粒，经振动筛脱水后形成预交联料成品。
交联剂DCP是强氧化剂，在预交联粒投入电缆制造环节之前的存储过程中，会有一定量的DCP自发分解掉，导致预交联料中的DCP含量下降。在预交联料的正式交联挤出中，DCP是交联反应的引发剂，对交联反应的效率及最终产品的交联密度有显著影响，所以存储时间不同的预交联料会由于DCP含量的不同存在活性上的差异，直接影响到成品电缆绝缘层的性能。
因此，预交联料的活性及存储寿命对电缆绝缘层的性能至关重要。但目前还没有成熟的检测方法来对高压交流电缆绝缘用预交联料的活性和存储寿命做出判断，也没有对预交联料进行加速老化试验所需老化时间及温度的确定方法。
发明内容
本发明实施例提供一种高压交流电缆绝缘用预交联料存储寿命检测方法， 能确定对预交联料进行加速老化试验所需老化时间及温度，以及对高压交流电缆绝缘用预交联料的存储寿命做出检测。
本发明一实施例提供一种高压交流电缆绝缘用预交联料存储寿命检测方法，包括：
取预交联料进行压片，得到参考交联聚乙烯，其中，所述预交联料为未经老化的新预交联料；
测量所述参考交联聚乙烯的交联度，得到交联度参考数据；
测试所述参考交联聚乙烯的力学特性，得到力学特性参考数据；
将所述预交联料在预设温度下加热预设时间以获得加速老化的预交联料；
将所述加速老化的预交联料压片，得到交联聚乙烯；
测量由所述加速老化的预交联料制得的交联聚乙烯的交联度，得到交联度检测数据；
测试由所述加速老化的预交联料制得的交联聚乙烯的力学特性，得到力学特性检测数据；
比较所述交联度参考数据和所述交联度检测数据，得到第一比较结果；
比较所述力学特性参考数据和所述力学特性检测数据，得到第二比较结果；
当所述第一比较结果落在第一误差允许范围内，并且所述第二比较结果落在第二误差允许范围内时，根据预设的步长延长加热的预设时间，重新测试得所述交联度检测数据和所述力学特性检测数据，并与所述交联度参考数据和所述交联度检测数据进行比较，直到所述第一比较结果没有落在所述第一误差允许范围内，或者，所述第二比较结果没有落在所述第二误差允许范围内；
当所述第一比较结果没有落在所述第一误差允许范围内，或者，所述第二比较结果没有落在所述第二误差允许范围内时，记录该加热时间，该加速老化的预交联料为过期预交联料；
获取基于预交联料中交联剂分解率的计算公式：
Figure PCTCN2021125231-appb-000001
其中，τ为在温度T下交联剂的半衰期，t为交联剂保存在温度T中经过的时间；
结合所述交联剂半衰期随温度变化的计算公式，将所述过期预交联料的加热时间减去所述步长后转化为常温时间，得到所述预交联料的存储寿命。
进一步的，测量所述参考交联聚乙烯的介电性能，得到介电性能参考数据，测量由所述过期预交联料制得的交联聚乙烯的介电性能，得到介电性能检测数据，比较所述介电性能参考数据和所述介电性能检测数据，验证所述过期预交联料的劣化。
其中，所述参考交联聚乙烯的交联度和所述加速老化的预交联料制得的交联聚乙烯的交联度通过DSC测试和热延伸试验进行测量。
而且，所述力学特性包括：拉伸强度、弹性模量及断裂伸长率；所述介电性能包括：直流电导率、交流击穿场强、相对介电常数及介质损耗角正切。
本发明对比现有技术有如下的有益效果，本发明实施例提供了高压交流电缆绝缘用预交联料存储寿命检测方法，取新的预交联料进行压片，得到交联聚乙烯，测量其交联度、力学特性及介电性能，将测量结果作为参考值；通过加热加速老化预交联料，并测量加速老化后的预交联料压片得的交联聚乙烯的交联度、力学特性及介电性能，将该测量结果与参考值对比，当结果落在误差允许范围内时，根据预设步长加长加热时间，直到结果不全落在误差允许范围内；根据交联剂分解率计算公式与半衰期随温度变化计算公式，将加热时间减去步长后转化为常温时间，得到预交联料存储寿命。本发明通过采取加热的方式进行加速老化，缩短了试验周期、减少了材料耗费量，根据测量加速老化的预交联料制得的交联聚乙烯的交联度、力学特性，与参考交联聚乙烯的交联度、力学特性进行对比，通过结合预交联料中的交联剂分解率和半衰期随温度变化而 变化的规律，从而确定对预交联料进行加速老化试验所需老化时间及温度，实现预交联料存储寿命的检测。
附图说明
图1是本发明一实施例提供的一种高压交流电缆绝缘用预交联料存储寿命检测方法流程示意图。
具体实施方式
下面将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作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。
为说明加速老化实验参数的确定和计算方法，这里先简要介绍交联剂DCP的半衰期及分解率计算方面的理论。
研究表明，聚乙烯的交联是一级反应，其反应动力学方程为
Figure PCTCN2021125231-appb-000002
式(1)中v为反应速率，C为DCP浓度，K为反应速率常数。
由式(1)可解得：
C＝C 0·e -K·t，     (2)
式(2)中C 0为预交联料中DCP初始浓度。
因此通过反应动力学理论可得到时刻t时，预交联料内DCP分解率X的计算公式为：
Figure PCTCN2021125231-appb-000003
式(3)说明，DCP的分解率随保存时间延长而增大，因此会影响到预交联料的活性。而反应速率常数K的计算公式可以由阿累尼乌斯公式得到：
Figure PCTCN2021125231-appb-000004
式(4)中R为气体常数，E为表观活化能，A为频率因子。因此在不同温度下，反应速率常数的比值为：
Figure PCTCN2021125231-appb-000005
DCP分解半衰期τ定义为在某一环境温下DCP浓度下降为初始浓度的一半所需的时间。将τ代入DCP分解率的计算公式可解得：
Figure PCTCN2021125231-appb-000006
将式(6)代入分解率计算公式(3)可得：
Figure PCTCN2021125231-appb-000007
同时由DCP分解半衰期τ和反应速率常数K的关系式(6)和反应速率常数比值的计算式(5)并结合已测量出的某温度下的DCP半衰期计算得到其他温度下预交联料中DCP的半衰期，计算公式为：
Figure PCTCN2021125231-appb-000008
式(8)中τ 0为已知某温度T 0下的DCP半衰期。
根据已有实验数据及结论可计算出常温(30℃)下DCP分解半衰期为490年，同样也能计算出其他温度下的半衰期，完整计算结果如下表1所示。
表1不同温度下预交联料内DCP分解半衰期
Figure PCTCN2021125231-appb-000009
结合表1数据和DCP分解率计算公式(7)便可计算得到在室温下存储一定时间后预交联料内DCP的含量。为在预交联料的加速老化实验中达到同样的 DCP分解率，以实现等效室温下存储相应时长的效果，还应该同时考虑到预交联料混合体系的稳定性和老化试验时长合理性的问题。
在此补充说明，提高存储温度的确可以加速DCP的自发分解，以实现加速老化预交联料这一目的。但同时也会影响到预交联料内的聚乙烯分子，使其由于预交联料混合体系中活性自由基数量增多自行发生微弱的交联，影响后续试验结果。但因为设定的加速老化试验温度通常小于实际交联工艺温度(约180℃)，所以老化过程中引发的聚乙烯交联现象可以忽略不计。而且从化学反应原理的角度考虑，由于交联反应是放热反应，因此提高温度，反应平衡会向左移动，交联反应也会在一定程度上受到抑制，交联产物在预交联料体系内所占比例也是减小的，可以认为加速老化实验对预交联料活性的影响主要还是由DCP自发分解而不是影响了聚乙烯分子本身所带来。
综合以上结论，我们选择70℃作为加速老化试验的试验温度。在此温度下，由表1可知DCP的分解半衰期为157天，由式(7)计算可知进行3.8小时的加速老化便可等效实现30℃下存储半年的效果，而老化77个小时(约3天)便可等效常温下存储10年。且70℃远小于交联工艺温度，因此这个老化温度兼顾了预交联料体系的稳定性和试验时长的合理性。
参见图1，是本发明一实施例提供的一种高压交流电缆绝缘用预交联料存储寿命检测方法流程示意图。所述方法包括：
S10、取预交联料进行压片，得到参考交联聚乙烯，其中，所述预交联料为未经老化的新预交联料。
S11、测量所述参考交联聚乙烯的交联度，得到交联度参考数据。
S12、测试所述参考交联聚乙烯的力学特性，得到力学特性参考数据。
示例地，步骤S10～S12具体可以是：
先将新出厂预交联料在180℃下交联，使用平板硫化机模压为厚度为0.2mm和1.0mm的薄片，之后使用切刀裁剪成圆形或哑铃形试样。其中0.2mm厚圆形试样用于介电性能测量，1.0mm厚哑铃形试样用于热延伸及力学性能的测量， 并按照GB/T 36965-2018中的DSC试验测量交联度方法得到新出厂预交联料制得交联聚乙烯试样的交联度，将测量结果作为后续评估预交联料活性和寿命的标准。
S13、将所述预交联料在预设温度下加热预设时间以获得加速老化的预交联料。
S14、将所述加速老化的预交联料压片，得到交联聚乙烯。
S15、测量由所述加速老化的预交联料制得的交联聚乙烯的交联度，得到交联度检测数据。
S16、测试由所述加速老化的预交联料制得的交联聚乙烯的力学特性，得到力学特性检测数据。
其中，可通过DSC测试和热延伸试验测量交联度；力学特性包括拉伸强度、弹性模量及断裂伸长率；介电性能包括直流电导率、交流击穿场强、相对介电常数及介质损耗角正切。
示例地，步骤S13～S16具体可以是：
进行新出厂预交联料的加速老化试验。将新出厂预交联料盛放于烧杯内，烧杯置于恒温烘箱中，烘箱温度设置为70℃，进行3.8小时的加速老化，等效30℃下存储半年。完成后得到老化预交联料，在室温环境下静置24小时。之后进行压片、交联度及力学性能的测试。
S17、比较所述交联度参考数据和所述交联度检测数据，得到第一比较结果。
S18、比较所述力学特性参考数据和所述力学特性检测数据，得到第二比较结果。
S19、当所述第一比较结果落在第一误差允许范围内，并且所述第二比较结果落在第二误差允许范围内时，根据预设的步长延长加热的预设时间，重新测试得所述交联度检测数据和所述力学特性检测数据，并与所述交联度参考数据和所述交联度检测数据进行比较，直到所述第一比较结果没有落在所述第一误 差允许范围内，或者，所述第二比较结果没有落在所述第二误差允许范围内。
S20、当所述第一比较结果没有落在所述第一误差允许范围内，或者，所述第二比较结果没有落在所述第二误差允许范围内时，记录该加热时间，该加速老化的预交联料为过期预交联料。
示例地，步骤S19～S20具体可以为：若老化预交联料及试样的性能测量结果和新出厂预交联料及试样相比基本保持不变，则表明该预交联料在室温下存储半年后仍保持了良好的活性，室温下存储寿命大于半年。
为得到该预交联料在常温下的存储寿命，以70℃下老化3.8小时为步长，即等效30℃下保存半年。逐步延长加速老化试验的老化时间，得到等效常温下保存时间更久的老化预交联料。完成延长老化时间的老化试验后进行相应材料的压片及试样交联度和力学性能测试，直至得到性能产生明显变化的试样为止。
进一步地，本测试方法还包括测量所述参考交联聚乙烯的介电性能，得到介电性能参考数据，测量由所述过期预交联料制得的交联聚乙烯的介电性能，得到介电性能检测数据，比较所述介电性能参考数据和所述介电性能检测数据，验证所述过期预交联料的劣化。
S21、获取基于所述预交联料中交联剂分解率的计算公式：
Figure PCTCN2021125231-appb-000010
其中，τ为在温度T下交联剂的半衰期，t为交联剂保存在温度T中经过的时间；
S22、结合所述交联剂半衰期随温度变化的计算公式，将所述过期预交联料的加热时间减去所述步长后转化为常温时间，得到所述预交联料的存储寿命。
示例地，步骤S22具体可以为：
将交联度和力学性能性能产生明显变化的试样的加速老化时间减去一个老化时间延长的步长并进行70℃与30℃下存储时间换算后得到该预交联料在30℃下的存储寿命。
本发明实施例提供了高压交流电缆绝缘用预交联料存储寿命检测方法，取新的预交联料进行压片，得到交联聚乙烯，测量其交联度、力学特性及介电性能，将测量结果作为参考值；通过加热加速老化预交联料，并测量加速老化后的预交联料压片得的交联聚乙烯的交联度、力学特性及介电性能，将该测量结果与参考值对比，当结果落在误差允许范围内时，根据预设步长加长加热时间，直到结果不全落在误差允许范围内；根据交联剂分解率计算公式与半衰期随温度变化计算公式，将加热时间减去步长后转化为常温时间，得到预交联料存储寿命。本发明通过采取加热的方式进行加速老化可缩短试验周期、减少材料耗费量，根据测量加速老化的预交联料制得的交联聚乙烯的交联度、力学特性，与参考交联聚乙烯的交联度、力学特性进行对比，通过结合预交联料中的交联剂分解率和半衰期随温度变化而变化的规律，从而确定对预交联料进行加速老化试验所需老化时间及温度，实现预交联料存储寿命的检测。
以上所述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，这些改进和润饰也视为本发明的保护范围。

Claims (6)

  1. 一种高压交流电缆绝缘用预交联料存储寿命检测方法，其特征在于，包括：
    取预交联料进行压片，得到参考交联聚乙烯，其中，所述预交联料为未经老化的新预交联料；
    测量所述参考交联聚乙烯的交联度，得到交联度参考数据；
    测试所述参考交联聚乙烯的力学特性，得到力学特性参考数据；
    将所述预交联料在预设温度下加热预设时间以获得加速老化的预交联料；
    将所述加速老化的预交联料压片，得到交联聚乙烯；
    测量由所述加速老化的预交联料制得的交联聚乙烯的交联度，得到交联度检测数据；
    测试由所述加速老化的预交联料制得的交联聚乙烯的力学特性，得到力学特性检测数据；
    比较所述交联度参考数据和所述交联度检测数据，得到第一比较结果；
    比较所述力学特性参考数据和所述力学特性检测数据，得到第二比较结果；
    当所述第一比较结果落在第一误差允许范围内，并且所述第二比较结果落在第二误差允许范围内时，根据预设的步长延长加热的预设时间，重新测试得所述交联度检测数据和所述力学特性检测数据，并与所述交联度参考数据和所述交联度检测数据进行比较，直到所述第一比较结果没有落在所述第一误差允许范围内，或者，所述第二比较结果没有落在所述第二误差允许范围内；
    当所述第一比较结果没有落在所述第一误差允许范围内，或者，所述第二比较结果没有落在所述第二误差允许范围内时，记录该加热时间，该加速老化的预 交联料为过期预交联料；
    获取基于所述预交联料中交联剂分解率的计算公式：
    Figure PCTCN2021125231-appb-100001
    其中，τ为在温度T下交联剂的半衰期，t为交联剂保存在温度T中经过的时间；
    结合所述交联剂半衰期随温度变化的计算公式，将所述过期预交联料的加热时间减去所述步长后转化为常温时间，得到所述预交联料的存储寿命。
  2. 如权利要求1所述的高压交流电缆绝缘用预交联料存储寿命检测方法，其特征在于，还包括，
    测量所述参考交联聚乙烯的介电性能，得到介电性能参考数据；
    测量由所述过期预交联料制得的交联聚乙烯的介电性能，得到介电性能检测数据；
    比较所述介电性能参考数据和所述介电性能检测数据，验证所述过期预交联料的劣化。
  3. 如权利要求1所述的高压交流电缆绝缘用预交联料存储寿命检测方法，其特征在于，测量所述参考交联聚乙烯的交联度，得到交联度参考数据，具体为：
    通过DSC测试和热延伸试验测量所述参考交联聚乙烯的交联度，得到交联度参考数据。
  4. 如权利要求1所述的高压交流电缆绝缘用预交联料存储寿命检测方法， 其特征在于，测量由所述加速老化的预交联料制得的交联聚乙烯的交联度，得到交联度检测数据，具体为：
    通过DSC测试和热延伸试验测量由所述加速老化的预交联料制得的交联聚乙烯的交联度，得到交联度检测数据。
  5. 如权利要求1所述的高压交流电缆绝缘用预交联料存储寿命检测方法，其特征在于，所述力学特性，包括：拉伸强度、弹性模量及断裂伸长率。
  6. 如权利要求1所述的高压交流电缆绝缘用预交联料存储寿命检测方法，其特征在于，所述介电性能，包括：直流电导率、交流击穿场强、相对介电常数及介质损耗角正切。
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