陈独旭¹,王冬至¹,葛曷一¹,刘小康²,杜润生²,韩凯洋¹

(1. 济南大学材料科学与工程学院,山东济南250022;2. 兰陵益新矿业科技有限公司,山东临沂277700)

引用格式：陈独旭,王冬至,葛曷一,等.碱处理对球形硅微粉性能的影响[J].中国粉体技术,2023,29(3)：81-91.

CHEN D X,WANG D Z,GE H Y,et al.Effect of alkali treatment on surface modification of spherical silicon powder[J].China Powder Science and Technology,2023,29(3)：81-91.

DOI：10.13732/j.issn.1008-5548.2023.03.008

收稿日期： 2022-01-01,修回日期：2022-01-15，在线出版时间：2023-04-12 14:47。

基金项目：山东省自然科学基金项目,编号：SZR2125。

第一作者简介：陈独旭(1997—),男,硕士研究生,研究方向为无机粉体的表面改性。E-mail：895037455@qq.com。

通信作者简介：王冬至(1978—),男,副教授,博士,硕士生导师,研究方向为树脂基复合材料。E-mail：mse-wangdz@ujn.edu.cn。

摘要： 使用硅烷偶联剂进行表面改性是1种工业上常用的球形硅微粉表面改性方法。然而球形硅微粉在生产过程中经过的高温球化工艺使其表面呈现化学惰性,需要一定的表面处理才能有更好的改性效果。为探究碱处理对球形硅微粉表面改性各项性能的影响,选用NaOH对球形硅微粉表面进行处理,通过表面形貌和表面接触角来确定最佳处理时间;选用γ-缩水甘油醚氧丙基三甲氧基硅烷(KH560)、γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH570)两种硅烷偶联剂对碱处理前后球形硅微粉进行表面改性并表征了吸油值、活化指数和接触角;将改性球形硅微粉与环氧树脂复合制成样品进行力学性能与导热系数测试。结果表明：碱处理后用3%质量分数的KH570、KH560分别对球形硅微粉进行改性,此时球形硅微粉的活化指数分别为78.9%、28.7%,接触角分别为126.51°、117.28°,吸油值分别为25.95%、26.70%;制得复合样品的弯曲强度分别提升18.2%、25.9%,冲击强度分别提升2.5%、21.6%,导热系数分别提升6.32%、11.82%。碱处理对KH560、KH570改性球形硅微粉的改性效果及其制成复合样品的力学导热性能均有提升。

关键词： 球形硅微粉;碱处理;硅烷偶联剂;表面改性;环氧树脂

Abstract：Surface modification with silane coupling agent is a commonly used surface modification method of spherical silicon powder in industry.However,the surface of spherical silicon micropowder is chemically inert due to the high-temperature spheroidization process in the production process,and a certain surface treatment is needed to have a better modification effect.In order to explore the influence of alkali treatment on the surface modification of spherical silicon powder,NaOH was used to treat the surface of spherical silicon powder,and the best treatment time was determined by surface morphology and contact angle.The silane coupling agents,γ-glycidyl ether oxy propyl trimethoxysilane (KH560) and γ-methacryloxy propyl trimethoxysilane (KH570),were used to modify the surface of spherical silica powder respectively before and after alkali treatment.The oil absorption value,the activation index and the contact angle were characterized.The mechanical properties and the thermal conductivity of modified spherical silicon powder/epoxy resin were tested.The results show that spherical silica powder is modified with 3% KH570 and KH560 respectively after alkali treatment.At this time,the activation index,contact angle and oil absorption of spherical silica powder are 78.9% and 28.7%,126.51° and 117.28° respectively,and 25.95% and 26.70% respectively.The bending strength,impact strength and thermal conductivity of the composite samples are increased by 18.2% and 25.9%,2.5% and 21.6%,6.32% and 11.82% respectively.Alkali treatment can improve the modification effect of the silica powder,the thermal mechanics and thermal conductivity of composite samples.

Keywords：spherical silicon micropowder;alkali treatment;silane coupling agent;surface modification;epoxy resin

参考文献(References)：

[1]YANG D G,JANSEN K M B,WANG L G,et al.Micromechanical modeling of stress evolution induced during cure in a particle-filled electronic packaging polymer[J].IEEE Transactions on Components and Packaging Technologies,2005,27(4)：676-683.

[2]张超,白瑞钦,马勇,等.电子封装用环氧树脂基复合材料研究进展[J].工程塑料应用,2019,47(10)：144-149.

ZHANG C,BAI R Q,M Y,et al.Progress on research in epoxy resin matrix composites for electronic packaging[J].Engineering Plastics Application,2019,47(10)：144-149.

[3]ZHENG Y,ZOU B,YUAN L J.Structure and properties of novel epoxy resins containing naphthalene units and aliphatic chains[J].Iranian Polymer Journal,2013,22(5)：325-334.

[4]戴宏程.二氧化硅改性及其填充聚合物复合材料性能研究[D].武汉：武汉理工大学,2002.

DAI H C.Study on the modification of silica and properties of composites formed by the silica and polymer[D].Wuhan：Wuhan University of Technology,2002.

[5]漆乐俊,宋亮,陈建升.高填充高导热环氧复合材料的制备与性能研究[J].内蒙古科技大学学报,2016,35(4)：319-322.

QI L J,SONG L,CHEN J S.Study on preparation and properties of the highly-filled conductive epoxy composites[J].Journal of Inner Mongolia University of Science and Technology,2016,35(4)：319-322.

[6]SARITA K,SUSHEEL K,ANNAMARIA C,et al.Surface modification of inorganic nanoparticles for development of organic-inorganic nanocomposites：A review[J].Progress in Polymer Science,2013,38(8)：1232-1261.

[7]陈精华,李国一,胡新嵩,等.硅微粉对有机硅电子灌封胶性能的影响[J].有机硅材料,2011,25(2)：71-75.

CHEN J H,LI G Y,HU X S,et al.Effects of silica powder on the properties of silicone encapsulant[J].Silicone Material,2011,25(2)：71-75.

[8]高佳齐.环氧塑封料用硅微粉的超细粉碎及改性研究[D].绵阳：西南科技大学,2022.

GAO J Q.Study on superfine grinding and modification of silicon powder for epoxy plastic sealant[D].Mianyang：Southwest University of Science and Technology,2022.

[9]孙宇鹏,武智鹏,陈晓峰,等.硅烷偶联剂TPTS和表面活性剂PEG-400协同改性白炭黑/天然橡胶复合材料的制备及性能研究[J].橡胶科技,2023,21(3)：115-122.

SUN Y P,WU Z P,CHEN X F,et al.Preparation and properties of silica/natural rubber composites modified by silane coupling agent TPTS and surfactant PEG-400[J].Rubber Science and Technology,2023,21(3)：115-122.

[10]杨珂珂,李晓冬,曹家凯,等.耐热表面改性球形硅微粉的制备及其性能[J].中国粉体技术,2020,26(5)：60-65.

YANG K K,LI X D,CAO J K,et al.Preparation and properties of heat-resistant surface modified spherical silica powder[J].China Powder Science and Technology,2020,26(5)：60-65.

[11]YUKI N,MANABU F,HIDEKI H.Surface modification of silica powder by mild ball milling[J].Colloids and Surfaces A：Physicochemical and Engineering Aspects,2022,652：129888.

[12]WANG J,SUN S J,DING H,et al.A semiconductor-insulator heterojunction induced by hydroxyl groups formed on the surface of SiO₂ microspheres[J].Applied Surface Science,2020,531：147385.

[13]ABU B N,MAT S M,ALI U A,et al.Direct deposition of silver nanoplates on quartz surface by sequence pre-treatment hydroxylation and silanisation[J].MethodsX,2017,4：486-491.

[14]王永明,文娟,李家柱,等.酸碱处理对SiC粉体表面性质的影响研究[J].硅酸盐通报,2016,35(5)：1361-1366.

WANG Y M,WEN J,LI J Z,et al.Surface quality analysis of sic powder treated by acid and alkali solution[J].Bulletin of the Chinese Ceramic Society,2016,35(5)：1361-1366.

[15]SMARANIKA D,VIKAS N T,ASHOK K,et al.Enhancing functional properties of PVDF-HFP/BZT-BCT polymer-ceramic composites by surface hydroxylation of ceramic fillers[J].Ceramics International,2021,47(23)：33563-33576.

[16]TOM F O M,MICHAEL A M.Hydroxylation methods for mesoporous silica and their impact on surface functionalisation[J].Microporous and Mesoporous Materials,2021,317(0)：110989.

[17]刘菊耀,王国政,王蓟.微通道板表面羟基化工艺研究[J].半导体光电,2022,43(2)：353-357.

LIU J Y,WANG G Z,WANG J.Research on hydroxylation process of microchannel plate[J].semiconductor optoelectronics,2022,43(2)：353-357.

[18]汪杰.SiO₂微球负载TiO₂和金属硫化物复合光催化剂制备及其表征[D].北京：中国地质大学(北京),2021.

WANG J.Preparation and characterization of TiO₂ and metal sulfide composite photocatalyst supported by SiO₂ microspheres[D].Beijing：China University of Geosciences(Beijing),2021.

[19]陈和生,孙振亚,邵景昌.八种不同来源二氧化硅的红外光谱特征研究[J].硅酸盐通报,2011,30(4)：934-937.

CHEN H S,SUN Z Y,SHAO J C.Investigation on FT-IR spectroscopy for eight different sources of SiO₂[J].Bulletin of the Chinese Ceramic Society,2011,30(4)：934-937.

[20]张栋栋,温绍国,汪鹏主,等.改性硅微粉在天然橡胶中的性能研究[J].应用化工,2015,44(8)：1506-1509,1514.

ZHANG D D,WEN S G,WANG P Z,et al.Study on the performance of natural rubber composites filled with modification silicon powder[J].Applied Chemical Industry,2015,44(8)：1506-1509,1514.

[21]梁朝,李茹春,李春全,等.硅酸钙表面有机改性和形貌对填充PP复合材料力学性能的影响及机理[J/OL].材料导报,2022,36(23)：207-214.

LIANG C,LI R C,LI C Q,et al.Effect of surface organic modification and morphology of calcium silicate on the properties of PP composites and its mechanism[J/OL].Materials Reports,2022,36(23)：207-214.

[22]MEHRA N,MU L W,JI T,et al.Thermal transport in polymeric materials and across composite interfaces(Review)[J].Applied Materials Today,2018,12：92-130.