Effect of Plasma Modification on Bonding Performance of Lithium Aluminosilicate Glass-Polyurethane Interface

doi:10.16552/j.cnki.issn1001-1625.2025.1149

Abstract

Abstract:

The interfacial bonding performance between lithium aluminosilicate glass and polyurethane films directly impacts the structural safety and service reliability of aerospace transparent components. Plasma surface modification serves is an effective method to enhance interfacial bonding performance. Through plasma surface modification at varying rates on lithium aluminosilicate glass surfaces， this paper characterized the effect of surface modification using static contact angle measurement， scanning electron microscopy， and X-ray photoelectron spectroscopy， while quantitatively evaluating interfacial bonding strength via peel-off tests. Environmental stability assessments were conducted through combined wet-heat aging and ultraviolet irradiation experiments. Results demonstrates that when the plasma surface modification rate is 5 mm/s， the polar component of the glass surface energy increases to 42.87 mN/m， forming a uniform nanoscale roughness morphology on the surface， and the oxygen-containing functional groups achieves peak content under these conditions， indicating optimal surface modification outcomes. The composite of lithium aluminosilicate glass and polyurethane film has high visible light transmittance and low haze， and the interfacial peel strength is 23 620 N/m. After aging in wet-heat and ultraviolet environments， the modified interfaces maintain superior stability and minimal performance degradation. By controlling plasma surface modification rates， the surface energy state and chemical composition of lithium aluminosilicate glass can be effectively regulated， significantly enhancing its interfacial bonding with polyurethane. These findings provide valuable guidance for reliability design and process optimization of aerospace transparent component interfaces.

Key words: plasma modification, lithium aluminosilicate glass, surface energy, interfacial chemical composition, oxygen-containing functional group, peel strength, interfacial stability

CLC Number:

TB332

XU Shuang, XU Chi, TIAN Haodong, SHI Runqi, ZU Chengkui. Effect of Plasma Modification on Bonding Performance of Lithium Aluminosilicate Glass-Polyurethane Interface[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2026, 45(3): 1094-1104.

Figures/Tables 14

Table 1 Surface tension values of deionized water and diiodomethane

Test liquid	$γ L$ /（mN·m^-1）	$γ L d$ /（mN·m^-1）	$γ L p$ /（mN·m^-1）
Deionized water（H₂O）	72.10	19.90	52.20
Diiodomethane（C₂I₂）	50.00	47.40	2.60

Table 1 Surface tension values of deionized water and diiodomethane

Test liquid	$γ L$ /（mN·m^-1）	$γ L d$ /（mN·m^-1）	$γ L p$ /（mN·m^-1）
Deionized water（H₂O）	72.10	19.90	52.20
Diiodomethane（C₂I₂）	50.00	47.40	2.60

Fig.1 Static contact angle and surface energy of glass at different plasma surface modification rates

Table 2 Static contact angle and surface energy of glass at different plasma surface modification rates

Plasma surface modification rate/（mm·s^-1）	Static contact angle/（°）		Surface energy/ （mN·m^-1）	Polar component/ （mN·m^-1）	Dispersive component/ （mN·m^-1）
Plasma surface modification rate/（mm·s^-1）	H₂O	C₂I₂	Surface energy/ （mN·m^-1）	Polar component/ （mN·m^-1）	Dispersive component/ （mN·m^-1）
Untreated	53.00	47.50	48.77	24.52	24.25
9	22.13	31.20	68.13	40.62	27.50
7	21.30	31.83	68.39	41.22	27.17
5	15.00	28.70	70.78	42.87	27.91
3	27.00	34.00	65.74	39.05	26.69
1	31.12	37.67	63.29	37.59	25.70

Fig.2 Surface microscopic morphology of glass samples at different plasma surface modification rates

Table 3 Changes in content of elements on glass surface at different plasma surface modification rates

Plasma surface modification rate/（mm·s^-1）	Mole fraction/%				Atomic ratio
Plasma surface modification rate/（mm·s^-1）	C	O	N	Si	O/C	N/C	O/Si
Untreated	33.16	46.78	0.79	19.28	1.41	0.02	2.41
9	31.38	52.05	2.47	14.11	1.65	0.08	3.68
7	28.01	51.45	2.31	18.43	1.83	0.08	2.79
5	25.90	52.22	2.68	19.20	2.02	0.10	2.71
3	31.22	49.25	2.67	16.40	1.57	0.09	3.00
1	32.06	51.02	1.25	15.57	1.56	0.04	3.23

Fig.3 C1s peak fitting spectra of glass at different plasma surface modification rates

Fig.4 Si2p peak fitting spectra of glass at different plasma surface modification rates

Table 4 Variation of carbon group content on glass surface at different plasma surface modification rates

Plasma surface modification rate/（mm·s^-1）	Mole fraction/%
Plasma surface modification rate/（mm·s^-1）	C—C	C—O/C—N	CO
Untreated	77.78	18.48	3.73
9	74.77	15.04	8.78
7	70.93	16.55	12.52
5	69.01	19.03	11.97
3	70.02	21.98	7.09
1	75.49	18.64	5.87

Table 5 Variation of silicon group content on glass surface at different plasma surface modification rates

Plasma surface modification rate/（mm·s^-1）	Mole fraction/%
Plasma surface modification rate/（mm·s^-1）	Si—OH	Si—O—Si	Si—O—C
Untreated	29.48	64.83	5.69
9	40.26	47.29	12.45
7	54.55	34.87	10.58
5	62.52	25.93	11.55
3	40.55	49.41	10.04
1	31.07	56.85	12.08

Fig.5 Optical properties of samples at different plasma surface modification rates

Fig.6 Peel strength of samples at different plasma surface modification rates

Table 6 Peel strength of samples at different plasma surface modification rates

Plasma surface modification rate/（mm·s^-1）	Untreated	9	7	5	3	1
Peel strength/（N·m^-1）	17 798	20 673	21 541	23 620	19 222	18 724
Strength enhancement/%	0	16.2	21.0	32.7	8.0	5.2

Fig.7 Interface 90° peel strength curves under different conditions

Table 7 Interface 90° peel strength data under different conditions

Plasma surface modification rate/（mm·s^-1）	Peel strength after 100 h/（N·m^-1）				Peel strength after 200 h/（N·m^-1）				Peel strength after 300 h/（N·m^-1）
Plasma surface modification rate/（mm·s^-1）	（a）	（b）	（c）	（d）	（a）	（b）	（c）	（d）	（a）	（b）	（c）	（d）
Untreated	14 122	15 610	16 410	17 423	11 202	14 562	14 933	16 819	8 638	13 399	14 226	16 583
9	18 235	19 016	17 520	20 642	16 603	18 157	16 394	20 340	14 848	17 644	15 733	19 673
7	19 698	20 615	18 701	20 801	17 821	20 024	17 805	20 657	16 386	19 039	16 875	20 427
5	22 113	23 104	21 606	23 117	20 871	22 591	20 728	22 821	19 635	22 005	19 934	22 841
3	17 630	17 928	17 816	18 703	15 812	17 523	16 837	18 719	14 354	16 645	15 786	18 386
1	16 786	17 101	17 645	18 530	15 113	16 611	16 015	18 118	12 800	15 967	15 384	17 861

References 33

[1]	DAR U A， ZHANG W H， XU Y J. FE analysis of dynamic response of aircraft windshield against bird impact［J］. International Journal of Aerospace Engineering， 2013， 2013（1）： 171768.
[2]	MOHAGHEGHIAN I， CHARALAMBIDES M N， WANG Y， et al. Effect of the polymer interlayer on the high-velocity soft impact response of laminated glass plates［J］. International Journal of Impact Engineering， 2018， 120： 150-170.
[3]	SAMADIAN M. Structural analysis of a high-performance aircraft windshield［D］. Long Beach： California State University， 1988.
[4]	LIU L Z， MA Z Z， PANG S H， et al. Effect of polyurethane with different elastic modulus on the response of aircraft windshield against bird strike［J］. Advanced Materials Research， 2011， 418/419/420： 179-184.
[5]	REZAEI M， AREZOO B， ZIAEI-RAD S. New design of materials， order and thicknesses of an aircraft windshield behaviour layers to increase its resistance against repeated bird impacts［J］. The Aeronautical Journal， 2024， 128（1328）： 2235-2260.
[6]	赵宸君，杨健，王星尔，等. 影响夹层玻璃脱胶因素研究分析［J］. 新型建筑材料， 2022， 49（5）： 20-24.
	ZHAO C J， YANG J， WANG X E， et al. An exploratory investigation into the factors triggering the debonding in laminated glass［J］. New Building Materials， 2022， 49（5）： 20-24 （in Chinese）.
[7]	冯　凯，崔　鹏，刘会超，等. PVB夹层玻璃分层脱胶的失效分析研究［J］. 玻璃， 2024， 51（1）： 41-51.
	FENG K， CUI P， LIU H C， et al. Failure analysis of delamination and degumming of PVB laminated glass［J］. Glass， 2024， 51（1）： 41-51 （in Chinese）.
[8]	刘　刚，戴向黎，王　舟. 飞机风挡玻璃结构分析与研究［C］//探索创新交流（第7集）——第七届中国航空学会青年科技论坛文集（下册）. 中山， 2016： 508-515.
	LIU G， DAI X L， WANG Z. Analysis and study of aircraft windshield structure［C］//Exploration， Innovation and Communication（7th）——Proceedings of the 7th China Aeronautical Society Youth Science and Technology Forum （Volume 2）. Zhongshan， 2016：508-515 （in Chinese）.
[9]	欧迎春，马晓娜，张延芳，等. 紫外辐照下透明聚氨酯胶片老化机理［J］. 航空材料学报， 2017， 37（1）： 93-98.
	OU Y C， MA X N， ZHANG Y F， et al. Degradation mechanisms of transparent polyurethane interlayer under UV irradiation［J］. Journal of Aeronautical Materials， 2017， 37（1）： 93-98 （in Chinese）.
[10]	欧迎春，黄友奇，冯海兵，等. 聚氨酯胶片在湿热环境下的性能［J］. 材料科学与工程学报， 2012， 30（1）： 1-4.
	OU Y C， HUANG Y Q， FENG H B， et al. Effects of damp heat on the properties of polyurethane/polyvinylbutyral interlayer［J］. Journal of Materials Science and Engineering， 2012， 30（1）： 1-4 （in Chinese）.
[11]	沈鹤飞，韩晓辉，尹承泽，等. 聚氨酯胶与玻璃界面粘接分子动力学研究［J］. 中国胶粘剂， 2023， 32（6）： 26-31.
	SHEN H F， HAN X H， YIN C Z， et al. Molecular dynamics study on the bonding of polyurethane sealant to glass interface［J］. China Adhesives， 2023， 32（6）： 26-31 （in Chinese）.
[12]	刘望子. 有机-无机层合玻璃界面结构调控及其力学性能研究［D］. 南昌：南昌航空大学， 2014.
	LIU W Z. The interfacial structure modulation and mechanical properties of organic-inorganic glass laminates［D］. Nanchang： Nanchang Hangkong University， 2014 （in Chinese）.
[13]	CHAI J， MING C， ZENG Y M， et al. Surface energy of glass and interfacial energy of glass with metals［J］. Physical Review B， 2025， 111（3）： 035433.
[14]	SUN C C， GU P， WAN H L， et al. Enhancements of physical microstructure and chemical activation on interfacial bonding strength of carbon fiber reinforced polymer［J］. Composites Part A： Applied Science and Manufacturing， 2025， 188： 108530.
[15]	CHEN M M， XU L， ZHU P L， et al. Effect of silane coupling agent on the performance of electrically conductive adhesives［C］//2023 24th International Conference on Electronic Packaging Technology （ICEPT）. August 8-11， 2023， Shihezi City， China. New York： IEEE， 2023： 1-4.
[16]	LEE S Y， KIM J S， LIM S H， et al. The investigation of the silica-reinforced rubber polymers with the methoxy type silane coupling agents［J］. Polymers， 2020， 12（12）： 3058.
[17]	SANG J， AISAWA S， MIURA K， et al. Adhesion of carbon steel and natural rubber by functionalized silane coupling agents［J］. International Journal of Adhesion and Adhesives， 2017， 72： 70-74.
[18]	CHEN T H， CHUNG F Y， JIANG W F， et al. A study of plasma power effects on surface activation of polystyrene［J］. Vacuum， 2021， 186： 110069.
[19]	ZHANG Y， YANG T， LI B B， et al. Surface modifications of zirconia with plasma pretreatment and polydopamine coating to enhance the bond strength and durability between zirconia and titanium［J］. Dental Materials Journal， 2023， 42（3）： 449-457.
[20]	KIM S H， LIM Y J， KIM D J， et al. Impact of different surface treatments on shear bond strength between two zirconia ceramics and a composite material［J］. Bioengineering， 2024， 11（10）： 1003.
[21]	BEDNARIK M， MIZERA A， MANAS M， et al. Influence of the β-radiation/cold atmospheric-pressure plasma surface modification on the adhesive bonding of polyolefins［J］. Materials， 2021， 14（1）： 76.
[22]	LIU G C， XU Y， YANG W F， et al. Bonding repair of CFRP based on cold plasma treatment surface modification［J］. Journal of Adhesion Science and Technology， 2020， 34（16）： 1796-1808.
[23]	CACERES W， DESTRIEUX A， RUSU A， et al. Surface modification of ethylene tetrafluoroethylene via atmospheric pressure nitrogen plasma for enhanced wettability and adhesive bonding［J］. Canadian Journal of Chemistry， 2025， 103（5）： 184-194.
[24]	SIHELNÍK S， KRUMPOLEC R， KELAR TUČEKOVÁ Z， et al. Atmospheric-pressure air plasma sources for cleaning and activation of float soda-lime glass： effects and comparison［J］. Surfaces and Interfaces， 2023， 40： 103080.
[25]	HOMOLA T， MATOUŠEK J， KORMUNDA M， et al. Plasma treatment of glass surfaces using diffuse coplanar surface barrier discharge in ambient air［J］. Plasma Chemistry and Plasma Processing， 2013， 33（5）： 881-894.
[26]	LI Y H， LIU H， BAI Q S， et al. Atomistic investigation on interfacial properties of glass surfaces modeling plasma modification and the influence of wettability conditions on adhesion［J］. International Journal of Adhesion and Adhesives， 2023， 122： 103330.
[27]	LI D， XIONG M， WANG S， et al. Effects of low-temperature plasma treatment on wettability of glass surface： molecular dynamic simulation and experimental study［J］. Applied Surface Science， 2020， 503： 144257.
[28]	ABENOJAR J， MARTÍNEZ M A， ENCINAS N， et al. Modification of glass surfaces adhesion properties by atmospheric pressure plasma torch［J］. International Journal of Adhesion and Adhesives， 2013， 44： 1-8.
[29]	KORDOVA T. Use of atmospheric pressure plasma to improve the adhesive properties of glass and polyamide 6 in the bonding of additional parts in the automotive industry［J］. Ceramics-Silikaty， 2023： 334-347.
[30]	TRAMIS O， MERLINGE N， HASSOUNE-RHABBOUR B， et al. Tack properties of nanostructured epoxy-amine resins on plasma-treated glass substrates［J］. ACS Omega， 2023， 8（41）： 37842-37851.
[31]	HU H， ZHAO S， WANG W S， et al. Prediction of adhesion between randomly rough surfaces by order statistics［J］. Applied Physics Letters， 2021， 119（7）： 071603.
[32]	SHAEVICH R B. Measurement of the specific free surface energy of solids［J］. Measurement Techniques， 2007， 50（10）： 1121-1123.
[33]	XIAN A P. Thermodynamic discussion on Young’s equation in wetting［J］. International Journal of Materials Research， 2000， 91（4）： 316-322.