Carbon-Bridge Incorporation in Organosilicate Coatings Using Oxidative Atmospheric Plasma Deposition

Cui, Lele; Dubois, Géraud; Dauskardt, Reinhold H.

doi:10.1021/acsami.5b09971

Cited by 11 publications

(11 citation statements)

References 51 publications

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“…This would produce more binding sites on the precursor species and favor chemical incorporation and increase the deposition rate. This is similar to our previous findings that the surface reaction favored the incorporation of bridged over unbridged species with increasing BTESE delivery rate …”

Section: Resultssupporting

confidence: 92%

“…The dual precursors layer showed higher intensity of peaks at 1380, 1420, or 1430 cm −1 , which refer to Si–CH 2 –Si, Si–(CH 2 ) 2 –Si or Si–(CH 2 ) 6 –Si peaks . The carbon bridge structure are very sensitive to oxidative plasma environment, which was proved in our previous paper . The higher intensity of these peaks suggests that the incorporation of CYC precursor into plasma reduced the reaction energy and possibility of carbon bridge structure decomposition.…”

Section: Resultssupporting

confidence: 63%

“…This is similar to our previous findings that the surface reaction favored the incorporation of bridged over unbridged species with increasing BTESE delivery rate. [7] For the adhesive layer deposited using single precursor, the deposition rate of BTMSH (75.3 AE 2.1 nm min À1 ) was lower than that of BTESE (89.0 AE 4.5 nm min À1 ). The vapor pressure for BTMSH (0.8 Torr at 130 8C, the upper limit of our precursor delivery system) was lower than BTESE (1.6 Torr at 120 8C).…”

Section: Deposition Ratementioning

confidence: 92%

“…The bilayer coatings’ adhesion with PMMA was twice that of commercial polysiloxane sol–gel coatings and exhibited a three‐ to fivefold increase in Young's modulus. An important capability developed in these studies has been the ability to control the incorporation of carbon bridges into the coating structure in the highly oxidative atmospheric plasma environment …”

Section: Introductionmentioning

confidence: 99%

“…An important capability developed in these studies has been the ability to control the incorporation of carbon bridges into the coating structure in the highly oxidative atmospheric plasma environment. [7] In this study, we investigated the influence of carbon chain length of bridges in the precursor on the chemical composition, deposition rate, adhesion to the plastic substrates, and mechanical properties. We also investigated the use of an organic ring-structure precursor CYC along with the carbon bridge precursor during deposition.…”

Section: Introductionmentioning

confidence: 99%

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Role of Carbon Bridge Length of Organosilicate Precursors on the Atmospheric Plasma Deposition of Transparent Bilayer Protective Coatings on Plastics

Dong

Han

Zhao

et al. 2016

Plasma Process. Polym.

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We demonstrate the deposition of transparent organosilicate protective bilayer coatings on poly methyl methacrylate (PMMA) substrates with different carbon chain length dipodalsilane precursors using atmospheric plasma deposition in ambient air. The bottom adhesive layer was a hybrid organosilicate coating deposited using either only carbon bridge organosilicate precursor or accompanied with a ring structure 1,5‐cyclooctadiene precursor. The top layer was a dense silica coating with high elastic modulus and hardness deposited with only carbon bridge precursor. The adhesion energy of bottom layer increased with increasing carbon bridge length of precursors while the density, hardness, and elastic modulus of top hard layer decreased. The deposited bilayer structure showed ∼3 times the adhesion energy and four times the elastic modulus of commercial polysiloxane sol–gel coatings.

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Section: Resultssupporting

confidence: 92%

Section: Resultssupporting

confidence: 63%

Section: Deposition Ratementioning

confidence: 92%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Role of Carbon Bridge Length of Organosilicate Precursors on the Atmospheric Plasma Deposition of Transparent Bilayer Protective Coatings on Plastics

Dong

Han

Zhao

et al. 2016

Plasma Process. Polym.

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Surface Chemical Functionalization to Achieve Extreme Levels of Molecular Confinement in Hybrid Nanocomposites

Wang

Isaacson

Wang

et al. 2019

Adv Funct Materials

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Polymer confinement is realized in hybrid nanocomposites where individual polymer molecules are confined by a nanoporous matrix to dimensions less than the molecular size of the polymer. Here it is shown that by functionalizing the interior pore surfaces of a nanoporous organosilicate matrix, the pores can be filled with polystyrene molecules to achieve extreme levels of molecular confinement not previously possible. This provides opportunities for unique thermal and mechanical properties. It is shown that pore surface functionalization markedly impacts the polymer mobility during polymer infiltration by affecting the polymer-pore surface interaction, addressing the challenge of filling high-molecular-weight polymer molecules into nanoscaleconfined spaces. This allows for achieving extreme levels of molecular confinement with the loss of interchain entanglement and extensive polymer elongation along the pore axis. The glass transition temperature of the polymer is suppressed compared to bulk polymer melt, and is significantly affected by the polymer-surface interaction, which changes the polymer segmental mobility. The polymer-surface interaction also affects the interfacial polymer-pore sliding shear stress during polymer pullout from the nanopores, markedly affecting the fracture resistance of the nanocomposite.of the polymer, which has been shown to reduce entanglements, [4] form ordered morphology, [5] influence T g , [6] improve polymer diffusivity, [7] and enhance fracture resistance of the nanocomposites. [8] A fundamental limit of these studies, however, has been to achieve extreme levels of molecular confinement and the ability to control the interfacial interaction of the confined polymer with the matrix pores.Here we demonstrate that pore surface chemical functionalization allows us to achieve extreme levels of molecular confinement and manipulate the nanocomposite thermal and mechanical properties by controlling the interaction of the polymer with the pore surface (Figure 1). We show that the polymer filling rate can be significantly improved through selection of appropriate surface chemistry, which enables filling polymers with unprecedentedly high molecular weight (M w ) into the porous matrix to create extreme levels of molecular confinement not previously possible. This induces polymer hyperconfinement [[8a]] in which polymer chains entirely lose interchain entanglements and elongate extensively along the pore axis. [9] We also show that T g of the polymer is decreased by hyperconfinement, and can be significantly affected by tuning the polymer-surface interaction to impact the polymer segmental mobility.In addition, we show that the polymer-surface interaction affects the fracture of the nanocomposites where molecular bridging that involves the pullout and stretching of individual confined polymer chains from the nanopores leads to a marked increase in fracture resistance. The surface chemical functionalization significantly changes the sliding shear stress at the polymer/pore surface interfac...

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Optically Transparent Protective Coating for Plastics Using Dual Spray and Atmospheric Plasma Deposition

Ding

Dong

Han

et al. 2018

Adv Materials Inter

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deposited coatings are also low because of the low molecular network connectivity.To achieve coatings with better mechanical properties, we recently demonstrated an atmospheric plasma enhanced deposition technique for depositing transparent organosilicate coatings on plastic substrates with tunable mechanical properties. [9][10][11][12] The optimized bilayer coatings exhibited a twofold increase in adhesion energy with poly(methyl methacrylate) (PMMA) and a three-to fivefold improvement in surface hardness compared to the commercial sol-gel polysiloxane coatings. However, the debond interface still remained adhesively at the polymer and coating interface. Coatings with better adhesive properties which can drive cracks to propagate cohesively within the polymer substrate are highly desirable as it can provide better reliability and durability.In this study, we show the successful deposition of a bilayer protective coating on plastics using a combined spray and atmospheric plasma deposition method. A thin highly adhesive inorganic-organic hybrid coating on plastics was deposited using (3-glycidyloxypropyl) trimethoxysilane (GPTMS) and tetrapropyl zirconate (TPOZ) as precursors with spray coating deposition in air. Among different solution-based processing methods, spray deposition is highly desirable for making large-area, uniform coatings on various kinds of substrates through a simple and cost-effective process. [13] It is also able to coat complex 3D microstructures such as cantilevers and nonplanar surfaces for microelectromechanical systems applications. [14,15] It relies less on solution characteristics than substrate-contact based techniques and provides more flexibility on solvent choice, making it a more versatile process with less environment pollution. [16] Once hydrolyzed, the GPTMS precursor can form an inorganic molecular network via condensation reaction and an organic network via epoxide opening polymerization reaction. TPOZ precursor works as an effective catalyst to the epoxide opening reaction [17][18][19] and also acts as an inorganic network former to increase the inorganic network connectivity of the hybrid coating. After curing of the bottom spray layer, a hard top layer was deposited with atmospheric plasma deposition using tetraethyl orthosilicate (TEOS) as the precursor.The successful processing of bilayer protective coatings on plastics using a combined spray and atmospheric plasma deposition method is shown. The base layer is a spray deposited coating with high adhesion using (3-glycidyloxypropyl) trimethoxysilane and tetrapropyl zirconate (TPOZ) precursors. The top dense layer is deposited by atmospheric plasma deposition with a tetraethyl orthosilicate precursor. The coating deposition rate, chemical composition, elastic modulus, hardness, and adhesion to poly(methyl methacrylate) (PMMA) substrates are investigated. The adhesion to the polymer substrate is found to decrease with increasing TPOZ content in the precursor solution, while the elastic modulus and hardness of the base layer ...

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Carbon-Bridge Incorporation in Organosilicate Coatings Using Oxidative Atmospheric Plasma Deposition

Cited by 11 publications

References 51 publications

Role of Carbon Bridge Length of Organosilicate Precursors on the Atmospheric Plasma Deposition of Transparent Bilayer Protective Coatings on Plastics

Role of Carbon Bridge Length of Organosilicate Precursors on the Atmospheric Plasma Deposition of Transparent Bilayer Protective Coatings on Plastics

Surface Chemical Functionalization to Achieve Extreme Levels of Molecular Confinement in Hybrid Nanocomposites

Optically Transparent Protective Coating for Plastics Using Dual Spray and Atmospheric Plasma Deposition

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