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Polylactic acid (PLA)/cellulose nanocrystal (CNC) composite foams have attracted much attention due to their biodegradability and potential to replace petroleum-based foams. However, the dispersion of (unmodified) CNCs in PLA remains challenging. Here, we used the Pickering emulsion templating method of unmodified CNCs to stabilize PLA microspheres and prepare a concentrated masterbatch. This masterbatch was used in conventional melt blending of pristine PLA to obtain well-dispersed CNCs in PLA with a CNC loading of up to 5 wt %. In comparison, PLA/CNC composites prepared by direct melt blending of CNCs in PLA showed visual agglomerates of CNCs. PLA/CNC composites were batch foamed with CO2 as a physical blowing agent. We demonstrate that the good CNC dispersion obtained by the Pickering emulsion route is favorable for preparing PLA foams with smaller and more uniform cell sizes and with a higher cell density. These results demonstrate that the Pickering emulsion approach to prepare CNC masterbatches for subsequent dispersion in thermoplastics by conventional processing seems promising for numerous industrial applications.

We describe an in situ facile synthetic approach to prepare carbon quantum dot (CQD) fluorescent markers (FMs) for polyethylene (PE) in the presence of agglomerated silica nanoparticles (SiO2 NPs) under mild reaction conditions. First SiO2 NPs, prepared by the Stöber method, were dispersed in toluene. This dispersion was added to a PE solution in toluene. After heating (either in air or under Ar) a fluorescent mixture was obtained. After drying, PE films were obtained by compression molding, which showed strong blue fluorescence, attributed to CQDs. SiO2 NPs loading values varied between 0.5 and 4 wt %. Subsequent to isolation, the fluorescent CQDs were characterized by TEM, UV-vis, and fluorescence spectroscopy. TEM imaging unveiled a lattice spacing value of 0.21 nm of the isolated fluorescent particles which is typical for (100) graphite plane lattice spacing in CQDs. UV spectroscopy and fluorescence measurements show characteristic absorption and excitation spectra for the aromatic core and oxidized surface defects typically observed for CQDs. The emission maximum for PE/CQD samples increased from 394 to 408 nm when the reaction temperature was decreased from 110 to 90 °C, which is attributed to increasing oxygen content in the reaction mixture upon decreasing the reaction temperature. When the reaction was performed under Ar, the PE/CQD samples emitted in the ultraviolet region (286 nm). Finally, we demonstrated that PE samples marked with CQDs can be easily visually identified upon irradiating with 367 nm light. Thus, the marked PE can be used, for example, as a labeling ingredient in master batches for component identification and in recycling.

Molecular interactions in polymer/metal oxide interfaces are of paramount interest in polymer composite applications, including comolding of polymer-metal joints, additive manufacturing, and mold release. This study shows the potential of biomimetic polydopamine (PDA) layers to control polymer-metal adhesion covering a range from strong bonding to release for poly(lactic acid) (PLA) adhering to two metals of significant commercial importance, i.e., titanium (Ti) and stainless steel (SS). The results show that even though PLA bonds significantly weaker to Ti than to SS surfaces, both metals exhibit considerably higher and similar adhesion values following deposition of a PDA layer. In addition, a simple thermal annealing of the PDA-coated wires before the comolding process results in a sharp increase of the bonding strength at low annealing temperatures, followed by a gradual drop at higher annealing temperatures. This observation opens the possibility to provide control of adhesion in polymer-metal interfaces. As PDA forms strongly bound adhesive layers on a wide range of materials, this study proposes that the phenomenon described here can be successfully applied to surfaces other than metals, raising high expectations for future polymer composite applications.

The interface between nucleating agents and polymers plays a pivotal role in heterogeneous cell nucleation in polymer foaming. We describe how interfacial engineering of nucleating particles by polymer shells impacts cell nucleation efficiency in CO2 blown polymer foams. Core–shell nanoparticles (NPs) with a 80 nm silica core and various polymer shells including polystyrene (PS), poly(dimethylsiloxane) (PDMS), poly(methyl methacrylate) (PMMA), and poly(acrylonitrile) (PAN) are prepared and used as heterogeneous nucleation agents to obtain CO2 blown PMMA and PS micro- and nanocellular foams. Fourier transform infrared spectroscopy, thermogravimetric analysis, and transmission electron microscopy are employed to confirm the successful synthesis of core–shell NPs. The cell size and cell density are determined by scanning electron microscopy. Silica NPs grafted with a thin PDMS shell layer exhibit the highest nucleation efficiency values, followed by PAN. The nucleation efficiency of PS- and PMMA-grafted NPs are comparable with the untreated particles and are significantly lower when compared to PDMS and PAN shells. Molecular dynamics simulations (MDS) are employed to better understand CO2 absorption and nucleation, in particular to study the impact of interfacial properties and CO2-philicity. The MDS results show that the incompatibility between particle shell layers and the polymer matrix results in immiscibility at the interface area, which leads to a local accumulation of CO2 at the interfaces. Elevated CO2 concentrations at the interfaces combined with the high interfacial tension (caused by the immiscibility) induce an energetically favorable cell nucleation process. These findings emphasize the importance of interfacial effects on cell nucleation and provide guidance for designing new, highly efficient nucleation agents in nanocellular polymer foaming.

We describe a successful strategy to substantially enhance cell nucleation efficiency in polymer foams by using designer nanoparticles as nucleating agents. Bare and poly(dimethylsilane) (PDMS)-grafted raspberry-like silica nanoparticles with diameters ranging from ∼80 nm to ∼200 nm were synthesized and utilized as highly efficient cell nucleators in CO2-blown nanocellular polymethyl methacrylate (PMMA) foams. The successful synthesis of core–shell nanoparticles was confirmed by Fourier transform infrared spectroscopy, thermogravimetric analysis, Brunauer–Emmett–Teller measurements, and transmission electron microscopy. The cell size and cell density of the obtained PMMA micro- and nanocellular foams were determined by scanning electron microscopy. The results show that increased surface roughness enhances the nucleation efficiency of the designer silica particles. This effect is ascribed to a decreased nucleation free energy for foam cell nucleation in the nanocavities at the melt–nucleator interface. For PDMS grafted raspberry-like silica nanoparticles with diameters of 155 and 200 nm, multiple cell nucleation events were observed. These hybrid particles had nucleation efficiencies of 3.7 and 6.2, respectively. The surprising increase in nucleation efficiency to above unity is ascribed to the significant increase in CO2 absorption and capillary condensation in the corresponding PMMA during saturation. This increase results in the presence of large amounts of the physical blowing agent close to energetically favorable nucleation points. Additionally, it is shown that as a consequence of cell coalescence, the increased number of foam cells is rapidly reduced during the first seconds of foaming. Hence, the design of highly efficient nucleating particles, as well as careful selection of foam matrix materials, seems to be of pivotal importance for obtaining polymer cellular materials with cell dimensions at the nanoscale. These findings contribute to the fabrication of polymer foams with high thermal insulation capacity and have relevance in general to the area of cellular materials.

Hydrated salts (salt hydrates) are highly promising low-temperature phase change materials (PCMs) due to their high cohesive energy density and low cost. However, they exhibit phase separation, liquid leakage, and inherent supercooling, which hinder their applications in sustainable building technology. Here, we describe the design of a highly stable emulsion gel system (EmulGels) that exhibits nonflammable and shape-memory characteristics. Oleophilic paraffin and hydrophilic hydrated salts, both of which are excellent PCMs typically existing in separate phases, are combined harmoniously in a gel by a templating water-in-oil Pickering emulsion. Latent heat values of the prepared EmulGels were up to 213.2 J/g (eicosane/disodium hydrogen phosphate dodecahydrate = 1:3). No leakage of eicosane was noticed after heating the EmulGels at 60 °C for 30 min, and the latent heat value remained almost unchanged following 500 thermal cycles. The EmulGel was specifically designed to enable dual-phase crosslinking, which effectively enhanced its shape stability, slowed down loss of water of crystallization in hydrated salts, and decreased the degree of supercooling. Nonflammable characteristic typically found in hydrated salts was also exhibited by the EmulGel, in combination with good mechanical properties. The materials characteristics make EmulGels ideal candidates to serve as building construction interlayers for effective thermal building management.

Joints that connect thermoplastic polymer matrices (TPMs) and metals, which are obtained by comolding, are of growing importance in numerous applications. The overall performance of these constructs is strongly impacted by the TPM-metal interfacial strength, which can be tuned by tailoring the surface chemistry of the metal prior to the comolding process. In the present work, a model TPM-metal system consisting of poly(methyl methacrylate) (PMMA) and titanium is used to prepare comolded joints. The interfacial adhesion is quantified by wire pullout experiments. Pullout tests prior to and following surface modification are performed and analyzed. Unmodified wires show poor interfacial strength, with a work of adhesion (Ga) value of 3.8 J m-2. To enhance interfacial adhesion, a biomimetic polydopamine (PDA) layer is first deposited on titanium followed by a second layer of a poly(methyl methacrylate-co-methacrylic acid) (P(MMA-co-MAA)) copolymer prior to comolding. During processing, the MAA moieties of the copolymer thermally react with PDA, forming amide bonds, while MMA promotes the formation of secondary bonds and molecular interdigitation with the PMMA matrix. Control testing reveals that neither PDA nor the copolymer provides a substantial increase in adhesion. However, when used in combination, a significant increase in adhesion is detected. This observation indicates a pronounced synergistic effect between the two layers that strengthens the PMMA-titanium bonding. Enhanced adhesion is optimized by tuning the MMA-to-MAA ratio of the copolymer, which shows a maximum at a 24% MAA content and a greatly increased Ga value of 155 J m-2; this value corresponds to a 40-fold increase. Further growth in the Ga values at higher MAA contents is hindered by the thermal cross-linking of MAA; MAA contents above 24% restrict the formation of secondary bonds and molecular interdigitation with the PMMA chains. Our results provide new design principles to produce thermoplastic-metal comolded joints with strong interfaces.

A robust approach for modification of TiO2 nanoparticles with polymer brushes by atom transfer radical polymerization (ATRP) is presented. TiO2 surface was first coated with polydopamine (PDA) followed by immobilization of an ATRP initiator, α-bromoisobutyryl bromide (BiBB). Poly(methyl methacrylate) (PMMA) and poly(butyl acrylate) (PBA) were then grafted from the PDA-modified TiO2 of different size (25 and 300 nm) in DMF at room temperature via supplemental activator reducing agent (SARA) ATRP using only 100 ppm of the copper catalyst. Hybrid core-shell particles with high organic contents (40–88 wt%) and grafting densities (0.16–0.25 nm−2) were obtained. Reaction conducted in the presence of sacrificial initiator confirmed excellent control over the polymerization and produced PMMA and PBA with narrow molecular weight distributions (Mw/Mn < 1.25). Obtained particles were tested as lubricating additives in pipe dope compositions. Addition of polymer-grafted TiO2 to the base grease resulted in a reduced coefficient of friction (COF) and wear over uncoated TiO2 as revealed by reciprocating pin-on-disc tests. The model pipe dopes with PMMA-grafted particles were found to perform on par with commercial American Petroleum Institute (API) dope.

Adhesion of nanoparticles to polymer films plays a key role in various polymer technologies. Here we report experiments that reveal how silica nanoparticles adhere to a viscoelastic PMMA film above the glass transition temperature. The polymer was swollen with CO2, closely matching the conditions of nanoparticle-nucleated polymer foaming. It is found that the degree by which the particles sink into the viscoelastic substrate is strongly size dependent and can even lead to complete engulfment for particles of diameter below 12 nm. These findings are explained quantitatively by a thermodynamic analysis, combining elasticity, capillary adhesion, and line tension. We argue that line tension, here proposed for the first time in elastic media, is responsible for the nanoparticle engulfment.

Core-shell nanoparticles consisting of silica as core and surface-grafted poly(dimethylsiloxane) (PDMS) as shell with different diameters were prepared and used as heterogeneous nucleation agents to obtain CO2-blown poly(methyl methacrylate) (PMMA) nanocomposite foams. PDMS was selected as the shell material as it possesses a low surface energy and high CO2-philicity. The successful synthesis of core-shell nanoparticles was confirmed by Fourier transform infrared spectroscopy, thermogravimetric analysis, and transmission electron microscopy. The cell size and cell density of the PMMA micro- and nanocellular materials were determined by scanning electron microscopy. The cell nucleation efficiency using core-shell nanoparticles was significantly enhanced when compared to that of unmodified silica. The highest nucleation efficiency observed had a value of ∼0.5 for nanoparticles with a core diameter of 80 nm. The particle size dependence of cell nucleation efficiency is discussed taking into account line tension effects. Complete engulfment by the polymer matrix of particles with a core diameter below 40 nm at the cell wall interface was observed corresponding to line tension values of approximately 0.42 nN. This line tension significantly increases the energy barrier of heterogeneous nucleation and thus reduces the nucleation efficiency. The increase of the CO2 saturation pressure to 300 bar prior to batch foaming resulted in an increased line tension length. We observed a decrease of the heterogeneous nucleation efficiency for foaming after saturation with CO2 at 300 bar, which we attribute to homogenous nucleation becoming more favorable at the expense of heterogeneous nucleation in this case. Overall, it is shown that the contribution of line tension to the free energy barrier of heterogeneous foam cell nucleation must be considered to understand foaming of viscoelastic materials. This finding emphasizes the need for new strategies including the use of designer nucleating particles to enhance the foam cell nucleation efficiency.

Printing arrays of responsive spots for multiplexed sensing with electrochemical readout requires new molecules and precise, high-throughput deposition of active compounds on microelectrodes with spatial control. We have designed and developed new redox-responsive polymers, featuring a poly(ferrocenylsilane) (PFS) backbone and side groups with disulfide units, which allow an efficient and stable bonding to Au substrates, using sulfur-gold coupling chemistry in a "grafting-to" approach. The polymer molecules can be employed for area selective molecular sensing following their deposition by high-precision inkjet printing. The new PFS derivatives, which serve as "molecular inks", were characterized by 1H NMR, 13C NMR, and FTIR spectroscopies and by gel permeation chromatography. The viscosity and surface tension of the inks were assessed by rheology and pendant drop contact angle measurements, respectively. Commercial microelectrode arrays were modified with the new PFS ink by using inkjet printing in the "drop-on-demand" mode. FTIR spectroscopy, AFM, and EDX-SEM confirmed a successful, spatially localized PFS modification of the individual electrodes within the sensing cells of the microelectrode arrays. The potential application of these devices to act as an electrochemical sensor array was demonstrated with a model analyte, ascorbic acid, by using cyclic voltammetry and amperometric measurements.

The synthesis of low surface energy polymer grafted silica nanoparticles is reported for the utilization as highly efficient cell nucleation agents to obtain nanocellular, CO2 blown polystyrene (PS) and poly(methyl methacrylate) (PMMA) films in a batch process. For nanoparticle surface functionalization hydroxyl-terminated perfluoropolyether and poly(dimethylsiloxane) (PDMS) were used. Their successful grafting to silica nanoparticles was confirmed by Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA) and transmission electron microscopy (TEM). Following melt blending of the modified silica nanoparticles with PS or PMMA their dispersions were evaluated by scanning electron microscopy (SEM) analyses. We demonstrate that proper selection of the polymer grafts results in nucleation efficiencies of up to approximately 0.5 (i.e. 1 foam cell per 2 particles on average), which is the highest value reported so far for nanofillers as nucleation agents. This number was confirmed by the presence of only 2 to 4 nanoparticles per cell in nanocellular PS and PMMA foams containing SiO2 nanoparticles with a PDMS shell as was observed in cross sectional SEM images. The lowest density foam we obtained (∼0.32 g cm−3) had a nanocellular morphology with a cell size and cell density of ∼440 nm and 1.85 × 1013 cells cm−3, respectively. It is shown that the use of a low surface energy thin shell around silica nanoparticles is beneficial for cell nucleation compared to untreated particles.

Tip-enhanced nanoscale optical imaging techniques such as apertureless scanning near-field optical microscopy (a-SNOM) and scanning near-field ellipsometric microscopy (SNEM) applications can suffer from a steady degradation in performance due to adhesion of atmospheric contaminants to the metal coated tip. Here, we demonstrate that a self-assembled monolayer (SAM) of ethanethiol (EtSH) is an effective means of protecting gold-coated atomic force microscopy (AFM) probe tips from accumulation of surface contaminants during prolonged exposure to ambient air. The period over which they yield consistent and reproducible results for scanning near-field ellipsometric microscopy (SNEM) imaging is thus extended. SNEM optical images of a microphase separated polystyrene-block-poly (methylmethacrylate) (PS-b-PMMA) diblock copolymer film, which were captured with bare and SAM-protected gold-coated AFM probes, both immediately after coating and following five days of storage in ambient air, were compared. During this period the intensity of the optical signals from the untreated gold tip fell by 66%, while those from the SAM protected tip fell by 14%. Additionally, gold coated AFM probe tips were modified with various lengths of alkanethiols to measure the change in intensity variation in the optical images with SAM layer thickness. The experimental results were compared to point dipole model calculations. While a SAM of 1-dodecanethiol (DoSH) was found to strongly suppress field enhancement we find that it can be locally removed from the tip apex by deforming the molecules under load, restoring SNEM image contrast.

We report on the morphology evolution during heating and melting of lamellar poly(isoprene)-block-poly(ferrocenyldimethylsilane) (PI76-b-PFDMS76) raft crystals deposited at the native oxide surface of silicon (SiO2) or at a highly ordered pyrolytic graphite (HOPG) surface, studied by in situ temperature controlled atomic force microscopy. Crystals deposited on hydrophilic SiO2 surfaces revealed an irreversible decrease in length at temperatures of up to tens of degrees above their expected melting temperature, while maintaining their platelet-like structure. Crystals deposited on hydrophobic HOPG surfaces initially decreased in length below their expected melting temperature, while at 120 °C and above a typical molten morphology was observed. In addition, the irreversible formation of a PI76-b-PFDMS76 wetting layer around the crystals was observed upon increasing the temperature. These observations in the morphological behavior upon heating emphasize the role of interfacial energy between a surface deposited block copolymer based macromolecular nanostructure and its supporting substrate.

Scanning near field ellipsometric microscopy (SNEM) was used to simultaneously obtain optical images and tapping mode topography images of the microphase separated morphology of PS-b-P2VP block copolymer thin films. Optical images revealed a spatial resolution well below the diffraction limit. The SNEM setup used consisted of an AFM and an ellipsometer that were commercially available and that did not require major changes in their design to build the hybrid microscope. The observed increase in optical contrast for gold coated tips compared to silicon AFM probe tips was in qualitative agreement with the calculated increase in scattering amplitude according to the point dipole model for a gold AFM probe tip compared to a bare silicon AFM probe tip of the same size. The dielectric constant difference between the two blocks of the diblock copolymer was increased by selectively staining the P2VP block with iodine vapor. This resulted in an increase in the optical contrast between the PS and P2VP domains. Furthermore, the decrease in optical contrast as a function of increasing tip-sample separation was studied. It was observed that at 50 nm tip sample separation the optical contrast was significantly reduced. The non-linear decay of the near-field amplitude signal as a function of the tip-sample separation calculated with the point dipole model supported this experimental result. The use of tapping mode in SNEM opens novel opportunities to study soft matter down to the macromolecular level.

Here, reactive imprint lithography (RIL) is introduced as a new, one-step lithographic tool for the fabrication of large-area topographically patterned, chemically activated polymer platforms. Films of polystyrene-block-poly(tert-butyl acrylate) (PS-b-PtBA) are imprinted with PDMS master stamps at temperatures above the corresponding glass transition and chemical deprotection temperatures to yield structured films with exposed carboxylic acid and anhydride groups. Faithful pattern transfer is confirmed by AFM analyses. Transmission-mode FTIR spectra shows a conversion of over 95% of the tert-butyl ester groups after RIL at 230 °C for 5 minutes and a significantly reduced conversion to anhydride compared to thermolysis of neat films with free surfaces in air or nitrogen. An enrichment of the surface layer in PS is detected by angle-resolved X-ray photoelectron spectroscopy (XPS). In order to demonstrate application potentials of the activated platforms, a 7 nm ± 1 nm thick NH2-terminated PEG layer (grafting density of 0.9 chains nm−2) is covalently grafted to RIL-activated substrates. This layer reduces the non-specific adsorption (NSA) of bovine serum albumin by 95% to a residual mass coverage of 9.1 ± 2.9 ng cm−2. As shown by these examples, RIL comprises an attractive complementary approach to produce bio-reactive polymer surfaces with topographic patterns in a one-step process.

In this paper, we report on the local thermal activation of thin polymer films for area-selective surface chemical modification on micrometer and nanometer length scales. The thermally induced activation of tert-butyl ester moieties in polystyrene- block-poly(tert-butyl acrylate) (PS- b-PtBA) block copolymer films leads to the formation of pending carboxylic acid groups, which are among the versatile functionalities for subsequent bioconjugation. From Fourier transform infrared (FTIR) spectroscopic analyses, the apparent activation energy (Ea) for the tert-butyl ester deprotection in thin films was calculated to be 93 +/- 12 kJ/mol, which is in good agreement with values reported for the bulk. The availability of the deprotected carboxylic acid groups in subsequent wet chemical grafting reactions on neat thermolyzed films was confirmed by covalently immobilizing fluoresceinamine and amino end-functionalized poly(ethylene glycol) (PEG-NH2) using established 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC)/N-hydroxysuccinimide (NHS) chemistry. Local thermal deprotection on micrometer and sub-micrometer length scales was achieved by scanning thermal microscopy using an atomic force microscope with heatable probe tips. Passivating PEG and fluoresceinamine layers were selectively covalently coupled to locally deprotected areas as small as 370 nm x 580 nm.

Low density, nanocellular polymer nanocomposite foams are considered as a promising new class of materials with many promising applications, for example to passively enhance the energy efficiency of buildings. This paper discusses recent developments in this field of polymer materials science. Particular attention will be devoted to CO2 based foaming strategies. Emphasis is on new insights concerning heterogeneous nucleation at the macromolecular length scale and the thermal insulation performance of nanocellular polymer foams. Furthermore, we discuss the limitations and challenges that remain to be solved before these highly promising nanocomposites become available on a commercially viable scale. The shortcomings in the understanding the fundamental principles involved in cell nucleation in polymer nanocomposites at the nanoscale are elucidated.

In this study a scanning near-field ellipsometric microscope (SNEM), a hybrid device of an atomic force microscope (AFM) and an ellipsometer, is used to obtain optical images of heterogeneous polymer thin films with a resolution below the diffraction limit of light. SNEM optical images of a microphase separated PS-b-P2VP block copolymer film collected with gold coated and bare silicon AFM probe tips were compared to obtain a deeper insight into the nature of the SNEM contrast mechanism. Furthermore, intensity vs. distance curves were recorded on a PS-b-PMMA block copolymer film simultaneously during the acquisition of force-displacement curves to study the far-field contribution of the optical signal to the optical image.

In this paper, we report on the development of tailored polymer films for high-resolution atomic force microscopy based scanning thermal lithography (SThL). In particular, full control of surface chemical and topographical structuring was sought. Thin cross-linked films comprising poly(tert-butyl methacrylate) (MA(20)) or poly(tert-butyl acrylate) (A(20)) were prepared via UV initiated free radical polymerization. Thermogravimetric analysis (TGA) and FTIR spectroscopy showed that the heat-induced thermal decomposition of MA(20) by oxidative depolymerization is initially the primary reaction followed by tert-butyl ester thermolysis. By contrast, no significant depolymerization was observed for A(20). For A(20) and MA(20) (at higher temperatures and/or longer reaction times) the thermolysis of the tert-butyl ester liberates isobutylene and yields carboxylic acid groups, which react further intramolecularly to cyclic anhydrides. The values of the apparent activation energies (E(a)) for the thermolysis were calculated to be 125 ± 13 kJ mol(-1) and 116 ± 7 kJ mol(-1) for MA(20) and A(20), respectively. Both MA(20) and A(20) films showed improved thermomechanical stability during SThL compared to non cross-linked films. Carboxylic acid functionalized lines written by SThL in A(20) films had a typically ~10 times smaller width compared to those written in MA(20) films regardless of the tip radius of the heated probe and did not show any evidence for thermochemically or thermomechanically induced modification of film topography. These observations and the E(a) of 45 ± 3 kJ mol(-1) for groove formation in MA(20) estimated from the observed volume loss are attributed to oxidative thermal depolymerization during SThL of MA(20) films, which is considered to be the dominant reaction mechanism for MA(20). The smallest line width values obtained for MA(20) and A(20) films with SThL were 83 ± 7 nm and 21 ± 2 nm, whereas the depth of the lines was below 1 nm, respectively.

We report on Scanning Thermal Lithography (SThL), a recently introduced lithographic tool, for local thermochemistry on tert-butyl acrylate based polymer films featuring chemical cross links. The tailored polymer films afford platforms for controlled high molecular density coupling and surface immobilization of biologically relevant molecules, such as proteins. The thermally labile tert-butyl ester groups in tert-butyl acrylate based polymer films can be cleaved in air at temperatures above 150 °C to yield carboxylic acid functional groups for further (bio)- conjugation. The films were optimized to avoid plastic deformation at the elevated temperatures used during SThL. Exploiting these properties patterns with length scales as small as 35 ± 6 nm have been successfully thermally activated with SThL. Hence SThL comprises an attractive approach for the development of e.g. (bio)sensors and platforms for cell surface interaction studies with nanoscale patterns.