Silane Effects on Adhesion Enhancement of 2K Polyurethane Adhesives.

With excellent properties such as great flexibility, outstanding chemical resistance, and superb mechanical strength, two-part polyurethane (2K PU) adhesives have been widely applied in many applications, including those in transportation and construction. Despite the extensive use, their adhesion to nonpolar polymer substrates still needs to be improved and has been widely studied. The incorporation of silane molecules and the use of plasma treatment on substrate surfaces are two popular methods to increase the adhesion of 2K PU adhesives, but their detailed adhesion enhancement mechanisms are still largely unknown. In this research, sum frequency generation (SFG) vibrational spectroscopy was used to probe the influence of added or coated silanes on the interfacial structure at the buried polypropylene (PP)/2K PU adhesive interface in situ. How plasma treatment on PP could improve adhesion was also investigated. To achieve maximum adhesion, two methods to involve silanes were studied. In the first method, silanes were directly mixed with the 2K PU adhesive before use. In the second method, silane molecules were spin-coated onto the PP substrate before the PU adhesive applied. It was found that the first method could not improve the 2K PU adhesion to PP, while the second method could substantially enhance such adhesion. SFG studies demonstrated that with the second method silane molecules chemically reacted at the interface to connect PP and 2K PU adhesive to improve the adhesion. With the first method, silane molecules could not effectively diffuse to the interface to enhance adhesion. In this research, plasma treatment was also found to be a useful method to improve the adhesion of the 2K PU adhesive to nonpolar polymer materials.

Antiadhesive Copolymers at Solid/Liquid Interfaces: Complementary Characterization of Polymer Adsorption and Protein Fouling by Sum Frequency Generation Vibrational Spectroscopy and Quartz-Crystal Microbalance Measurements with Dissipation Monitoring.

Amphiphilic copolymers comprising hydrophilic segments of poly(ethylene glycol) and hydrophobic domains that are able to adhere to solid/liquid interfaces have proven to be versatile ingredients in formulated products for various types of applications. Recently, we have reported the successful synthesis of a copolymer designed for modifying the surface properties of polyesters as mimics for synthetic textiles. Using sum frequency generation (SFG) spectroscopy, it was shown that the newly developed copolymer adsorbs effectively on the targeted substrates even in the presence of surfactants as supplied by common detergents. In the present work, these studies were extended to evaluate the ability of the formed copolymer adlayers to passivate polyester surfaces against undesired deposition of bio(macro)molecules, as represented by fibrinogen as model protein foulants. In addition, SFG spectroscopy was used to elucidate the structure of fibrinogen at the interface between polyester and water. To complement the obtained data with an independent technique, analogous experiments were performed using quartz-crystal microbalance with dissipation monitoring for the detection of the relevant interfacial processes. Both methods give consistent results and deliver a holistic picture of brush copolymer adsorption on polyester surfaces and subsequent antiadhesive effects against proteins under different conditions representing the targeted application in home care products.

Corn Oil-Water Separation: Interfacial Behavior of Extended Surfactant and Glutelin.

The purification and collection of various products from oil/water mixtures are routine procedures. However, the presence of emulsifiers that can displace other surface active components in the mixtures can significantly influence the efficiency of such procedures. Previously, we investigated interfacial mechanisms of zein protein-induced emulsification and the opposing surfactant-induced demulsification related to corn oil refinement. In this paper, we further investigated a different class of protein, glutelin, inside corn and proved that glutelin acts as an oil/water emulsifier in an acidic water environment. Furthermore, an extended surfactant's protein disordering and removal ability was tested and compared with a conventional surfactant. An extended surfactant contains a poly(propylene oxide) or poly(propylene oxide)-poly(ethylene oxide) chain inserted between the hydrophilic head and the hydrophobic tail. In this study, a nonlinear optical spectroscopic technique, sum frequency generation (SFG) vibration spectroscopy, was used to study the behavior of glutelin and extended as well as regular surfactants at the corn oil/water or aqueous solution interface. In most cases, the conventional surfactant shows better protein disordering or removal ability than the extended surfactant. However, with the addition of heat and salt to an extended surfactant solution, the experiment resulted in a substantial increase in the extended surfactant's protein disorder or removal ability.

Methylene diphenyl diisocyanate occupational exposure data in industry (1998-2020): A descriptive summary from an industrial hygiene perspective.

This paper provides an overview of airborne methylene diphenyl diisocyanate (MDI) concentrations in workplaces across North America and Europe. A total of 7649 samples were collected between 1998 and 2020 by producers of MDI during product stewardship activities at customer sites, primarily using validated OSHA or ISO sampling and analysis techniques. As would be expected from the low vapor pressure of MDI, 80% of the concentrations were less than 0.01 mg/m3 (1 ppb) and 93% were less than 0.05 mg/m3 (5 ppb). Respiratory protection is an integral part of Industrial Hygiene practices; therefore, its use was studied and summarized. While covering a variety of MDI applications, a large number of samples was obtained from composite wood manufacturing facilities, offering specific insight into potential exposures associated with different process sections and job types in this industry sector. Given the potential presence in industrial processes of MDI-containing dust or aerosols, future work should place increased emphasis on also investigating dermal exposure. The data reported in this paper provide valuable information for product stewardship and industrial hygiene purposes throughout the MDI-processing industry.

Patterns of microparticles in blank samples: A study to inform best practices for microplastic analysis.

Quality assurance and quality control (QA/QC) techniques are critical to analytical chemistry, and thus the analysis of microplastics. Procedural blanks are a key component of QA/QC for quantifying and characterizing background contamination. Although procedural blanks are becoming increasingly common in microplastics research, how researchers acquire a blank and report and/or use blank contamination data varies. Here, we use the results of laboratory procedural blanks from a method evaluation study to inform QA/QC procedures for microplastics quantification and characterization. Suspected microplastic contamination in the procedural blanks, collected by 12 participating laboratories, had between 7 and 511 particles, with a mean of 80 particles per sample (±SD 134). The most common color and morphology reported were black fibers, and the most common size fraction reported was 20-212 µm. The lack of even smaller particles is likely due to limits of detection versus lack of contamination, as very few labs reported particles <20 µm. Participating labs used a range of QA/QC techniques, including air filtration, filtered water, and working in contained/'enclosed' environments. Our analyses showed that these procedures did not significantly affect blank contamination. To inform blank subtraction, several subtraction methods were tested. No clear pattern based on total recovery was observed. Despite our results, we recommend commonly accepted procedures such as thorough training and cleaning procedures, air filtration, filtered water (e.g., MilliQ, deionized or reverse osmosis), non-synthetic clothing policies and 'enclosed' air flow systems (e.g., clean cabinet). We also recommend blank subtracting by a combination of particle characteristics (color, morphology and size fraction), as it likely provides final microplastic particle characteristics that are most representative of the sample. Further work should be done to assess other QA/QC parameters, such as the use of other types of blanks (e.g., field blanks, matrix blanks) and limits of detection and quantification.

The influence of complex matrices on method performance in extracting and monitoring for microplastics.

Previous studies have evaluated method performance for quantifying and characterizing microplastics in clean water, but little is known about the efficacy of procedures used to extract microplastics from complex matrices. Here we provided 15 laboratories with samples representing four matrices (i.e., drinking water, fish tissue, sediment, and surface water) each spiked with a known number of microplastic particles spanning a variety of polymers, morphologies, colors, and sizes. Percent recovery (i.e., accuracy) in complex matrices was particle size dependent, with ∼60-70% recovery for particles >212 µm, but as little as 2% recovery for particles <20 µm. Extraction from sediment was most problematic, with recoveries reduced by at least one-third relative to drinking water. Though accuracy was low, the extraction procedures had no observed effect on precision or chemical identification using spectroscopy. Extraction procedures greatly increased sample processing times for all matrices with the extraction of sediment, tissue, and surface water taking approximately 16, 9, and 4 times longer than drinking water, respectively. Overall, our findings indicate that increasing accuracy and reducing sample processing times present the greatest opportunities for method improvement rather than particle identification and characterization.

Probing Interfacial Behavior and Antifouling Activity of Adsorbed Copolymers at Solid/Liquid Interfaces.

Polymers containing poly(ethylene glycol) (PEG) units can exhibit excellent antifouling properties, which have been proposed/used for coating of biomedical implants, separation membranes, and structures in marine environments, as well as active ingredients in detergent formulations to avoid soil redepositioning in textile laundry. This study aimed to elucidate the molecular behavior of a copolymer poly(MMA-co-MPEGMA) containing antiadhesive PEG side chains and a backbone of poly(methyl methacrylate), at a buried polymer/solution interface. Polyethylene terephthalate (PET) was used as a substrate to model polyester textile surfaces. Sum frequency generation (SFG) vibrational spectroscopy was applied to examine the interfacial behavior of the copolymer at PET/solution interfaces in situ and in real time. Complementarily, copolymer adsorption on PET and subsequent antiadhesion against protein foulants were probed by quartz-crystal microbalance experiments with dissipation monitoring (QCM-D). Both applied techniques show that poly(MMA-co-MPEGMA) adsorbs significantly to the PET/solution interface at bulk polymer solution concentrations as low as 2 ppm, while saturation of the surface was reached at 20 ppm. The hydrophobic MMA segments provide an anchor for the copolymer to bind onto PET in an ordered way, while the pendant PEG segments are more disordered but contain ordered interfacial water. In the presence of considerable amounts of dissolved surfactants, poly(MMA-co-MPEGMA) could still effectively adsorb on the PET surface and remained stable at the surface upon washing with hot and cold water or surfactant solution. In addition, it was found that adsorbed poly(MMA-co-MPEGMA) provided the PET surface with antiadhesive properties and could prevent protein deposition, highlighting the superior surface affinity and antifouling performance of the copolymer. The results obtained in this work demonstrate that amphiphilic copolymers containing PMMA anchors and PEG side chains can be used in detergent formulations to modify polyester surfaces during laundry and reduce deposition of proteins (and likely also other soils) on the textile.

Molecular Behavior of 1K Polyurethane Adhesive at Buried Interfaces: Plasma Treatment, Annealing, and Adhesion.

One-part (1K) polyurethane (PU) adhesive has excellent bulk strength and environmental resistance. It is therefore widely used in many fields, such as construction, transportation, and flexible lamination. However, when contacting non-polar polymer materials, the poor adhesion of 1K PU adhesive may not be able to support its outdoor applications. To solve this problem, plasma treatment of the non-polar polymer surface has been utilized to improve adhesion between the polymer and 1K PU adhesive. The detailed mechanisms of adhesion enhancement of the 1K PU adhesive caused by plasma treatment on polymer substrates have not been studied extensively because adhesion is a property of buried interfaces which are difficult to probe. In this study, sum frequency generation (SFG) vibrational spectroscopy was used to investigate the buried PU/polypropylene (PP) interfaces in situ nondestructively. Fourier-transform infrared spectroscopy, the X-ray diffraction technique, and adhesion tests were used as supplemental methods to SFG in the study. The 1K PU adhesive is a moisture-curing adhesive and usually needs several days to be fully cured. Here, time-dependent SFG experiments were conducted to monitor the molecular behaviors at the buried 1K PU adhesive/PP interfaces during the curing process. It was found that the PU adhesives underwent rearrangement during the curing process with functional groups gradually becoming ordered at the interface. Stronger adhesion between the plasma-treated PP substrate and the 1K PU adhesive was observed, which was achieved by the interfacial chemical reactions and a more rigid interface. Annealing the samples increased the reaction speed and enhanced the bulk PU strength with higher crystallinity. In this research, molecular mechanisms of adhesion enhancement of the 1K PU adhesive caused by the plasma treatment on PP and by annealing the PU/PP samples were elucidated.

Quantitative assessment of visual microscopy as a tool for microplastic research: Recommendations for improving methods and reporting.

Microscopy is often the first step in microplastic analysis and is generally followed by spectroscopy to confirm material type. The value of microscopy lies in its ability to provide count, size, color, and morphological information to inform toxicity and source apportionment. To assess the accuracy and precision of microscopy, we conducted a method evaluation study. Twenty-two laboratories from six countries were provided three blind spiked clean water samples and asked to follow a standard operating procedure. The samples contained a known number of microplastics with different morphologies (fiber, fragment, sphere), colors (clear, white, green, blue, red, and orange), polymer types (PE, PS, PVC, and PET), and sizes (ranging from roughly 3-2000 µm), and natural materials (natural hair, fibers, and shells; 100-7000 µm) that could be mistaken for microplastics (i.e., false positives). Particle recovery was poor for the smallest size fraction (3-20 µm). Average recovery (±StDev) for all reported particles >50 µm was 94.5 ± 56.3%. After quality checks, recovery for >50 µm spiked particles was 51.3 ± 21.7%. Recovery varied based on morphology and color, with poorest recovery for fibers and the largest deviations for clear and white particles. Experience mattered; less experienced laboratories tended to report higher concentration and had a higher variance among replicates. Participants identified opportunity for increased accuracy and precision through training, improved color and morphology keys, and method alterations relevant to size fractionation. The resulting data informs future work, constraining and highlighting the value of microscopy for microplastics.

Interfacial Structure and Interfacial Tension in Model Carbon Fiber-Reinforced Polymers.

Carbon fiber-reinforced plastics (CFRPs) are widely used materials with outstanding mechanical properties. The wettability between the polymer matrix and carbon fiber in the interphase region significantly influences the strength of the composite. Sizing agents consisting of multiple components are therefore frequently applied to improve wetting and interfacial adhesion between polymers and carbon fiber in CFRPs. However, the complex compositions of sizing solutions make detailed interpretations of their impacts on interfacial wetting difficult. In this work, surface-sensitive sum frequency generation (SFG) spectroscopy was utilized to characterize the sizing/polymer and sizing/carbon fiber interfacial structures to gain molecular-level understandings of the wetting improvements afforded by sizing. A mixture sizing solution containing polyethylenimine (PEI, adhesion promoter) and Lutensol (surfactant) was investigated when contacting nylon (model plastics), polypropylene (model plastics), and graphite (model carbon fiber). Our results demonstrated that although the addition of the surfactant led to an interfacial tension decrease (in comparison to pure PEI solution) on nylon and polypropylene, the interfacial tension was surprisingly increased on graphite, contrasting with the commonly accepted function of surfactants. SFG characterizations revealed the multilayer molecular structures at these buried interfaces. The peculiar interfacial tension increase at the graphite/sizing interface was then correlated to the strong amine-π interactions between PEI and graphite. PEI was therefore demonstrated to be an effective adhesion promoter for carbon fiber. This article reports the first investigation of (polymer + surfactant) complex structures at solid-liquid interfaces. The valuable structural insights obtained by SFG analysis enable more accurate understandings of the composition-wettability (structure-function) relationship. These detailed understandings of interactions between sizing and the substrates promote more informed and optimized selections of sizing formulae.

Corn Oil-Water Separation: Interactions of Proteins and Surfactants at Corn Oil/Water Interfaces.

Purification and collection of industrial products from oil-water mixtures are commonly implemented processes. However, the efficiencies of such processes can be severely influenced by the presence of emulsifiers that induce the formation of small oil droplets dispersed in the mixtures. Understanding of this emulsifying effect and its counteractions which occur at the oil/water interface is therefore necessary for the improvement of designs of these processes. In this paper, we investigated the interfacial mechanisms of protein-induced emulsification and the opposing surfactant-induced demulsification related to corn oil refinement. At corn oil/water interfaces, the pH-dependent emulsifying function of zein protein, which is the major storage protein of corn, was elucidated by the surface/interface-sensitive sum frequency generation (SFG) vibrational spectroscopy technique. The effective stabilization of corn oil droplets by zein protein was illustrated and correlated to its ordered amide I group at the oil/water interface. Substantial decrease of this ordering with the addition of three industrial surfactants to corn oil-zein solution mixtures was also observed using SFG, which explains the surfactant-induced destabilization and coalescence of small oil droplets. Surfactant-protein interaction was then demonstrated to be the driving force for the disordering of interfacial proteins, either by disrupting protein layers or partially excluding protein molecules from the interface. The ordered zein proteins at the interface were therefore revealed to be the critical factor for the formation of corn oil-water emulsion.

Low-Volatility Model Demonstrates Humidity Affects Environmental Toxin Deposition on Plastics at a Molecular Level.

Despite the ever-increasing prevalence of plastic debris and endocrine disrupting toxins in aquatic ecosystems, few studies describe their interactions in freshwater environments. We present a model system to investigate the deposition/desorption behaviors of low-volatility lake ecosystem toxins on microplastics in situ and in real time. Molecular interactions of gas-phase nonylphenols (NPs) with the surfaces of two common plastics, poly(styrene) and poly(ethylene terephthalate), were studied using quartz crystal microbalance and sum frequency generation vibrational spectroscopy. NP point sources were generated under two model environments: plastic on land and plastic on a freshwater surface. We found the headspace above calm water provides an excellent environment for NP deposition and demonstrate significant NP deposition on plastic within minutes at relevant concentrations. Further, NP deposits and orders differently on both plastics under humid versus dry environments. We attributed the unique deposition behaviors to surface energy changes from increased water content during the humid deposition. Lastly, nanograms of NP remained on microplastic surfaces hours after initial NP introduction and agitating conditions, illustrating feasibility for plastic-bound NPs to interact with biota and surrounding matter. Our model studies reveal important interactions between low-volatility environmental toxins and microplastics and hold potential to correlate the environmental fate of endocrine disrupting toxins in the Great Lakes with molecular behaviors.

The molecular interfacial structure and plasticizer migration behavior of "green" plasticized poly(vinyl chloride).

Tributyl acetyl citrate (TBAC), a widely-used "green" plasticizer, has been extensively applied in products for daily use. In this paper, a variety of analytical tools including sum frequency generation vibrational spectroscopy (SFG), coherent anti-Stokes Raman spectroscopy (CARS), contact angle goniometry (CA), and Fourier transform infrared spectroscopy (FTIR) were applied together to investigate the molecular structures of TBAC plasticized poly(vinyl chloride) (PVC) and the migration behavior of TBAC from PVC-TBAC mixtures into water. We comprehensively examine the effects of oxygen and argon plasma treatments on the surface structures of PVC-TBAC thin films containing various bulk percentages of plasticizers and the leaching behavior of TBAC into water. It was found that TBAC is a relatively stable PVC plasticizer compared to traditional non-covalent plasticizers but is also surface active. Oxygen plasma treatment increased the hydrophilicity of TBAC-PVC surfaces, but did not enhance TBAC leaching. However, argon plasma treatment greatly enhanced the leaching of TBAC molecules from PVC plastics to water. Based on our observations, we believe that oxygen plasma treatment could be applied to TBAC plasticized PVC products to enhance surface hydrophilicity for improving the biocompatibility and antibacterial properties of PVC products. The structural information obtained in this study will ultimately facilitate a molecular level understanding of plasticized polymers, aiding in the design of PVC materials with improved properties.

Interfacial molecular restructuring of plasticized polymers in water.

Upon water contact, phthalate-plasticized poly(vinyl chloride) (PVC) surfaces are highly unstable because the plasticizer molecules are not covalently bound to the polymer network. As a result, it is difficult to predict how the surface polymer chains and plasticizers may interact with water without directly probing the plastic/water interface in situ. We successfully studied the molecular surface restructuring of 10 wt% and 25 wt% bis 2-ethylhexyl phthalate (DEHP)-plasticized and pure PVC films (deposited on solid substrates) in situ due to water contact using sum frequency generation (SFG) vibrational spectroscopy. SFG spectral signals from both the top and the bottom of the plastic film were obtained simultaneously, so a thin-film model spectral analysis was applied to separately identify the molecular changes of plastics at the surface and the plastic/substrate interface in water. It was found that in water both the structures of the plastic surface and the buried plastic/substrate interface changed. After removing the samples from the water and exposing them to air again, the surface structures did not completely recover. Further SFG experiments confirmed that small amounts of DEHP were transferred into the water. The leached DEHP molecules could reorder and permanently transfer to new surfaces through water contact. Our studies indicate that small amounts of phthalates can transfer from surface to surface through water contact in an overall scope of minutes. This study yields vital new information on the molecular surface structures of DEHP plasticized PVC in water, and the transfer behaviors and environmental fate of plasticizers in polymers.

Molecular structural changes of plasticized PVC after UV light exposure.

Plasticized poly(vinyl chloride) (PVC) materials for industrial, medical, and household use are often intentionally exposed to UV light, though its impact on the molecular integrity and toxicity of the surface and bulk of PVC materials is still not well understood. This paper investigates the surface and bulk molecular changes of plasticized PVC films with 25, 10, or 0 wt % bis-2-ethylhexyl phthalate (DEHP) plasticizer after exposure to short wave (254 nm) or long wave (365 nm) UV light. Surface analytical techniques including sum frequency generation vibrational spectroscopy (SFG) revealed short wave UV exposure induced major molecular changes on the plasticized PVC surfaces, resulting in increased surface hydrophilicity and decreased CH3 content with increasing exposure time. Additionally, it was deduced from multiple techniques that the surface and the bulk of the plastic exposed to short wave UV contained phthalic monoesters and phthalic acid formed from multistep radical reactions. In contrast, when exposed to long wave UV, molecular content and ordering on the surfaces of the plastic remained relatively unchanged and the introduction of DEHP in plastic helped protect PVC chains from degradation. Results from this study demonstrate short wave UV exposure will result in plastic surfaces containing phthalates and phthalate-related products accessible to contact by living organisms.

Molecular surface structural changes of plasticized PVC materials after plasma treatment.

In this research, a variety of analytical techniques including sum frequency generation vibrational spectroscopy (SFG), coherent anti-Stokes Raman spectroscopy (CARS), and X-ray photoelectron spectroscopy (XPS) have been employed to investigate the surface and bulk structures of phthalate plasticized poly(vinyl chloride) (PVC) at the molecular level. Two types of phthalate molecules with different chain lengths, diethyl phthalate (DEP) and dibutyl phthalate (DBP), mixed with PVC in various weight ratios were examined to verify their different surface and bulk behaviors. The effects of oxygen and argon plasma treatment on PVC/DBP and PVC/DEP hybrid films were investigated on both the surface and bulk of films using SFG and CARS to evaluate the different plasticizer migration processes. Without plasma treatment, SFG results indicated that more plasticizers segregate to the surface at higher plasticizer bulk concentrations. SFG studies also demonstrated the presence of phthalates on the surface even at very low bulk concentration (5 wt %). Additionally, the results gathered from SFG, CARS, and XPS experiments suggested that the PVC/DEP system was unstable, and DEP molecules could leach out from the PVC under low vacuum after several minutes. In contrast, the PVC/DBP system was more stable; the migration process of DBP out of PVC could be effectively suppressed after oxygen plasma treatment. XPS results indicated the increase of C═O/C-O groups and decrease of C-Cl functionalities on the polymer surface after oxygen plasma treatment. The XPS results also suggested that exposure to argon plasma induced chemical bond breaking and formation of cross-linking or unsaturated groups with chain scission on the surface. Finally, our results indicate the potential risk of using DEP molecules in PVC since DEP can easily leach out from the polymeric bulk.

Molecular level understanding of adhesion mechanisms at the epoxy/polymer interfaces.

It is important to understand the buried interfacial structures containing epoxy underfills as such structures determine the interfacial adhesion properties. Weak adhesion or delamination at such interfaces leads to failure of microelectronic devices. Sum frequency generation (SFG) vibrational spectroscopy was used to examine buried interfaces at polymer/model epoxy and polymer/commercial epoxy resins (used as underfills in flip chip devices) at the molecular level. We investigated a model epoxy: bisphenol A digylcidyl ether (BADGE) at the interfaces of poly (ethylene terephthalate) (PET) before and after curing. Furthermore, small amounts of different silanes including (3-glycidoxypropyl) trimethoxysilane (γ-GPS), (3-Aminopropyl)trimethoxysilane (ATMS), Octadecyltrimethoxysilane (OTMS(18C)), and Octyltrimethoxysilane (OTMS(8C)) were mixed with BADGE. Silane influences on the polymer/epoxy interfacial structures were studied. SFG was also used to study molecular interfacial structures between polymers and two commercial epoxy resins. The interfacial structures probed by SFG were correlated to the adhesion strengths measured for corresponding interfaces. The results indicated that a small amount of silane molecules added to epoxy could substantially change the polymer/epoxy interfacial structure, greatly affecting the adhesion strength at the interface. It was found that ordered methyl groups at the interface lead to weak adhesion, and disordered interfaces lead to strong adhesion.

Sum frequency generation and coherent anti-Stokes Raman spectroscopic studies on plasma-treated plasticized polyvinyl chloride films.

Polyvinyl chloride (PVC) is a widely used polymer to which various phthalates are extensively applied as plasticizers. PVC materials are often treated with plasma to vary the hydrophobicity or for cleaning purposes, but little is known of the nature of the surface molecular structures after treatment. This research characterizes molecular surface structures of PVC and bis-2-ethylhexyl phthalate (DEHP)-plasticized PVC films in air before annealing, after annealing, and after exposure to air-generated glow discharge plasma using sum frequency generation (SFG) vibrational spectroscopy. In addition, we compare the vibrational molecular signatures on the surfaces of PVC with DEHP (at a variety of percent loadings) to those of the bulk detected using coherent anti-Stokes Raman scattering (CARS). X-ray photoelectron spectroscopy (XPS) and contact angle measurements have been used to analyze PVC surfaces to supplement SFG data. Our results indicate that DEHP was found on the surfaces of PVC films even at low weight percentages (5 wt %) and that DEHP segregates on surfaces after annealing. The treatment of these films with glow discharge plasma resulted in surface-sensitive reactions involving the removal of chlorine atoms, the addition of oxygen atoms, and C-H bond rearrangement. CARS data demonstrate that the bulk of our films remained undisturbed during the plasma treatment. For the first time, we probed the molecular structure of the surface and the bulk of a PVC material using combined SFG and CARS studies on the same sample in exactly the same environment. In addition, the methodology used in this research can be applied to characterize various plasticizers in a wide variety of polymer systems to understand their surface and bulk structures before and after systematic applications of heat, plasma, or other treatments.