ChatGPT: Evaluating answers on contrast media related questions and finetuning by providing the model with the ESUR guideline on contrast agents.

OBJECTIVE: This study aimed to assess the feasibility of GPT-4 for answering questions related to contrast media with and without the context of the European Society of Urogenital Radiology (ESUR) guideline on contrast agents. The overarching goal was to determine whether contextual enrichment by providing guideline information improves answers of GPT-4 for clinical decision-making in radiology. METHODS: A set of 64 questions, based on the ESUR guideline on contrast agents mirroring pertinent sections, was developed and posed to GPT-4 both directly and after providing the guideline using a plugin. Responses were graded by experienced radiologists for quality of information and accuracy in pinpointing information from the guideline as well as by radiology residents for utility, using Likert-scales. RESULTS: GPT-4's performance improved significantly with the guideline. Without the guideline, average quality rating was 3.98, which increased to 4.33 with the guideline (p = 0036). In terms of accuracy, 82.3% of answers matched the information from the guideline. Utility scores also reflected a significant improvement with the guideline, with average scores of 4.1 (without) and 4.4 (with) (p = 0.008) with a Fleiss´ Kappa of 0.44. CONCLUSION: GPT-4, when contextually enriched with a guideline, demonstrates enhanced capability in providing guideline-backed recommendations. This approach holds promise for real-time clinical decision-support, making guidelines more actionable. However, further refinements are necessary to maximize the potential of large language models (LLMs). Inherent limitations need to be addressed.

Prevalence of burnout among German radiologists: a call to action.

OBJECTIVES: In the presence of escalating global concerns regarding physician burnout, this study aims to analyze the prevalence and associated factors of burnout among radiologists in Germany. METHODS: A comprehensive online survey, inclusive of 73 targeted questions including a German-modified version of the Maslach Burnout Inventory, was distributed among all members of the German Radiological Society and the German Interventional Radiological Society between May and August 2023. The survey encompassed aspects of employment, workload, well-being, and coping mechanisms. Data from 172 completed surveys were analyzed, with correlations explored via crosstabs and the Pearson-chi-square test. RESULTS: In total, 76.7% of participating radiologists were identified to be burnt out. The prevalence was significantly associated with increased workload, reduced sleep quality, suboptimal working conditions, reduced job satisfaction, and the negative interplay between work, family life, and health. Median work satisfaction was described as "satisfied" while median workload was assessed as "frequently overwhelming of work." A total of 41.9% of respondents noted facing daily time pressure. Radiologists' concerns about work interfering with private family life were voiced by approximately 70%, and 73.3% highlighted the perceived negative effects on their health. CONCLUSION: The pronounced prevalence of burnout among German radiologists demonstrates an urgent, unmet need for comprehensive interventions and systemic changes. Our findings act as a catalyst for initiating targeted, multifaceted strategies and dialogs, essential for fostering a resilient and effective healthcare ecosystem. Further large-scale systematic studies should follow to analyze the findings in broad. CLINICAL RELEVANCE STATEMENT: Consistent with other countries, there is a high prevalence of burnout among radiologists in Germany. A call for further investigation is recommended to help mitigate adverse outcomes associated with physician burnout. KEY POINTS: • The prevalence of burnout has yet not been evaluated for German radiologists. • German radiologists have a high prevalence of burnout. • Steps must be implemented to engage this problem to prevent worsening.

Feasibility of GPT-3 and GPT-4 for in-Depth Patient Education Prior to Interventional Radiological Procedures: A Comparative Analysis.

PURPOSE: This study explores the utility of the large language models, GPT-3 and GPT-4, for in-depth patient education prior to interventional radiology procedures. Further, differences in answer accuracy between the models were assessed. MATERIALS AND METHODS: A total of 133 questions related to three specific interventional radiology procedures (Port implantation, PTA and TACE) covering general information as well as preparation details, risks and complications and post procedural aftercare were compiled. Responses of GPT-3 and GPT-4 were assessed for their accuracy by two board-certified radiologists using a 5-point Likert scale. The performance difference between GPT-3 and GPT-4 was analyzed. RESULTS: Both GPT-3 and GPT-4 responded with (5) "completely correct" (4) "very good" answers for the majority of questions ((5) 30.8% + (4) 48.1% for GPT-3 and (5) 35.3% + (4) 47.4% for GPT-4). GPT-3 and GPT-4 provided (3) "acceptable" responses 15.8% and 15.0% of the time, respectively. GPT-3 provided (2) "mostly incorrect" responses in 5.3% of instances, while GPT-4 had a lower rate of such occurrences, at just 2.3%. No response was identified as potentially harmful. GPT-4 was found to give significantly more accurate responses than GPT-3 (p = 0.043). CONCLUSION: GPT-3 and GPT-4 emerge as relatively safe and accurate tools for patient education in interventional radiology. GPT-4 showed a slightly better performance. The feasibility and accuracy of these models suggest their promising role in revolutionizing patient care. Still, users need to be aware of possible limitations.

Feasibility of the chick chorioallantoic membrane model for preclinical studies on tumor radiofrequency ablation.

BACKGROUND: We evaluated the feasibility of a chick chorioallantoic membrane (CAM) tumor model for preclinical research on tumor radiofrequency ablation (RFA). METHODS: Fertilized chicken eggs were incubated and divided into five cohorts: RFA for 30 s (n = 5), RFA for 60 s (n = 5), RFA for 120 s (n = 4), sham (n = 8), and controls (n = 6). Xenografting using pancreatic neuroendocrine tumor cells of the BON-1 cell line was performed on embryonic day (ED) 8. The RFA was performed on ED 12. Survival, stereomicroscopic observations, and histological observations using hematoxylin-eosin (H&E) and Ki67 staining were evaluated. RESULTS: The survival rates in the 30-s, 60-s, and 120-s, sham and control cohort were 60%, 60%, 0%, 100%, and 50%, respectively. Signs of bleeding and heat damage were common findings in the evaluation of stereomicroscopic observations. Histological examination could be performed in all but one embryo. Heat damage, bleeding, thrombosis, and leukocyte infiltration and hyperemia were regular findings in H&E-stained cuts. A complete absence of Ki67 staining was recorded in 33.3% and 50% of embryos in the 30-s and 60-s cohorts that survived until ED 14, respectively. CONCLUSIONS: The CAM model is a feasible and suiting research model for tumor RFA with many advantages over other animal models. It offers the opportunity to conduct in vivo research under standardized conditions. Further studies are needed to optimize this model for tumor ablations in order to explore promising but unrefined strategies like the combination of RFA and immunotherapy. RELEVANCE STATEMENT: The chick chorioallantoic membrane model allows in vivo research on tumor radiofrequency ablation under standardized conditions that may enable enhanced understanding on combined therapies while ensuring animal welfare in concordance with the "Three Rs." KEY POINTS: • The chorioallantoic membrane model is feasible and suiting for tumor radiofrequency ablation. • Radiofrequency ablation regularly achieved reduction but not eradication of Ki67 staining. • Histological evaluation showed findings comparable to changes in humans after RFA. • The chorioallantoic membrane model can enable studies on combined therapies after optimization.

Safety and efficacy of interventional treatment of acute limb ischemia in Germany 2021.

PURPOSE: Interventional procedures have become a mainstay in the therapy of acute limb ischemia caused by embolism or arterial thrombosis. Treatment options include pharmacological thrombolysis (PT) and mechanical thrombectomy (MT). The aim of this study was to evaluate success and major complication rates of interventional radiological treatments of arterial embolism and thrombosis in Germany in 2021 and to compare their results with accepted international quality standards. MATERIALS AND METHODS: Data for PT and MT for 2021 was obtained from the quality management system of the German interventional radiological society (DeGIR). 2431 PT and 1582 MT procedures were documented for 2021, with 459 combinations of PT and MT. Data was analysed for technical and clinical success rates, as well as major complication rates such as intracranial bleeding, major bleeding, distal embolization, aneurysm formation, organ-failure and cardiac-decompensation. RESULTS: PT alone had technical and clinical success rate of 90.21% and 81.08%, respectively. MT alone had technical and clinical success rates of 97.41% and 95.39%, respectively. MT&PT had technical and clinical success rates of 91.07% and 84.75%, respectively. Major complications were: distal embolization (PT:2.02%; MT:1.74%; PT&MT:2.61%), major bleeding (PT:0.94%; MT:1.14%; PT&MT:0.87%), aneurysm formation (PT:0.33%;MT: 1.14%;PT&MT: 0%), intracranial bleeding (PT:0.16%;MT:0%;PT&MT:0.22%), cardiac-decompensation (PT:0.21%;MT: 0.06%;PT&MT:0%) and organ-failure (PT:0%;MT:0.06%;PT&MT:0.22%). Technical and clinical success rates were higher, while complication rates were lower than the corresponding threshold recommended by the Society of Interventional Radiology for percutaneous management of acute lower-extremity ischemia. CONCLUSION: Treatment of arterial embolism and thrombosis performed by interventional radiologists in Germany is effective and safe with outcomes exceeding internationally accepted standards.

pTEVAR of an aorto-esophageal fistula in esophageal cancer: Case report and review of the literature.

An aorto-esophageal fistula (AEF) is a rare and life-threatening situation, associated with aneurysms, foreign bodies, infiltrating tumors, and radiotherapy. The ideal management is unclear. Open surgery of AEF has a high mortality and morbidity. Thoracic endovascular aortic repair (TEVAR) of an AEF is an effective and safe emergency treatment for these patients. We describe a case of AEF due to esophageal cancer successfully treated the first time by total percutaneous TEVAR (pTEVAR). A 70-year-old male patient presented with massive hematemesis at the emergency department. The patient had a known history of esophageal cancer previously treated by radiochemotherapy which was completed 3 days before. Emergency upper gastrointestinal endoscopy failed to stop the bleeding. Subsequent contrast-enhanced computed tomography revealed an aorto-esophageal fistula and emergency pTEVAR was performed. The bleeding stopped directly after stent graft placement and the patient was discharged after 10 days later. He died 3 months after pTEVAR from cancer progression. pTEVAR is an effective and safe treatment option for AEF. It can be applied as a first-line treatment and offers the potential to improve survival in the emergency setting.

Comparison of the radiation protection effect of different radiation protection aprons made of different materials.

OBJECTIVE: The objective of this study is to examine the performance of new generation protection aprons as alternative to conventional lead aprons regarding their radiation protection effectiveness. METHOD AND MATERIALS: Radiation protection aprons made of lead-containing and lead-free materials from a total of seven companies were compared. Furthermore, different lead equivalent values of 0.25, 0.35 and 0.5 mm were compared. For quantitative assessment, radiation attenuation was determined with increasing voltage in steps of 20 kV from 70 kV up to 130 kV. RESULTS: New generation aprons and conventional protection lead aprons showed a similar shielding performance at lower tube voltages below 90 kVp. When tube voltage was increased above 90 kVp, significant (p < 0.05) differences between the three apron types were observed, with conventional lead material as best shielding performer over lead composite and lead-free aprons. CONCLUSION: We observed a similar radiation protection performance between conventional lead aprons and new generation aprons at low intensity radiation workplaces, with lead aprons being dominant for all energies. Only new generation aprons of 0.5 mm thickness would adequately replace 0.25 and 0.35 mm conventional lead aprons. For healthy radiation protection, the possibility of using weight-reduced X-ray aprons is very limited.

Monitoring autochthonous lung tumors induced by somatic CRISPR gene editing in mice using a secreted luciferase.

BACKGROUND: In vivo gene editing of somatic cells with CRISPR nucleases has facilitated the generation of autochthonous mouse tumors, which are initiated by genetic alterations relevant to the human disease and progress along a natural timeline as in patients. However, the long and variable, orthotopic tumor growth in inner organs requires sophisticated, time-consuming and resource-intensive imaging for longitudinal disease monitoring and impedes the use of autochthonous tumor models for preclinical studies. METHODS: To facilitate a more widespread use, we have generated a reporter mouse that expresses a Cre-inducible luciferase from Gaussia princeps (GLuc), which is secreted by cells in an energy-consuming process and can be measured quantitatively in the blood as a marker for the viable tumor load. In addition, we have developed a flexible, complementary toolkit to rapidly assemble recombinant adenoviruses (AVs) for delivering Cre recombinase together with CRISPR nucleases targeting cancer driver genes. RESULTS: We demonstrate that intratracheal infection of GLuc reporter mice with CRISPR-AVs efficiently induces lung tumors driven by mutations in the targeted cancer genes and simultaneously activates the GLuc transgene, resulting in GLuc secretion into the blood by the growing tumor. GLuc blood levels are easily and robustly quantified in small-volume blood samples with inexpensive equipment, enable tumor detection already several months before the humane study endpoint and precisely mirror the kinetics of tumor development specified by the inducing gene combination. CONCLUSIONS: Our study establishes blood-based GLuc monitoring as an inexpensive, rapid, high-throughput and animal-friendly method to longitudinally monitor autochthonous tumor growth in preclinical studies.

Partial p53 reactivation is sufficient to induce cancer regression.

BACKGROUND: Impaired p53 function is one of the central molecular features of a tumor cell and even a partial reduction in p53 activity can increase the cancer risk in mice and men. From a therapeutic perspective it is noteworthy that tumor cells often become addicted to the absence of p53 providing a rationale for developing p53 reactivating compounds to treat cancer patients. Unfortunately, many of the compounds that are currently undergoing preclinical and clinical testing fail to fully reactivate mutant p53 proteins, raising the crucial question: how much p53 activity is needed to elicit a therapeutic effect? METHODS: We have genetically modelled partial p53 reactivation using knock-in mice with inducible expression of the p53 variant E177R. This variant has a reduced ability to bind and transactivate target genes and consequently causes moderate cancer susceptibility. We have generated different syngeneically transplanted and autochthonous mouse models of p53-deficient acute myeloid leukemia and B or T cell lymphoma. After cancer manifestation we have activated E177R expression and analyzed the in vivo therapy response by bioluminescence or magnetic resonance imaging. The molecular response was further characterized in vitro by assays for gene expression, proliferation, senescence, differentiation, apoptosis and clonogenic growth. RESULTS: We report the conceptually intriguing observation that the p53 variant E177R, which promotes de novo leukemia and lymphoma formation, inhibits proliferation and viability, induces immune cell infiltration and triggers cancer regression in vivo when introduced into p53-deficient leukemia and lymphomas. p53-deficient cancer cells proved to be so addicted to the absence of p53 that even the low-level activity of E177R is detrimental to cancer growth. CONCLUSIONS: The observation that a partial loss-of-function p53 variant promotes tumorigenesis in one setting and induces regression in another, underlines the highly context-specific effects of individual p53 mutants. It further highlights the exquisite sensitivity of cancer cells to even small changes in p53 activity and reveals that changes in activity level are more important than the absolute level. As such, the study encourages ongoing research efforts into mutant p53 reactivating drugs by providing genetic proof-of-principle evidence that incomplete p53 reactivation may suffice to elicit a therapeutic response.

Digital Variance Angiography in Selective Lower Limb Interventions.

PURPOSE: To evaluate the potential benefits of digital variance angiography (DVA) in selective lower limb angiography and to compare the performance of 2 DVA algorithms (conventional DVA1 and the recently developed DVA2) to that of digital subtraction angiography (DSA). MATERIALS AND METHODS: From November 2019 to May 2020, 112 iodinated contrast media (ICM) and 40 carbon dioxide (CO2) angiograms were collected from 15 and 13 peripheral artery disease patients, respectively. The DVA files were retrospectively generated from the same unsubtracted source file as DSA. The objectively calculated contrast-to-noise ratio (CNR) and the subjective visual image quality of DSA, DVA1, and DVA2 images were statistically compared using the Wilcoxon signed-rank test. The images were evaluated by 6 radiologists (R.P.T., S.V., A.M.K., S.S.A., O.E., and J.S.) from 2 centers using a 5-grade Likert scale. RESULTS: Both DVA algorithms produced similar increase (at least 2-fold) in CNR values (P < .001) and significantly higher image quality scores than DSA, independent of the contrast agent used. The overall scores with ICM were 3.61 ± 0.05 for DSA, 4.30 ± 0.04 for DVA1, and 4.33 ± 0.04 for DVA2 (each P < .001 vs DSA). The scores for CO2 were 3.10 ± 0.14 for DSA, 3.63 ± 0.13 for DVA1 (P < .001 vs DSA), and 3.38 ± 0.13 for DVA2 (P < .05 vs DSA). CONCLUSIONS: DVA provides higher CNR and significantly better image quality in selective lower limb interventions irrespective of the contrast agent used. Between DVA algorithms, DVA1 is preferred because of its identical or better image quality than DVA2. DVA can potentially help the interventional decision process and its quality reserve might allow dose management (radiation/ICM reduction) in the future.

ADAM 8 as a novel target for doxorubicin delivery to TNBC cells using magnetic thermosensitive liposomes.

Metastatic breast cancer is one of the most common causes of cancer-related death in women worldwide. The transmembrane metalloprotease-disintegrin (ADAM8) protein is highly overexpressed in triple-negative breast cancer (TNBC) cells and potentiates tumor cell invasion and extracellular matrix remodeling. Exploiting the high expression levels of ADAM8 in TNBC cells by delivering anti-ADAM8 antibodies efficiently to the targeted site can be a promising strategy for therapy of TNBC. For instance, a targeted approach with the aid of ultra-high field magnetic resonance imaging (UHF-MRI) activatable thermosensitive liposomes (LipTS-GD) could specifically increase the intracellular accumulation of cytotoxic drugs. The surface of doxorubicin-loaded LipTS-GD was modified by covalent coupling of MAB1031 antibody (LipTS-GD-MAB) in order to target the overexpressed ADAM8 in ADAM8 positive MDA-MB-231 cells. Physicochemical characterization of these liposomes was performed using size, surface morphology and UHF-MRI imaging analysis. In vitro cell targeting was investigated by the washing and circulation method. Intracellular trafficking and lysosomal colocalization were assessed by fluorescence microscopy. Cell viability, biocompatibility and in-ovo CAM assays were performed to determine the effectiveness and safety profiles of liposome formulations. Our results show specific binding and induction of doxorubicin release after LipTS-GD-MAB treatment caused a higher cytotoxic effect at the cellular target site.

Magnetic resonance activatable thermosensitive liposomes for controlled doxorubicin delivery.

To limit the massive cytotoxicity of chemotherapeutic agents, it is desirable to establish an appropriate subtle blend of formulation design based on a dual-responsive strategy. In this study, a combined therapeutic platform based on magnetic thermosensitive liposomes (LipTS-GD) was developed. The incorporation of chelated-gadolinium imparted magnetic properties to thermosensitive liposomes (LipTS). The application of an ultra high field magnetic resonance imaging (UHF-MRI) induced hyperthermia, thus provided an improved chemotherapeutic effect of Doxorubicin (DOX). The paramagnetic platform demonstrated thermal sensitivity over a narrow temperature range starting at 37.8 °C, hence the release of DOX from LipTS-GD can be well triggered by inducing hyperthermia using UHF-MRI application. The prepared LipTS-GD were below 200 nm in diameter and an adequate release of DOX reaching 68% was obtained after 1 h UHF-MRI exposure. Profoundly, triple-negative breast cancer (TNBC) cells that were treated with LipTS-GD and subjected thereafter to UHF-MRI exposure for 60 min showed 36% viability. Hemocompatibility studies of LipTS-GD showed a physiological coagulation time and minimal hemolytic potential. Conclusively, LipTS-GD guided local delivery of DOX to solid tumors will potentially raise the therapeutic index, thus reducing the required dose and frequency of DOX administered systemically without influencing the adjacent tissues.

Effectiveness of a new radiation protection system in the interventional radiology setting.

OBJECTIVES: The goal of this study was to examine a new weightless-like radiation protection garment regarding its radiation protection efficacy and to compare it to a conventional two-piece apron suit plus thyroid collar and standard ancillary shields. MATERIAL AND METHODS: All measurements were carried out using a clinical angiography system with a standardized fluoroscopy protocol for different C-arm angulations. An anthropomorphic torso phantom served as a scattering body. In addition, an ionization chamber was used to measure the radiation exposure on five different representative heights and at two different positions of an examiner during a typical fluoroscopic-guided intervention. RESULTS: The new weightless-like radiation protection garment and the conventional protection concept showed a mean dose reduction of 98.1% (p < 0.01) and 90.1% (p < 0.01) when compared to no shielding, respectively. By adding ancillary shields to both systems, an average reduction of 99.0% (p < 0.01) and 98.2% (p < 0.01) was found. In addition, the efficacy of both systems varied depending on the height, the C-arm angulation and position of the examiner. CONCLUSION: Combined with ancillary shields as an overall protection system, the recently introduced weightless-like radiation protection garment showed a significant better radiation protection efficacy when compared to conventional radiation protection measures.

Age-related differences in skeletal muscle microvascular response to exercise as detected by contrast-enhanced ultrasound (CEUS).

BACKGROUND: Aging involves reductions in exercise total limb blood flow and exercise capacity. We hypothesized that this may involve early age-related impairments of skeletal muscle microvascular responsiveness as previously reported for insulin but not for exercise stimuli in humans. METHODS: Using an isometric exercise model, we studied the effect of age on contrast-enhanced ultrasound (CEUS) parameters, i.e. microvascular blood volume (MBV), flow velocity (MFV) and blood flow (MBF) calculated from replenishment of Sonovue contrast-agent microbubbles after their destruction. CEUS was applied to the vastus lateralis (VLat) and intermedius (VInt) muscle in 15 middle-aged (MA, 43.6±1.5 years) and 11 young (YG, 24.1±0.6 years) healthy males before, during, and after 2 min of isometric knee extension at 15% of peak torque (PT). In addition, total leg blood flow as recorded by femoral artery Doppler-flow. Moreover, fiber-type-specific and overall capillarisation as well as fiber composition were additionally assessed in Vlat biopsies obtained from CEUS site. MA and YG had similar quadriceps muscle MRT-volume or PT and maximal oxygen uptake as well as a normal cardiovascular risk factors and intima-media-thickness. RESULTS: During isometric exercise MA compared to YG reached significantly lower levels in MFV (0.123±0.016 vs. 0.208±0.036 a.u.) and MBF (0.007±0.001 vs. 0.012±0.002 a.u.). In the VInt the (post-occlusive hyperemia) post-exercise peaks in MBV and MBF were significantly lower in MA vs. YG. Capillary density, capillary fiber contacts and femoral artery Doppler were similar between MA and YG. CONCLUSIONS: In the absence of significant age-related reductions in capillarisation, total leg blood flow or muscle mass, healthy middle-aged males reveal impaired skeletal muscle microcirculatory responses to isometric exercise. Whether this limits isometric muscle performance remains to be assessed.

Self-stratification during film formation from latex blends driven by differences in collective diffusivity.

Coatings with vertical gradients in composition were produced by drying an aqueous polymer dispersion containing both charged and neutral particles. After drying, the neutral component was enriched at the film/air interface. The spontaneous vertical segregation between the two types of particles goes back to a difference in collective diffusivity. As the film dries, a layer enriched in polymer develops at the top. Due to their mutual repulsion, charged spheres escape from this layer more quickly than their neutral counterparts. Provided that the total time of drying is between the times of diffusion for the two types of particles (approximately H(0)(2)/D(c) with H(0) the initial film thickness and D(c) the collective diffusivity of the respective species), a concentration gradient persists after the film has turned dry. This effect can be used to create a functionally graded material (FGM) in a single coating step.

Stress fluctuations in drying polymer dispersions.

Drying polymer dispersions usually experience tensile stress, induced by the reduction in volume and by the rigid substrate. Due to edge-in drying, the stress is usually heterogeneous over the film. Stress peaks play a decisive role in the formation of cracks. This work relies on membrane bending, a technique that provides spatially resolved stress maps. In the experiments reported here, stress fluctuations on the order of 10% on the time scale of a few seconds were found. The stress fluctuations occur coherently over the entire drying front. Fluctuations go back to slight fluctuations in humidity of the environment (as opposed to local stress relaxations due to reorganizations of the particle network). The stress fluctuations disappear when covering the sample with a lid. They can be enhanced by blowing humid or dry air across the sample surface. Modeling builds on the assumption that all stresses go back to capillary pressure created at the menisci in between different spheres at the film-air interface. The local radius of curvature changes in response to slight variations in ambient humidity according to the Kelvin equation. The fluctuations are observed under a wide variety of drying conditions and should be included in film formation models.

Dilational lateral stress in drying latex films.

Drying latex films usually experience tensile stress due to the reduction in volume. While an unconstrained film would shrink affinely in all three dimensions, a coating can only shrink along the vertical and therefore exerts tensile stress onto the substrate. Using an instrument capable of producing maps of the stress distribution, we found that dilational stress sometimes develops as well. The in-plane stress was monitored by spreading the latex dispersion on a flexible membrane. Usually, the membrane bends upward under the tensile stress exerted by the film, but it may also bend downward. Dilational stress was only found with samples showing a strong coffee stain effect, that is, samples in which there is a significant lateral flow from the center to the edge while the film dries. During drying, particles consolidate first at the edge because of the lower height in this region. Continued evaporation from the consolidated region results in a water flow toward the edge, exerting a force onto the latex particles. At the time, when the network is formed, any single sphere must be in a force-balance condition: the network must exert an elastic force onto the sphere which just compensates the viscous drag. Pictorially speaking, a spring (an elastic network) is created while an external force acts onto it. Once the flow stops, the drag force vanishes and the internal stress, which previously compensated the drag, expands the film laterally. This phenomenon can lead to buckling. Given that lateral flow of liquid while films dry is a rather common occurrence, this mode of structure formation should be widespread. It requires lateral flow in conjunction with elastic recovery of the particle network.

A comparison of tackified, miniemulsion core-shell acrylic latex films with corresponding particle-blend films: structure-property relationships.

Tackifying resins (TRs) are often added to pressure-sensitive adhesive films to increase their peel strength and adhesion energy. In waterborne adhesives, the TR is dispersed in water using surfactants and then blended with colloidal polymers in water (i.e., latex). In such waterborne systems, there are problems with the colloidal stability and difficulty in applying coatings of the particle blends; the films are often hydrophilic and subject to water uptake. Here, an alternative method of making waterborne, tackified adhesives is demonstrated. The TR is incorporated within the core of colloidal polymer particles via miniemulsion polymerization. Atomic force microscopy (AFM) combined with force spectroscopy analysis reveals there is heterogeneity in the distribution of the TR in films made from particle blends and also in films made from miniemulsion polymers. Two populations, corresponding to TR-rich and acrylic-rich components, were identified through analysis of the AFM force-displacement curves. The nanoscale maximum adhesion force and adhesion energy were found to be higher in a miniemulsion film containing 12 wt % tackifying resin in comparison to an equivalent blended film. The macroscale tack and viscoelasticity are interpreted by consideration of the nanoscale structure and properties. The incorporation of tackifying resin through a miniemulsion polymerization process not only offers clear benefits in the processing of the adhesive, but it also leads to enhanced adhesion properties.

Heterogeneous drying of colloidal polymer films: dependence on added salt.

Using magnetic resonance profiling coupled with dynamic light scattering, we have investigated the mechanisms leading to the formation of a partly coalesced surface layer, or "open skin", during film formation from waterborne polymer dispersions. We present the first use of the skewness of the distribution of free water as a model-free indicator of the spatial nonuniformity of drying. The skewness reaches a maximum at the same time at which a strong, static component, presumably originating from a skin at the film/air interface, appears in the light scattering data. Addition of salt to the dispersion increases both the skewness of the distribution of free water and the propensity for skin formation. Surprisingly, the drying is influenced not only by the concentration and valency of the ions in the salt but also by the particular ion. At intermediate particle densities, added salt strongly lowers the cooperative diffusion coefficient, Dcoop. When the particles reach close packing, Dcoop sharply increases. If the particles readily coalesce, the effects of the increased diffusivity will be counteracted, thereby inducing the formation of a skin. A modified Peclet number, Pe, using Dcoop, is proposed, so that the presence of salt is explicitly considered. This modified Pe is able to predict the nonuniformity in drying that leads to skin formation.

Measurements of interfacial viscoelasticity with a quartz crystal microbalance: influence of acoustic scattering from a small crystal-sample contact.

We discuss the influence of a limited contact size on measurements of high-frequency interfacial viscoelasticity performed with a combination of a quartz crystal microbalance (QCM) and the Johnson-Kendall-Roberts (JKR) apparatus. In this instrument, a sphere-plate contact is established between an elastomeric lens and a quartz resonator. The analysis is carried out in the frame of the sheet-contact model, which states that both the shift of resonance frequency and the bandwidth are proportional to the contact area as long as the contact area is much smaller than the crystal itself. In particular, the ratio of the shift in bandwidth and the shift in frequency (termed the D-f ratio) is predicted to be constant and independent of geometry. However, the experiment does show a slight increase in the D-f ratio with the contact radius when the contact radius is comparable to the wavelength of sound inside the crystal. This effect can be explained by acoustic scattering.