IgG4-related disease (IgG4-RD) is a newly recognized autoimmune systemic disorder characterized by elevated levels of serum IgG4 and abundant infiltration of IgG4-positive plasmacytes in the affected organs. The liver, biliary system and pancreas are the most commonly affected organs. However, involvement of the digestive tract is very rare. To date, only a few cases of isolated gastric IgG4-RD have been reported.We present a case of IgG4-RD of the liver, gallbladder, pancreas and duodenum, which was clinically misinterpreted and thereafter over-treated. A 52-year-old male presented with obstructive jaundice for 3 years, melena for 5 months and hematemesis for 10 days. Three years prior, the patient had undergone biopsies of pancreatic lesions, liver lesions, cholecystectomy and choledochojejunostomy. Histopathology showed chronic inflammatory changes. Endoscopy at admission revealed a duodenal ulcer with active bleeding. Despite medical management, the patient presented with repeated gastrointestinal bleeding. Upon evaluation, serum IgG4 levels were found to be elevated. Histopathology of the duodenal ulcer biopsy and repeated examination of the gallbladder and pancreatic and liver biopsies confirmed IgG4 positive plasma cell infiltration. A definitive diagnosis of IgG4-RD was made and steroid administration was initiated. At last follow up, 11 months to-the-day after initiating steroid treatment, the patient was asymptomatic.Notably, IgG4-RD of multiple digestive organs is still very rare. As a systemic disease, it is characterized by the infiltration of IgG4-bearing plasma cells and raised IgG4 levels. Histopathology findings remain the diagnostic gold standard for this disorder. IgG4-related disease (IgG4-RD) is a relatively recently recognized chronic multi-organ autoimmune disease of unknown origin with a tendency to develop lesions at multiple sites throughout the body . It is kA 52-year-old male from southwest China presented with obstructive jaundice for 3 years, melena for 5 months and hematemesis for 10 days. The patient had been diagnosed with type 2 diabetes mellitus for 4 years, which was treated with metformin. The patient was a chronic tobacco (10 cigarettes per day) and alcohol consumer over the previous 20 years but had quit smoking and drinking for the past 3 years. Three years prior to admission to our hospital, he developed obstructive jaundice, which was investigated with abdominal computed tomography (CT) and revealed multiple hypodense lesions in the liver and pancreatic head mass. He underwent cholecystectomy, choledochojejunostomy and biopsies from the liver and pancreatic lesions. Histopathology revealed chronic cholecystitis with lymphocytic, plasmacytic and eosinophilic infiltration of the gallbladder, liver and pancreatic parenchyma.9/L, 30.0 g/L albumin levels, and serum potassium levels of 3.20 mmol/L . Laboratory tests revealed hemoglobin levels of 75 g/L, a platelet count of 80 × 109 L and serum albumin 25.8 g /L. The day after admission, the patient again developed hematemesis of about 500 mL, for which he was treated with somatostatin, terlipressin and pantoprazole infusion. Sengstaken-Blakemore tube were placed to hemostasis by compression and tube feeding hemostatic medicine. After 4 days of medical intervention, the patient’s gastrointestinal bleeding gradually stopped. Esophagogastroduodenoscopy revealed a duodenal ulcer (A1 stage) with active bleeding, gastric mucosal erosions and esophageal varices (mild). Contrast enhanced computed tomography of the abdomen with three-dimensional reconstruction exposed multiple nodular dense shadows with dilatation of the main pancreatic duct in the tail region and IgG(8~ 15.5 g/L)were found to be 29.200 g/L and 24.50 g/ L respectively and IgG4 disease was suspected  type I. Subsequently, IgG4-RD was found to affect other organs . At presNotably, the biliary tract and pancreas are the organs most frequently affected by IgG4-RD . Few stuA recent review of IgG4-RD cases reporting on gastrointestinal lesions showed that most patients present with multiple organ disease involvement, including the stomach, duodenum, liver, bile duct, esophagus, jejunum, lymph nodes and pancreas Table . Six patIgG4-RD can affect multiple gastrointestinal organs simultaneously or over different time periods. The clinical manifestations can mimic malignancy or other benign diseases such as portal hypertension, acid peptic disease. A high index of suspicion is required to make an accurate diagnosis and avoid unnecessary surgical interventions.


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Thiobacillus thioparus was the first of the acidifying bacteria to colonize the sulfur concrete, decreasing the pH of the environment. The molds Penicillium chrysogenum, Aspergillus versicolor and Cladosporium herbarum were able to grow on the surface of the tested composites only in the presence of an organic carbon source (glucose). During incubation, they produced organic acids and acidified the environment. However, no morphological changes in the concretes were observed suggesting that sulfur–organic copolymers containing styrene could be used as engineering materials or be applied as binders in sulfur-concretes.The aim of this study was to develop new sulfur-copolymer concrete composites using waste compounds that have good mechanical characteristics and show a resistance to biocorrosion. The comonomers used to synthesize the sulfur–organic copolymers were—90 wt. % sulfur; 5 wt. % dicyclopentadiene (DCPD); 5 wt. % organic monomers, styrene (SDS), 1-decene (SDD), turpentine (SDT), and furfural (SDF). The concrete composites based on sulfur–organic copolymers were filled with aggregates, sand, gravel, as well as additives and industrial waste such as fly ash or phosphogypsum. The sulfur–organic copolymers were found to be chemically stable . Partial replacement of DCPD with other organic comonomers did not change the thermal stability markedly but did make the copolymers more elastic. However, the materials became significantly stiffer after repeated melting. All the tested copolymers were found to be resistant to microbial corrosion. The highest resistance was exhibited by the SDS-containing polymer, while the SDF polymer exhibited the greatest change due to the activity of the microorganisms . The concrete composites with sulfur–organic copolymers containing DCPD, SDS, SDF, fly ash, and phosphogypsum were mechanically resistant to compression and stretching, had low water absorbance, and were resistant to factors, such as temperature and salt. Resistance to freezing and thawing (150 cycles) was not confirmed. The concrete composites with sulfur–organic copolymers showed resistance to bacterial growth and acid activity during 8 weeks of incubation with microorganisms. No significant structural changes were observed in the SDS composites after incubation with bacteria, whereas composites containing SDF showed slight changes . The concrete composite containing sulfur, DCPD, SDS, sand, gravel, and fly ash was the most resistant to microbiological corrosion, based on the metabolic activity of the bacteria and the production of ergosterol by the molds after eight weeks of incubation. It was found that  Under ambient conditions, sulfur is a crystalline material of yellow color. The most common crystalline form of sulfur is composed of eight atom rings. When subjected to heating, sulfur undergoes spontaneous radical self-polymerization at 159 °C via decomposition of the crystalline rings. The addition of selenium to sulfur decreases the polymerization temperature. For example, the addition of 25% selenium results in a decrease in the polymerization temperature from 159 °C to ca. 122 °C . HoweverHowever, perhaps the most interesting comonomer for synthesis of sulfur–organic copolymers is 1,3-diizopropylobenzene . ApplicaSulfur–organic copolymers can also be applied in the field of civil engineering as an alternative binder for concretes. Sulfur concrete has a wide range of possible applications including road construction, structures exposed to aggressive chemical environments utilized in chemical, petroleum and food industries, and in farming ,18,19,20The properties of sulfur concretes are provided by the sulfur polymer binder, which is produced in the process of ordinary sulfur synthesis with variable modifiers. However, initial results have shown that the new material has a tendency to lose its mechanical properties during prolonged exposure to thermal treatment or other energy transfer, due to degradation of the internal sulfur–polymer bonds . To solvThe aim of the present study was to develop new sulfur–copolymer concrete composites using waste compounds that have good mechanical properties and show a high resistance to biocorrosion. Due to increasing stockpiles, there is a great interest in finding new applications for the sulfur that remains after industrial processes ,25. AccoSulfur organic copolymers were synthesized using a laboratory reactor . Sulfur Sulfur–concrete composites based on sulfur–organic copolymers filled with aggregates and additives were prepared using a VSM-C Labmix low-speed internal mixer , operating with a rotational speed of 20 rpm at 135–145 °C, for about 1 hr. The aggregate fillers were—normalized granulated sand (fraction 2–8 mm) and gravel. The additives were industrial wastes, fly ash , or phosphogypsum  . A fine aggregate heated to a temperature of 130 °C (266 °F) was gradually added to the liquidized binder, resulting in a drop in temperature to 125 °C (257 °F). The additives  were then dosed before the heated coarse aggregate was added. The mixture was stirred at a temperature of at least 120 °C (248 °F), until a homogeneous consistency was achieved. Finally, it was cast in steel molds heated to 130 °C (266 °F). The sulfur concrete specimens were ready after 24 h of cooling at room temperature. Each full load portion of the mixer produced sixteen cubic specimens (of 100 mm (4 in) side length) and twelve cuboid specimens (40 × 40 × 160 mm) (1.5 in × 1.5 in × 6.25 in). These were then tested for their mechanical and physico-chemical characteristics. The main criteria for selecting the aggregates and additives were the mechanical parameters of the sulfur–concrete product. Economic considerations were of secondary importance.Acidithiobacillus ferroxidans ATCC 23270, Acidithiobacillus thiooxidans ATCC 19377 and Thiobacillus thioparus ATCC 8158, as well as the molds Penicillium chrysogenum ATCC 60739, Aspergillus versicolor ATCC 9577, and Cladosporium herbarum ATCC 6506, were used.Microorganisms known for their corrosive activity against concretes were selected from the American Type Culture Collection (ATCC). The sulfur-oxidizing bacteria The softening temperature of the materials was determined using a Zwick-Roell HDT/Vicat  instrument, according to ISO 306 and ASTM D 1525. Discs 3 mm high and 10 mm in diameter were placed in an oil bath, where they were subjected to 10 N perpendicular indentation. The samples were heated at a rate of dT/dt = 50 deg/h, from room temperature. The temperature reflecting 1 mm penetration of the indenter into the sample was registered as the softening point of the material.3/min.The thermal stability of the materials was studied by thermogravimetric analysis (TGA). Tests were performed using a Netzsch TG 209  instrument, equipped with a TASC 414/3A controller . Samples of around 9–10 mg were tested in a temperature range from 40 to 500 °C, with a heating rate of 10 deg/min, in air atmosphere, and with a gas flow rate of 25 cm3/min. The amount of recrystallized sulfur in the copolymers was analyzed by wide-angle X-ray scattering (WAXS). Tests were carried out using an Empyrean System, equipped with a Cu lamp and Johansson monochromator . The experimental procedure used corundum as an internal standard. Each sample was enriched with an added 20% of corundum powder. The Rietveld procedure was used to calculate the content of each phase-amorphous and crystalline. The amorphous phase content was calculated as the complementary part to 100%.The melting point of the crystalline phase of the materials was determined from calorimetric analyses. Experiments were performed using a differential scanning calorimeter Netzsch DSC 204  instrument, equipped with a TASC 414/3A controller . Samples of about 9–10 mg were tested in a temperature range from −100 to 160 °C, and with a heating rate of 5 deg/min, in air atmosphere and with a gas flow rate of 15 cmThe shore D hardness of the materials was measured using a Zwick/Roell  instrument, according to ISO 4649 . The comThe compressive strength of the sulfur concrete was determined using cubic specimens (10 × 10 × 10 cm (4 in)) in accordance with the PN-EN 12390-3:2011 Standard . CompresFreeze–thaw resistance tests were conducted in accordance to the PN-88 B-06250 Standard  on cubicIn the first test method, cubic specimens from each batch were divided into two series—a reference series, kept at a room temperature of 20 ± 2 °C (68 °F) with relative humidity of 35 ± 5%, and a second series subjected to freeze–thaw cycles in air at a temperature of −20 °C (−4 °F), and in water at a temperature of +20 °C (68 °F). Each cycle took 6 h (4 h of freezing and 2 h for thawing). Freeze–thaw resistance was defined as the integrity of the external surface of the specimen after the freeze–thaw cycles (without any scratches or cracks), with a mean compressive strength of not less than 80% of the mean strength of the reference samples. The second type of test determines resistance to the alternating freezing and thawing in the presence of a deicing agent, and was conducted according to the EN 1338 Standard . The amoAbrasion resistance was studied using two different methods—using a wide wheel and using a Böhme abrasion wheel, according to the EN 1338, EN 1339, and EN 1340 Standards ,36. AbraAbrasion resistance tests using the Böhme abrasion wheel were conducted on cubic specimens with side lengths of 7.0 ± 1.5 mm (2.75 in). A total of 20 g of abrasive was applied to abrasive belt. The abrasive disc performed 22 turns in one cycle. The whole test consisted of 16 cycles. Abrasion was defined as the volume loss (ΔV) from the test sample calculated on the basis of the previously determined density (ρR) and the mass loss after 16 cycles (Δm). Another portion of the powder was applied and the cube was mounted again in a diverted position. The weight of the cleaned sample was measured every 4 cycles and after the final cycle.6 CFU/mL in a Mo1 mineral medium . The density of the suspensions was determined by microscopy . An inoculum mixture of mold suspensions was prepared in an equal volume. The impact of the molds on the polymers was investigated in accordance with the standard  medium  for 5 days at 27 ± 2 °C. Mold suspensions were then prepared, with a density of 10846 2002 ) for liqAcidithiobacillus thiooxidans—(NH4)2SO4 0.2 g, KH2PO4 3 g, MgSO4 × 7H2O 0.5 g, CaCl2 × 6H2O 0.025 g, FeSO4 × 7H2O 0.01 g, sulfur 10 g, water 1 L, pH = 4.0); Acidithiobacillus ferroxidans—(NH4)2SO4 3 g, KCl 0.1 g, K2HPO4 0.5 g, MgSO4 × 7H2O 0.5 g, Ca(NO3)2 0.01 g, FeSO4 × 7H2O 44.2 g, H2SO4 1N 10 mL, water 1L, pH = 2.3); and Thiobacillus thioparus—2SO4 0.1 g, CaCl2 0.03 g, FeCl3 0.02 g, MnSO4 0.2 g, Na2S2O3 10 g, water 1 L, pH = 6.6). The cultures were cultivated for 2 months at a temperature of 27 ± 2 °C, using a Unimax 1010 shaker  at 125 rpm. Bacterial growth was controlled by measuring metabolic activity based on the ATP concentration, using a HY-LITE 2 luminometer . After 1 and 2 months, changes in the morphology and chemical structure of the composite samples were assessed, and the pH of the culture fluid was measured.The growth of microorganisms, molds, and bacteria on three composites containing sulfur polymers was assessed. Samples of the sulfur polymer concrete composites were inoculated with 1 mL of a mold mixture, prepared as described above, and incubated for 2 months in a BINDER climatic chamber . After 1 and 2 months, the growth of the molds was assessed based on measurement of their ergosterol content . Extraction of the ergosterol was carried out in accordance with the methodology developed for building materials . The erg2PO4 1.0 g, (NH4)SO4 0.3 g, MgSO4 × 7H2O 5.0 g, glucose 5 g, yeast extract 10.0 g, water 1 L), with the addition of sulfur concrete composites under the following conditions—1 mL of mold inoculum, incubation time 2 months, temperature of 27 ± 2 °C. After 1 and 2 months, the pH of the medium was measured and the samples were tested for the presence of acid metabolites produced by the molds. The pH of the liquid media, with and without the addition of sulfur polymer concrete composites, was measured using an CP-411 pH meter . The acid activity was determined using a 10-fold concentration of the medium after the mold culture. The tests were carried out by HPLC–MS , using a Surveyor liquid chromatograph with ThermoScientific PDA and RI detectors and a mass spectrometer , in accordance with a previously method described [The acid activity of the molds on the sulfur polymer concrete composites was investigated in a liquid culture, using an Mo2 medium , at 100 × magnification, with an additional source of reflected light. Comparative analyses of the chemical structure were made by FTIR using a Fourier Transform Infrared Spectroscope , with an ATR  for rapid analysis.The thermal parameters of the copolymers are presented in DSC studies of sulfur–organic copolymers revealed structural changes in the copolymers due to their repeated melting. Except for 2 SDS, melting lowered the melting enthalpy of the materials .Copolymerization of sulfur with organic monomers decreased its ability to recrystallize by almost half. This effect was most pronounced when pure sulfur was repeatedly melted, whereas it was hardly noticeable in the case of sulfur–styrene–DCPD copolymers (sample number 5). Partial replacement of DCPD with other monomers, especially turpentine or furfural, resulted in significant decreases in the melting enthalpy of the material. The degree of crystallinity can be used as a measure of the efficiency and stability of copolymerization in sulfur–organic copolymers, since it reflects the extent and durability of sulfur bonding with particular comonomers. The only component able to crystallize is “free” sulfur, which does not take part in the copolymerization reaction. DCPD is the basic component in sulfur–organic copolymers and is indispensable for ensuring the mechanical strength of the materials. At the same time, it is responsible for stiffness and possibly fragility. Partial replacement of DCPD makes the copolymers more resistant to compression and improves their thermal stability, while turpentine, 1-decene or furfural makes them less stiff. Given the importance of the thermal “history” of the materials, the mechanical and dynamical parameters of the sulfur–organic copolymers were determined, before and after thermal treatment (air/72 h/70 °C). The influence of thermal aging on the performance of the materials is presented in The mechanical and dynamical properties of the sulfur–organic copolymers changed significantly due to their thermal ageing of the materials. These changes were in agreement with the results for structural modification of the copolymers. The influence of changes in the degree of crystallinity, a function result of thermal aging, on the mechanical and dynamical properties of the materials was confirmed . Sulfur–No mold growth on the tested sulfur copolymers was observed during cultivation with Mo liquid medium, either with or without the addition of glucose, nor on the solid medium without glucose. This shows that sulfur copolymers are not a source of carbon for molds. Only with the use of solid Mo medium with glucose was mycelium observed on the sulfur copolymers, in places that had been inoculated with molds. In the cases of polymer samples number 2–4, there were changes in the mycelium color and limited production of spores, compared to the control (mycelium on Mo solid). In the case of sample number 5, the mold mycelium covered the medium and the copolymer .Measurements of the dry mass of the mold mycelia on liquid Mo media containing polymers, both with and without glucose, showed the highest biomass in the case of the medium with SDT copolymer (number 3) and the lowest on the medium with SDD copolymer (number 4). However, the differences in the dry masses of the mycelium were not statistically significant, which indicates that the polymers neither provided a carbon source for these microorganisms, nor released substances into the medium that inhibited mold growth .Polymers number 2–4 showed no morphological changes after incubation with molds. Slight sulfur crystallization was observed only on the surface of polymer number 5, incubated with molds .−1 wave range. These differences also occurred on the solid medium, after incubation with molds (800–2400 cm−1)  .The results indicated that copolymers number 2–4 are the most resistant to molds and can be used as raw materials for the production of sulfur concrete. In the case of copolymer number 5, mold growth led to structural changes. Therefore, in the next stage, two variants (number 2–3) of the sulfur copolymers were used. Sample number 4, based on copolymer 5 (SDF), was used for the purposes of comparison , while sThe use of additives, such as dust and good quality aggregates, can ensure that the product does not absorb water and has a high strength. Dust additives  improve tightness and, thereby, reduce water absorption. The addition of fillers to sulfur concrete does not have any negative effects on the final product. The use of 2–8 mm aggregate (number 10—0.375 in) had a strong effect on the mean cube compressive strength of the sulfur concrete . The mean cube compressive strength of the sulfur mortar, consisting of elementary sulfur with sand and fly ash or phosphogypsum, ranged from 49.6 MPa to 57.0 MPa. Modification of the sulfur with styrene (SDS) significantly increased the compressive strength of the sulfur mortar in samples 2–3, in comparison to mortar based on elementary sulfur, to 46.5 MPa. In the case of sample number 4 with furfural (SDF), the increase in compressive strength was not as high. In comparison to the mortar based on elementary sulfur, the difference in mean compressive strength was around 20%. With some exceptions, the strength of the sulfur concretes was significantly higher than that of the mortars. The test results indicate that the compressive strength of sulfur-concrete, based on a binder modified with dicyclopentadiene and furfural (number 4), was lower than that for sulfur concrete modified with dicyclopentadiene or styrene (number 2–3). As expected, the curing time of the sulfur concrete did not significantly affect the compressive and bending tensile strength. Full compressive strength was reached in the first 2–4 days, while 90% strength was reached during the first 24 h from casting. Only slight increases in compressive strength (compared to the early strength) were observed over 28 days.The elasticity modulus of the sulfur concrete was higher than that of C50/60 class cement concrete ).This study also set out to determine the freeze–thaw resistance of the sulfur concrete. Concrete members for road infrastructure generally require freeze–thaw resistance of F150, corresponding to 150 cycles of freezing and thawing in water. After the test, the decrease in the strength of the frozen samples should not exceed 20% in comparison to the reference samples. Our results indicated a 35%–46% decrease in compressive strength, in comparison to the reference samples . One rea2 (0.0614 lb/ft2), after 56 cycles. Concrete is considered to be freeze–thaw resistant to deicing salts if the total amount of surface peeling after 56 cycles is less than 1 kg/m2 (0.2048 lb/ft2)  . Given tAbrasion resistance is an extremely important parameter determining the durability and long-term requirements of the sulfur concrete product. Our results confirmed that the different sulfur concrete compositions had very good resistance to abrasion, meeting the highest, Class 4, requirements  Tab.Sulfur concrete is composed of sulfur as the binder, general aggregates  and additives. All kinds of wastes can be used to make this material, irrespective of their quality. Compared to general concrete based on cement, sulfur concrete exhibits relatively high compressive and tensile strengths and a high corrosion resistance. Unlike general concrete cement (which reaches full concrete strength after 28 days), the final compressive and tensile strength of sulfur can be obtained a short time after solidification.Acidithiobacillus ferroxidans, Acidithiobacillus thiooxidans, and Thiobacillus thioparus, on the sulfur concrete samples after 1 month of incubation, showed a slight color change towards yellow for some samples .Due to the different environments in which sulfur concrete might be used, an important feature is resistance to biocorrosion. Observations of bacterial growth by  samples . No chanAcidithiobacillus ferroxidans. This bacterium is known for its corrosive properties, producing sulfuric acid and oxidizing iron [Microscopic observations confirmed the recrystallization and deposition of sulfur on concrete number 4, after two months . The smaing iron .−1 after 1 month and about 1,000cm−1 after 2 months) for samples 3 and 4, with both A. ferroxidans and A. thiooxidans bacteria. However, these changes were not significant.The FTIR spectra for concrete composite number 2 did not show any changes before and after 1 and 2 months of incubation with bacteria in a liquid medium . There wAcidithiobacillus ferroxidans was at the same level as that in the control sample, which suggests a lack of or very low metabolic activity in the case of this strain. In the cases of Acidithiobacillus thiooxidans and Thiobacillus thioparus, the ATP content was high, in the range of 320–13,500 Relative Light Unit (RLU). The highest concentration of ATP was measured in media with composites numbers 3 and 4. The ATP content increased with the incubation time, which might indicate favorable conditions for the growth of these two bacteria. The lowest concentration of ATP was measured in the medium with composite number 2. In this case, the ATP level decreased after 2 months for all tested bacteria, which might indicate unfavorable conditions on the surface of this sulfur concrete.The growth of bacteria on media containing composites was measured on the basis of metabolic activity, indicated by the ATP content . The ATPThe growth of molds on the sulfur concrete samples was measured on the basis of the content of ergosterol . After 4T. thioparus did the pH decrease, from 6.23 to 5.28. This bacterium is the first colonizer of concretes. It produced polythionic acid and sulfuric acid, which caused pH decreases, enabling the growth of further sulfur bacteria. This was particularly important due to the fact that metabolites biosynthesized by Acidithiobacillus thiooxidans have the greatest impact in the biocorrosion process [The acid activity of the bacteria and molds on the media with the addition of sulfur concrete samples was also tested . There w process . These b process ,41. The Acidification of the environment was observed on all media with molds. The pH decreased from 4.56–5.40 to 2.09–3.57 . AnalysiIn this study, sulfur–organic copolymers containing 90 wt.% of sulfur and 5 wt.% of DCPD were produced, completed with 5 wt.% of an organic monomer—styrene (SDS), turpentine (SDT), 1-decene (SDD), or furfural (SDF). The polymeric materials were found to be chemically stable. Partial replacement of DCPD with other organic comonomers did not change the thermal stability markedly but did make the copolymers more elastic. However, the materials became significantly stiffer after repeated melting. Partial replacement of DCP with 1-decene, turpentine, or furfural reduced this effect under dynamic conditions. All the tested copolymers were found to be resistant to microbial corrosion. The highest resistance to mold growth was noted for the SDS-containing polymer. Polymers containing SDT and SDD showed less resistance, while the SDF polymer underwent the greatest changes  after incubation with microorganisms. Sulfur–organic copolymers containing styrene can be used as engineering materials or applied as binders in sulfur-concretes.The concrete composites with sulfur–organic copolymers containing DCPD, SDS, SDF, fly ash, and phosphogypsum were mechanically resistant to compression and stretching, had low water absorbance, and were resistant to factors such as temperature and salt. Resistance to freezing and thawing (150 cycles) was not confirmed.T. thioparus was the first of the acidifying bacteria to colonize the sulfur concrete, decreasing the pH of the environment. The molds P. chrysogenum, A. versicolor, and C. herbarum were able to grow on the surface of the tested composites only in the presence of an organic carbon source (glucose). During incubation, they produced organic acids and acidified the environment. However, no morphological changes in the concretes were observed. Such changes might occur in the case of contact with sewage, agricultural waste, or soil, over extended periods. The concrete composites with sulfur–organic copolymers showed resistance to bacterial growth and acid activity during 8 weeks of incubation with microorganisms. No significant structural changes were observed in the SDS composites after incubation with bacteria, whereas composites containing SDF showed slight changes . The concrete composite containing sulfur, DCPD, SDS, sand, gravel, and fly ash was the most resistant to microbiological corrosion, based on the metabolic activity of the bacteria and the production of ergosterol by the molds, after 8 weeks of incubation. It was found that In summary, the ecological concrete composites are suitable for use in the construction of internal elements, such as small prefabricated elements, due to their good strength parameters and resistance to external factors. However, their use is not recommended under conditions of external exposure to changing atmospheric parameters (freezing and thawing cycles) or contact with sewage and soil .Kotynia, R.; Wlendziak, R.; Pawlica, J.; Berlowska, J.; Dziugan, P.; Palka, K.; Tynenski Z. Application in Polish Patent Office No P.422745 “Sulfur concrete mix”.Gozdek, T.; Imiela, M.; Sicinski, M. Tynenski Z.; Palka, K.; Bielinski, D.; Anyszka, R. Application in Polish Patent Office No P.422745 “Method for obtaining stable polymeric sulfur that is a binder for sulfur concretes and the stable polymeric sulfur that is a binder for sulfur concretes”.


IgG4‐related sclerosing disease (IgG4‐RD) occasionally involves breast entity, which is often difficult to distinguish from malignant tumor, as both radiologically resembles. We report a case of a breast mass diagnosed as IgG4‐related mastopathy (IgG4‐RM) through needle biopsy, which responded well to glucocorticoid therapy. Unnecessary excision should be avoided. The laboratory data showed serum IgG4 levels of 515 mg/dL, IgG levels of 2018 mg/dL, IgE (RIST) levels of 230 mg/dL, and negativity for anti‐SS‐A, B antibody. The patient was suspected to be suffering from IgG4‐related sclerosing disease and was introduced to the Department of Rheumatology in our hospital. The positron emission tomography (PET)‐CT scan showed a right breast mass and right axillary lymph nodes with high fluorodeoxyglucose (FDG) uptake  , IgG4 was positive in 85% of the IgG‐positive cells (Seventy IgG4‐positive cells per high power field) Figures  and 4. F4Over the 8 weeks of prednisolone treatment, the breast mass almost disappeared completely under ultrasonography and MRI Figure . We will5The present case showed a breast mass that was diagnosed with IgG4‐related mastopathy (IgG4‐RM) as a part of systemic IgG4‐related sclerosing disease (IgG4‐RD) and responded well to glucocorticoid therapy.IgG4‐RD can involve one or multiple organs. Multiple organs are affected in 60%‐90% of the patients. Patients of IgG4‐RD often present a mass in the affected organ  or diffuse enlargement of an organ . IgG4‐RD occasionally involves breast entity.IgG4‐RM or IgG4‐related sclerosing disease of the breast has been described as “sclerosing mastitis” or “inflammatory pseudotumor” in the literature.It is important to recognize this IgG4‐related entity of the breast, regardless of whether the breast entity is seen in systemic IgG4‐RD setting or in the breast as isolated organ, because the graphical appearance of the entity is similar to that of breast cancer, as in our case.In the literature, eight articles have reported 12 cases of IgG4‐related mastopathy (Table The diagnostic criteria of IgG4‐RD have not yet been established. Most of the current criteria include: (1) swelling or a mass lesion in one or more organs, (2) elevated level of serum IgG4, and (3) infiltration of the lymphoplasmacytes with abundant IgG4‐positive plasma cells. There have been attempts to establish clear diagnostic criteria since the concept of IgG4‐related disease was proposed in 2001 by Hamano et al.In terms of IgG‐RM, we need histological examination for the diagnosis, as its radiological findings resemble malignant tumor. When we face a case of breast involvement as an isolated organ, IgG4‐RM should be kept in mind as a differential diagnosis, as it is rare. On the other hand, when we face a case of breast involvement as a part of systemic disease, differential diagnosis with malignant tumor is essential, as radiological examination does not provide enough evidence for definitive diagnosis between the two. We have shown in this report that differential diagnosis is possible by the least invasive method: needle biopsy.In the previously‐reported cases of IgG4‐related sclerosing disease of the breast, half of the patients were treated with excision, rather than with steroid therapy.IgG4‐RD responds well to steroid therapy.6In conclusion, IgG4‐related sclerosing disease of the breast is rare. Recognizing this disease is very important, whether it is manifested as a part of systemic IgG4‐RD or as an isolated organ entity, because its clinical and radiological findings are similar to those of malignant tumors. IgG4‐RM can be readily diagnosed with needle biopsy and can be treated with steroid therapy. We would like to highlight that unnecessary surgical biopsy should be avoided.The authors declare that they have no competing interests.TY, TH, and EI: interacted with the patient. TY, TH, and EI: identified and acquired relevant reports. SM and KK: diagnosed pathologically. TY: drafted the report. TH, MK, RW, AN, HM, TT, TS, MT, EI, SM, KK, and YK: critically reviewed the report. All authors read and approved the final submitted version.


Excellent inter-session and inter-rater reliability, adequate absolute accuracy, almost perfect agreement and strong correlations were shown for caliper, US and their comparison for all SL dimensions. US measurements presented higher absolute accuracy than caliper measures for SL length and thickness dimensions, while caliper displayed greater absolute accuracy for SL width dimensions. Good repeatability (P > 0.05) was shown for all SL dimensions by US, caliper and their comparison, except for SL width dimension measured with US (P = 0.019). Both US and caliper could be recommended for all SL dimensions evaluation due to their excellent reliability and absolute accuracy in cadavers, although width dimensions should be considered with caution due to US repeatability differences.The purpose was to evaluate intra and inter-rater reliability, repeatability and absolute accuracy between ultrasound imaging (US) and caliper measures to determine Spring ligament (SL) dimensions in cadavers. SLs were identified from 62 human feet from formaldehyde-embalmed cadavers. Intra and inter-observer reliability, repeatability and absolute accuracy of SL width, thickness and length between US and caliper measurements were determined at intra and inter-session by intraclass correlation coefficients, Pearson´s correlation coefficients, Student  In addition, secondary structures such as plantar fascia, superficial deltoid ligament and other plantar ligaments in conjunction with the SL may be considered as the responsible anatomic structures to maintain the foot internal arch. SL is extended from the calcaneus to navicular bones forming a sling that stabilizes the hindfoot2.Spring ligament (SL), also called as plantar calcaneonavicular ligament, plays an important role as the main stabilizer of the foot internal arch with great repercussion in the hindfoot function4. Several studies have evaluated this anatomic structure by ultrasound imaging (US) and caliper measurements in cadavers8, although prior investigations have not yet analyzed the reliability for measuring SL dimensions using caliper and US to determine the anatomic correlation of the SL in cadaveric feet. Thus, given that there is existing literature correlating ultrasound measurements to clinical decisions and other imaging modalities8, absolute accuracy of the measurement needs to be determined due to the lack of studies about reliability and correlation between caliper and US measurements of the SL in cadaveric feet addressing width, thickness and length for a better accuracy of these evaluations and the improvement of ultrasound-guided procedures9. Both intra and inter-rater reliability needs to be detailed in order to determine absolute accuracy and repeatability of these measurements within a same evaluator and between both evaluators by both US and caliper13. Separately, both tools have shown appropriate reliability for SL dimensions measured by experienced raters, nevertheless US and caliper measures have not been compared as well as SL width dimensions have not yet been measured by US8. We hypothesized that caliper and US use may show an excellent reliability to analyze of the SL anatomic dimensions in cadaver. Thus, the study purpose was to evaluate the intra and inter-rater reliability between US and caliper measures to determine SL width, thickness and length in cadaveric feet at intra and inter-session.Indeed, SL injuries seem to be very common and related to the rupture of the ligament, leading to plantar flexion talus displacement and valgus hindfoot deformity, which may generate an adult acquired pes planus. Consequently, surgery may be required for this rupture after traumatic conditions or others factors such as degenerative disease, iatrogenic injury, infection or tumors on the hindfoot, which require a full understanding of the SL anatomy. In addition, SL reconstruction provides a good correction of the foot internal arch with main implications in the rehabilitation field. Accordingly, anatomic landmarks of the SL may be essential to play down surgery-associated lesions and deformities of the hindfoot14.A reliability study was carried out in order to determine the intra and inter-rater reliability between US and caliper measures detailing SL width, thickness and length in cadaveric feet at intra and inter-session. The Updated List of Essential Items for Reporting Diagnostic Accuracy Studies (STARD 2015) criteria were followed15.The minimum number of specimens required was calculated based on reliability testing to determine reliability. In this study, the ICCs were used for reliability testing at a target value of 0.8 and a 95% CI of 0.2. We calculated the sample size to be 36 specimens with a Bonett’s approximationThis research was approved by the local Research Ethical Committee in the University of Rey Juan Carlos (URJC), in the town of Móstoles, province of Madrid (Spain), with internal code 0801201800618. In addition, all methods were performed in accordance with the relevant guidelines and regulations. Consent for this study was previously obtained from the anatomy department.9. The mean (SD) age was 76.46 (6.46) years; range from 66 to 89 years old. The human cadaveric feet comprised 30 right and 32 left feet. The adult cadavers came from the Scientific Anatomy Center, S.L. in the town of Valencia (Spain) in the town of Valencia (Spain). Scientific Anatomy Center, S.L. which included informed consent as part of the cadaver donation process.Sixty-two feet from formaldehyde-embalmed human cadavers, 8 males and 26 females, without presence of any type of trauma were recruited in our research protocol16.The used preservation method for embalming the cadavers was perfusion through the femoral artery with a blending of formaldehyde, ethanol, methanol, phenol and glycerine that improve the longevity of the body and tissues, reducing the infection riskUS images were recorded by a Mindray Z6 Digital Ultrasonic Diagnostic System  by using a linear transducer type L4-P with a frequency bandwidth range of 5–10 MHz.All human cadaver feet were located at the same immobilized neutral position. Then, two independent and experienced musculoskeletal podiatrists  collected the US measurements to determine the width, thicknesses and length (cm) of the SL in cadaveric feet Fig. .Figure 1Thereafter, the foot cadaver dissection was carried out in order to expose the SL for its measurement with a digital LCD caliper  with the subtalar joint foot in neutral position. Two podiatrists recorded the width, thicknesses and length (cm) of the SL in cadaveric feet with this device Fig. .Figure 2st and 2nd sessions as well as 1st and 2nd observers were used to analyze the intra and inter-rater reliability at intra and inter-session. The podiatrists did not have access to the information records of the 1st session until recorded values were registered after the 2nd session.After two days, the protocol design was repeated identical to the first session of measure. The values of the measurements from 1P-value > 0.05 of the Kolmogorov-Smirnov test). Second, mean ± standard deviation (SD) as well as upper and lower limits for 95% confidence interval (CI) were used in order to describe all data. Finally, differences between two measurement values were analyzed by the Student t test for paired samples.Statistical analyses were carried out by the statistical package of SPSS 19.0 software for windows . First, the Kolmogorov-Smirnov test was used to assess normality. All variables were parametric data due to a normal distribution was shown (according to a r). Indeed, ICC values were interpreted as poor (ICC < 0.40), fair (ICC = 0.40–0.59), good (ICC = 0.60–0.74), and excellent (ICC = 0.75–1.0)17. In addition, r coefficient values were categorized as weak (r = 0.00–0.40), moderate (r = 0.41–0.69), and strong (r = 0.70–1.00)18.Reliability between two measurement values was determined by the Intraclass Correlation Coefficient (ICC) and Pearson´s correlation coefficient  between sessions and devices expressed the degree of error proportional to the mean of the measurement units, and these statistics were calculated using the methods described by Bland and Altman12. Furthermore, values of normality (VN) of the sample for all outcome measurements were obtained by the formula VN = Mean + /_1.96 * SD.Standard errors of measurement (SEM) were calculated to measure the range of error of each parameter. The SEM was calculated from the ICCs and SDs for each of the three measurements. SEM were calculated according to the formula SEM = SD × sqrt (1 − ICC). Indeed, the minimum detectable change (MDC) was calculated from the SEM values by the following formula MDC = 12 were calculated to display the agreement between US and caliper. These plots showed the difference between each pair of measurements on the y-axis against the mean of each pair of measurements on the x-axis. A P-value < 0.05 with a 95% CI was used for the data analysis.Finally, Bland-Altman plots(1-1) = 0.992–1.00) and inter-rater reliability (ICC(1-1) = 0.997–0.999) with a strong correlation  for length and thickness measurements. Nevertheless, poor to good intra-rater (ICC(1-1) = 0.545–0.612) and inter-rater reliability (ICC(1-1) = 0.279) with a weak non-significant correlation  was shown for width measurements. In addition, there were not statistically significant differences (P < 0.05) between sessions.Analysis of reliability of the SL morphology by US between the first and second session by first observer Table  showed e(1-1) = 0.875–1.00) and inter-rater reliability (ICC(1-1) = 0.958–0.996) with a strong correlation  for length, thickness and width measurements. In addition, there were not statistically significant differences (P > 0.05) between sessions.Analysis of reliability of the SL dimensions by caliper between the first and second session by first observer Table  showed e(1-1) = 0.987–0.999) and inter-rater reliability (ICC(1-1) = 0.995–0.998) with a strong correlation  for length and thickness measurements. Nevertheless, poor to fair intra-rater (ICC(1-1) = 0.276–0.540) and inter-rater reliability (ICC(1-1) = 0.213) with a weak non-significant correlation  was shown for width measurements. In addition, there were not statistically significant differences (P < 0.05) between sessions.Analysis of reliability of the SL dimensions by US between the first and second session by second observer Table  showed e(1-1) = 0.877–1.00) and inter-rater reliability (ICC(1-1) = 0.996) with a strong correlation  for length, thickness and width measurements. In addition, there were statistically significant differences (P < 0.05) between sessions for length, but not for thickness or width measurements (P > 0.05).Analysis of reliability of the SL dimensions by caliper between the first and second session by second observer Table  showed e(1-1) = 0.877–0.978) with a strong correlation  for length and thickness measurements. Nevertheless, poor intra-rater reliability (ICC(1-1) = 0.207) with a weak non-significant correlation  was shown for width measurements. In addition, there were inter-session statistically significant differences (P < 0.05) between US and caliper measurements for thickness and width, but not for length measurements (P > 0.05).Analysis of reliability of the SL dimensions by first observer between US and caliper measurements Table  showed e(1-1) = 0.862–0.996) with a strong correlation  for length and thickness measurements. Nevertheless, poor intra-rater reliability (ICC(1-1) = 0.232) with a weak non-significant correlation  was shown for width measurements. In addition, there were inter-session statistically significant differences (P < 0.05) between US and caliper measurements for thickness, but not for length and width measurements (P > 0.05).Analysis of reliability of the SL dimensions by second observer between US and caliper measurements Table  showed e(1-1) = 0.938–0.994) with a strong correlation  for length, thickness and width measurements. Nevertheless, there were inter-rater statistically significant differences (P < 0.05) between first and second observer for width measurements, but not for length and thickness measurements (P > 0.05).Analysis of reliability of the SL dimensions by US between inter-session first and second observer Table  showed e(1-1) = 0.825–0.998) with a strong correlation  for length, thickness and width measurements. In addition, there were not any inter-rater statistically significant differences (P > 0.05) between first and second observer for length and thickness, width measurements.Analysis of reliability of the SL dimensions by caliper between inter-session first and second observer Table  showed e(1-1) = 0.911–0.966) with a strong correlation  for length, thickness and width measurements. In addition, there were not inter-session statistically significant differences (P > 0.05) between US and caliper measurements length, thickness and width measurements.Analysis of reliability and correlation of the SL dimensions between inter-session US and caliper measurements for both observers Table  showed aThe LoA (95% CI) of the measurements using both devices, US and caliper, showed values for all dimensions which tended to almost perfect agreement, showing no variability. Figures 20, specially Mengiardi et al. described accurately the SL complex in asymptomatic cadaveric feet.Several investigations about dimensions of the SL have used magnetic resonance imaging (MRI) to evaluate the anatomy of this structure in cadaveric feet8, our study may be considered as the first study showing an excellent inter-session and inter-rater reliability 17, absolute accuracy showing adequate SEM , MDC  and VN  values12, and almost perfect agreement according to the 95% CI LoA  values and Bland-Altman plots distribution 18 between caliper and US to determine all SL dimensions in cadaveric feet.Despite both US and caliper measurements of SL dimensions have been previously carried out in cadavers13, our measurements showed good repeatability  for the SL dimensions by US . Despite SL width dimensions should be considered with caution due to these US repeatability differences, to the authors’ knowledge, our study may be considered as the first research work providing reliability, absolute accuracy, correlation and repeatability for SL width dimension measured by US, due to prior US reliability studies mainly focused on SL length and thickness8.According to repeatability analysesUS Table , caliperUS Table  and compUS Table  between US = 0.069 cm versus MDCCaliper = 0.083 cm), thickness  and width , showed that US measurements presented a higher absolute accuracy with lower MDC values than caliper measures for SL length and thickness dimensions, while caliper displayed greater absolute accuracy with lower MDC for SL width dimensions. According to MDC may be used as the change magnitude necessary to provide measuring confidence to be sure about these values are not the result secondary random variations or measurement errors12, these MDCs may be considered as cut-off reference values to determine SL dimensions modifications secondary to anatomic abnormalities8, ultrasound-guided invasive procedures9, and ligament injuries course after treatment22.In addition, MDC values for the SL dimensions, such as length (MDCet al. showed that US may be an effective imaging tool to evaluate SL abnormalities in patients with symptomatic posterior tibial tendon conditions compared to MRI as the gold standard tool23. In addition, Crim24 stated that MRI may be considered as the first-line evaluation procedure for the assessment of the SL conditions. Nevertheless, our study findings did not consider US and caliper measurements under SL conditions, while US and MRI have already been compared showing excellent findings23. As a future research line, we propose that both US and caliper reliability should be studied under SL pathologies.In accordance with our findings suggesting that these two techniques may be accurate for determining SL dimensions in human cadaveric feet, Harish 9. Future studies should consider these procedures in fresh-frozen cadavers as well as in vivo with healthy subjects and SL injured patients22.The present study supported an ultrasound technical study for SL dimensions evaluations compared with caliper measures as gold standard which may be used as a reference for ultrasound-guided procedures in formaldehyde-embalmed human cadavers9.Several limitations should be recognized regarding our approach for anatomical dissection and US procedures. Thus, we could not determinate the whole SL complex morphology and anatomic variations and further investigation is need in this field. First, only 2 observers were compared in the present study and future research studies should consider several observers for a better accuracy. Second, echogenicity changes could have modified the ability to perform the ultrasound measurements in ligament morphology, especially in the width dimensions showing a worse accuracy in the present study, given that the tissues have been infused with formalin for preservation due to this procedure can lead to asymmetric contraction of the tissue secondary to its anisotropic natureBoth US and caliper could be recommended for all SL dimensions evaluation due to their excellent reliability and strong correlation in cadavers, although width dimensions should be considered with caution due to US repeatability differences.


When the functionality of UHPC is considered, at case study level, two design options of a bridge are tested, which use either totally CC (CC design) or CC enhanced with UHPC (UHPC design). The results show that the UHPC design could provide a reduction of 14%, 27%, and 43% of carbon, material, and water footprint, respectively.There is a common understanding that the environmental impacts of construction materials should be significantly reduced. This article provides a comprehensive environmental assessment within Life Cycle Assessment (LCA) boundaries for Ultra-High-Performance Concrete (UHPC) in comparison with Conventional Concrete (CC), in terms of carbon, material, and water footprint. Environmental impacts are determined for the cradle-to-grave life cycle of the UHPC, considering precast and ready-mix concrete. The LCA shows that UHPC has higher environmental impacts per m The construction industry is recognized as an issue of the global environmental impact . Cement The innovation of Ultra-High-Performance Concrete (UHPC) is increasingly used ,12 for iHowever, UHPC provides a significant reduction in the ratio of mass to load-bearing capacity . It is pEnvironmental performance of construction materials could be comprehensively described by using LCA  based onThis article systematically investigates carbon, material, and water footprint of UHPC in comparison with CC, aiming to facilitate the decision-making process, undertaken by the construction planners. The footprints are assessed within cradle-to-grave life cycle stages according to EN 15804 .Specifications of concrete are regulated in DIN EN 206 . Two mixUHPC is known for its high compressive strength of more than 150 MPa with low water/cement ratio . SchmidtFor the CC mixtures, the average mixture of concrete in Germany is used as it has been described for the environmental product declarations (EPD) of the concrete by the German Federal Association of Concrete . For theThe Life Cycle Inventory (LCI) of UHPC in comparison with CC is described based on the Life Cycle Stages according to EN 15804 . LCI InpA1 life cycle stage of the concrete represents cradle-to-grave inventory (A1–A3) of its ingredient, for instance, A1–A3 production process of cement. Cement production includes raw material extraction (A1), transport of the raw materials (A2), and production process (A3), e.g., manufacturing of clinker, and cement grinding. Production process of quartz sand and quartz powder is defined within GaBi XIV construction materials . This prA2 life cycle stage represents the transport of concrete ingredients to the concrete plant. Transporting types and distances of cement, aggregate, fly ash, plasticizers are taken from an LCA study conducted by the German ready-mixed concrete association , while iA3 life cycle stage comprises the concrete mixing process. Concerning CC, life cycle inventories of electricity, diesel and fuel oil demand are analyzed according to data from a technical report of energetic optimization of concrete production of the ready-mix concrete plant done at the University of Stuttgart . The ele3. The modeling of the heat treatment is based on the expert’s interviews. Therefore, an amount of 3 L/m3 of fuel oil is required. 3 concrete.In addition, A3 life cycle stage of precast concrete includes compacting and heating treatment of the concrete. The research project of the Technical University of Cottbus  describeLCI of the A4 life cycle stage of CC and UHPC are the same. The ready-mix concrete is transported by a truck mixer from the concrete plant to the construction site. The GaBi database  does not3/h, with a utilization rate of 50%. This is equivalent to an operating period of 0.012 h/m3. Precast concrete is either installed by using a revolving tower crane or by using a mobile crane [The transport of the precast concrete is modeled by using a truck with a total weight of 34–40 t and a capacity of 27 t with fuel consumption of 0.46 L/km . Environ3/h according to the recommendations from experts. In terms of UHPC, there is no documented practical experience concerning the demolishing process [3/h.C1 life cycle stage of UHPC and CC refers to the deconstruction measures. They differ from each other in the type, the capacity, and the fuel consumption of excavator. CC could be demolished using an excavator with a total weight of 30 t and fuel consumption of 18 L/h . The cap process . A more Transport to the recycling plant represents C2 life cycle stage. In Germany, the construction waste is usually transported by trucks with a total weight of 40 t . The disLife cycle stage of C3 includes the treatment of the construction waste. The waste of CC is going to be pre-crushed with an excavator and transported to the processing plant by a wheel loader, related technical specifications are described by Heyn and Mettke . In case100) for defining the carbon footprint [2 equivalents. CFs are documented in the fifth assessment report (AR5) by the Intergovernmental Panel on Climate Change (IPCC) [The Joint Research Center (JRC) of the European Commission recommends using characterization factors (CFs) of a 100-year time horizon global warming potential (GWPootprint . The care (IPCC) . The elereport AR by the IMaterial footprint is defined in terms of Raw Material Input (RMI) and Total Material Requirement (TMR). RMI measures cumulative raw materials used within the whole process chain of a product ,56. UsedThe TMR thus measures the total amount of abiotic and biotic primary material required over the complete life cycle ,58. RegaCFs of RMI are developed by the Sustainable Resource Futures (SURF) group in the Center for Environmental Systems Research (CESR) at the University of Kassel ,59,60, wWater footprint is assessed according to the AWARE method , which i3/m2 * month of any basin is related to the world average to calculate regionalized CFs, which are available online http://www.wulca-waterlca.org/aware.html.AWARE aims at identifying the risk of freshwater depletion for any other water user in the same area. The resulting indicator Availability-Minus-Demand with the unit m3 world eq/m3. For instance, the German CF of 1.36 [The CFs represent “a relative value of the impact score of water consumption” ,  are tested ,64. The However, the design of the bridge is wholly described by Brühwiler et al. . An overThe system boundaries include the whole life cycle from the raw material extraction to the end-of-life phase of the bridge within the two design options. LCA calculations are done within the GaBi database. Regarding materials, which are not available in the GaBi database, i.e., steel fibers, they are modeled within the ecoinvent database . For theIn terms of the module A4, for the transportation modeling, van, truck, and road train are used for the transportation modeling. The choices of the transport type depend on the amount of transported material. Transportation distances are defined according to Lünser . An addiA5 represents the installation of precast and ready-mix concrete at the construction site. Diesel demand of the construction equipment and the amount of liquefied petroleum gas to install the bituminous asphalt sheeting are defined according to the expert’s interviews.The lifespan of the bridge, use phase B4, is assumed to be 90 years . Mainten3 in terms of CC [3 according to the experts’ interviews. A milling machine with 2.54 L/m3 diesel demand could be used for the deconstruction of the road surface, and the deconstruction of the sealing could be done using an excavator with 0.20 L/m2 diesel demand and 0.13 L/m2 liquefied petroleum gas demand [3 diesel demand, excavator with 0.30 L/m3 electricity demand of 18.26 L/m3 for other processes within a waste plant [3 and simultaneously 21.21 MJ/t of electricity is needed for other processes within the waste plant.For the deconstruction life cycle stage, C1, crowbar, excavator loader, hydraulic hammer, wheel loader, and cutters are assumed to be used; They require a diesel consumption of 17.6 L/mms of CC . To conss demand . The cons demand . Life cyte plant . Regardi3 of UHPC in comparison with CC will be discussed in ISO 14040  defined 3 of UHPC in comparison with 1 m3 of CC are shown in LCA results of the carbon footprint of 1 mLCA results of the material footprint (measured in RMI and TMR) are shown in The evaluation of the considered footprints shows that the UHPC (M2Q) has the highest environmental impact. The analysis results of UHPC ready-mix concrete (M3Q) show slightly lower environmental impacts but they are still higher than CC results. About CC, the concrete of compressive strength class C50/60 has more environmental impact. Furthermore, as a commonality of the three footprints can be seen that the highest environmental impact occurs in the production stage A1–A3. These contributed to more than 95% to the material footprint and 90% to the carbon and water footprint. Dominant processes of the carbon and water footprint are the production of cement and steel fibers, as well as the aggregates of the material footprint. The micro steel fibers have been also identified for the largest unused per used extractions.Type of cement.Production process of micro steel fibers.The sensitivity analysis will examine how the footprints are sensitive to changing the two dominants variants as follows:The CEM I 52.5 R-HS/NA is used as the type of cement for the UHPC . This isThe main part of steel production for instance in Germany takes place in the blast furnace route . Pig iroSensitivity of the footprints to the changing type of cement for all mixtures of UHPC and CC and type of production process of steel fibers for UHPC mixture will be shown in this section. Regarding material footprint, the sensitivity analysis indicates that a potential saving of 62% could be done within the UHPC mixtures as shown in 2 eq. when the UHPC is considered to enhance the design of the bridge (UHPC Design) as shown in The carbon footprint of the bridge with CC (CC-Design) could be decreased by about 40 t COWater footprint could be reduced by more than 30% when the UHPC design is considered, as shown in 3 of concrete mixtures . In contrast to the results for the environmental footprint of 1 mmixtures , the anaThis article provides a comprehensive LCA of carbon, material, and water footprint of UHPC in comparison with CC using precast and ready-mix concrete. The GaBi construction materials database is used altogether with openLCA software, which enhances significantly quantifying environmental footprints of constructions. Results are analyzed at the construction material level to enhance sustainability aspects within design of constructions. Higher environmental impact of UHPC is shown when only the quantitative aspects are considered for the formulation of the functional unit. At the case study level, results are analyzed to test the footprints of UHPC in relation to the functionality provided. Better environmental performance of UHPC could be indicated within the assessment of a practical application such as a bridge. Cumulative raw material demand in terms of RMI and total primary material extraction in terms of TMR, in addition to water use of UHPC, are provided for the first time by this article. UHPC shows relative lower footprint values when the use phase is considered. However, higher environmental impacts are shown within the end-of-life phase according to the high compressive strength. Policies and standards related to UHPC use need to be developed according to the current increase in the usage of new concrete technologies. Because of the relative high cost of UHPC, an economic analysis, e.g., life cycle costing of UHPC in comparison with CC, could be a crucial issue to be considered for future studies.


The present study reports on the use of three types of polyhedral oligomeric silsesquioxanes (POSS) nanoparticles with various organic substituents as fillers in a fluoroelastomer (FKM). A series of/POSS elastomer composite thin films is prepared. Microstructural SEM/TEM (scanning electron microscopy/transmission electron microscopy) imaging reveals a dispersion state allowing the presence of micron-sized domains. The influence of POSS content is studied in order to optimize thermal stability and mechanical properties of the composite thin films. Both POSS-A  and POSS-P (with eight phenyl substituents) lead to higher thermal stability and modulus of the composites, with respect to the unfilled FKM terpolymer matrix. covalent grafting of POSS-A onto the FKM network is found to play a critical role. Enhanced storage modulus in the rubbery plateau region (+210% at 200 °C for 20 phr) suggests that POSS-A is particularly suitable for high temperature applications. Since their first use, fluoroelastomers (FKM) have become of great interest. They are used for many applications in the building (as paints and coatings resistant to UV and graffiti), petrochemical and automotive industries, aerospace, and aeronautics , chemical engineering (high-performance membranes), optics , and treatment of textiles . This poHowever, improving the resistance of FKM based terpolymer is still required as they exhibit chemical degradation as well as thermal degradation at high temperature in demanding environment. This involves oxidation and thermolysis of the polymer that can occur on vinylidenefluoride groups and cross-linking bonds ,7. A way3SiO1.5)n oligomers in 1946, with other volatile compounds, by thermolysis of polymer products obtained from methyltrichlorosilane and silane dimethylchloro-cohydrolysis. POSS is described as a cubic cage with a silicon-to-oxygen ratio of 1:1.5, organic peripheral groups at each silicon atom [Polyhedral oligomeric silsesquioxanes (POSS) nanoparticles are particularly attractive as nanofillers. They were first developed by the United States Air Force for aerospace applications . Scott  isolatedcon atom ,15, and con atom . The numcon atom ,17. Thescon atom . When twcon atom ,22,23,24con atom . Despitecon atom . In anotcon atom .Here, three kinds of POSS nanoparticles, differing by their organic substituents, are used as nanofillers in a (HFP–TFE–VDF) fluoroelastomer terpolymer. The influence of specific POSS/FKM interactions on the FKM network structure and the thermal stability of the composites is studied for each type of POSS. The most appropriate fillers are selected and the amount is optimized in order to enhance the thermomechanical properties of the fluoroelastomer composites. The covalent grafting of POSS onto the fluoroelastomer network is found to lead to significant improvement.1.5)n were used: POSS-P Octaphenyl, POSS-F Trifluoropropyl and POSS-A Acryloisobutyl provided by Hybrid Plastics . POSS-F has a T12 cage structure (bearing 12 trifluoropropyl moieties (CF3-)), POSS-P possesses a T8 structure (with eight phenyl moieties (C6H5-)) and POSS-A has a T8 structure (with seven isobutyl moieties (C4H9-) and an acrylo functional group (-C6O2H10)). The three POSS have the appearance of a white powder.The matrix was a FKM terpolymer (HFP–TFE–VDF) provided by DuPont© , and it contained a tiny amount of barium sulfate. The crosslinking system was formed by an organic peroxide coupled with a crosslinking coagent. The peroxide was a diacyl peroxide Norperox DBPH-45 , with silicone carbonate as phlegmatizer hexane). The coagent was used to enhance the crosslinking process, the heat resistance and mechanical properties, with calcium carbonate as a phlegmatizer  Three types of POSS (RSiOThe nanocomposites were prepared by solution casting (Hand Coater). The ingredients were dispersed in acetone by magnetic stirring at room temperature in the following integration order: POSS, crosslinking system, and finally the matrix. The matrix solution concentration is 383 g/L. For each POSS, five loadings were studied: 5, 10, 15, 20, and 40 phr (per hundred rubber).R for the mixture of FKM gum and the crosslinking system; -FT for the mixture of gum, the crosslinking system, and POSS fillers, following by the POSS type  and the rate. For example: the FT composite with POSS-A at 15 phr was called: FTA-15.The composite designation was: -F for the FKM gum; -FRubber elaboration was carried out in thin films (350–400 µm), processing from solution using a Hand Coater  and dried for 13 days at room temperature . One shoA Zeiss field emission model Ultra Plus Scanning Electron Microscope (SEM) , operating at 5 kV, was used to examine the nanocomposites surface micro-structure and analyze particle dispersion. The samples are cleaved with a sharp razor and coated with a Platinum film to increase electrical conductivity. A Transmission Electron Microscopy (TEM)  was used to observe the particle dispersion inside the nanocomposite. The nanoparticles were dispersed in acetone, drop-casted on carbon coated copper grid, and were analyzed under an accelerating electron beam, after solvent evaporation. Cured nanocomposites were ultramicrometered using a diamond knife at −40 °C with a Leica Ultracut UCT . These ultra-thin sections were then transferred onto a copper grid covered with a very thin film of amorphous carbon.−1. A second cooling was performed from −80 °C to 250 °C at 20 °C·min−1. Systematically, two DSC measurements have been performed on each samples. The averaged values of glass transition temperature (Tg) and of cross-linking reaction enthalpy (ΔH) were reported. Thermal gravimetric analysis (TGA) is performed using a Mettler–Toledo instrument . Samples are characterized under two different atmospheres. For the first procedure, samples were heated from 25 °C to 600 °C under nitrogen atmosphere, then from 600 °C to 800 °C under air, at 20 °C·min−1. For the second procedure, samples are heated from 25 °C to 800 °C under air at 20 °C·min−1. Tonset , T5%, T20% (temperature for 5 and 20% of weight loss) and T50% (temperature of peak decomposition of the derivative curve) are measured. Theoretical ashes are calculated assuming a complete conversion of POSS to SiO2. The residues (in percent) calculated from each thermogram are also given. These residues correspond to ash content remaining after measurement. An average of three independent measurements was reported.Differential scanning calorimetry (DSC) was performed under a nitrogen atmosphere on a Netzch Instruments . The accuracy of the measures was ±1 °C. Samples are cooled down to −140 °C and heated up to 250 °C at 20 °C·min−1) at a constant frequency (1 Hz) and with an amplitude of displacement of ±0.5 µm. An average value of three independent measurements was reported: the glass transition temperature Tg taken at the maximum phase angle between stress and strain (tan δ), tan δ at (T = Tg), and the storage modulus (E’) at 100 °C and at 200 °C.The dynamic mechanical properties were analyzed with a thermal analysis instrument . Test specimens were taken from the post-cured thin film  and were submitted to a tension mode. Temperature sweeps were carried out over a temperature range from −30 °C to 250 °C  with computerized recording was used at room temperature to obtain the mechanical properties. The tests were carried out at a crosshead speed of 1 mm/min (or έ = 0.083%/s), and an average of at least 10 measurements for each compound was recorded. The test dumbbell-shaped specimens were taken from the post-cured thin film with a specific tensile specimen cutter developed in our laboratory, in order to optimize the mechanical response of the thin film on the test machine, and to enlarge the clamping area of the dumbbell-shaped specimens. The useful length and the width of dumbbell-shaped specimens is respectively 15 mm and 2 mm . The ave2CF(CF3)), TFE (CF2CF2) and VDF (CH2CF2). The various POSS investigated in this study are shown in The chemical structure of the FKM was composed of three monomers: HFP  and scanning (SEM) electron microscopy in order to determine the particles size, dispersion state, and the morphology of the nanocomposites.R (TA) and POSS-P (FTP) exhibited a smooth surface morphology, whereas FTF nanocomposite films presented a heterogeneous surface, with cracked and lamellar zones. This can be attributed to low filler/matrix compatibility. In FTA and FTP composites, the charges seemed well dispersed, indicating a better compatibility with the FKM. The typical micrometer-sized POSS-A crystals with rectangular faces were observed on TEM images  was clearly observed in all cases , it can be noticed that the Tg increased again with POSS-A and POSS-F, which may be related to a competing effect of POSS/FKM interactions [g of POSS-containing polymers was found to be strongly dependent on the nature of surface functional groups present on POSS particles [g that canceled the plasticizing effect of the filler. The average Tg values measured on the vulcanized samples were all analogous to, or even slightly higher than the Tg of the FKM matrix. The accuracy of the measure (±1 °C) did not allow to a particular trend related to the POSS type or amount in the composite to be determined.POSS filling was found to have only a limited influence on the glass transition temperature. The glass transition of the unfilled FKM matrix Fractions . Howeverarticles ,30. ThisTP compounds decreased when the filler content increased, indicating that POSS-P particles hamper the cross-linking reaction. It can also be noticed that the onset of the exothermic reaction peak was shifted toward higher temperature (ca. +10 °C at 20 phr loading)   b. On theloading) c. The te 125 °C) a. This p 125 °C) . Indeed,Grafting and cross-linking reactions are yet not straightforward to quantify, as the temperature range of those two phenomena seemed to overlap. Swelling tests were considered. With this technique, unreacted POSS could be released in the swelling solvent and could disturb the interpretation of the experiment by participating to the mass loss. Moreover, with this test, it would be difficult to distinguish the crosslinking reaction part to the grafting reaction.T modified with 5–40 phr of POSS were analyzed using TGA under oxidative atmosphere  followed by a vulcanization process increased the thermal properties by 6 °C under nitrogen, and by 32 °C under air  may provide a more appropriate assessment of thermal stability of the composites as it was likely to mostly reflect the degradation of the FKM network. Tonset, which represents the extrapolated starting temperature, i.e., the beginning of the degradation process involved, is also a common indicator [The fluorinated terpolymer matrix exhibits strong thermal stability. The FKM polymer F had a 5% decomposition temperature equal to 452 °C under nitrogen, and 398 °C under air . The addnder air . The TGAndicator . This cr5% of FTA and FTF composites consequently decreased upon addition of POSS. While the thermal resistance of POSS-P was better, this did not translate into higher T5% for FTP. Regardless of the atmosphere, POSS-P decomposed faster and completely in presence of the matrix once the FKM weight loss occurred  , as observed with a polystyrene matrix in the literature [2) layer on the surface, hence serving as a barrier and preventing further degradation of the matrix [50% showed a similar trend, with values reaching 493 °C (+5 °C) and 502 °C (+5 °C) for FTA under air and nitrogen, respectively. For FTP, T50% up to 496 °C (+8 °C) and 501 °C (+4 °C) were determined under air and nitrogen, respectively. Thus, based on the assumption that Tonset and T50% values provided insights into the degree of decomposition of the FKM network, it can be concluded that POSS-A and POSS-P fillers improved the thermal stability of the nanocomposites. At the same time, no significant enhancement was observed with POSS-F  . Similarterature . This ime matrix . T50% shh POSS-F .Given appropriate film forming properties and promising thermal behavior, POSS-A and POSS-P composites were selected for further investigations of their mechanical properties. Measurements were realized without the elimination of Mullins effect . The tenTA, a significant change in mechanical behavior, characterized by an increase of stiffness at the origin, was evidenced. The ultimate tensile stress increased by 35%, and a slight increase of tensile strain (3%) was observed at 5 phr in comparison with FR. The moduli at 10% and 100% elongation gradually increased with POSS-A loading. At 20 phr, the modulus at 100% elongation increased by 116% compared to the compound without fillers, while the tensile at break decreased by 19.5% versus the 5 phr sample.For FTP samples. The modulus at 10% of deformation remains relatively unaffected, whereas the modulus at 100%, tensile strength, and elongation at break decreased with increasing particle content . Thus, the DMA characteristics suggested less motions of the macromolecular structure in the network and confirmed that POSS grafting could play a significant role. Formation of rigid fillers network usually provided additional levels of reinforcement. Filler–matrix and filler–filler interactions are unanimously associated with the decrease of the dynamic modulus with the strain amplitude, which is known as the Payne effect. This reinforcement has been highlighted in a previous study [Secondly, the evolution of storage modulus E’ in temperature showed a strong improvement upon POSS loading at high temperature . The pheus study . The enhTA and FTP composites exhibit improved thermal stability, with 50% weight loss temperature values reaching 493 °C and 502 °C for FTA under air and nitrogen, respectively (+5 °C vs. the unfilled FKM matrix). Based on film morphology and thermal properties of the composites, POSS-A and POSS-P are selected as the most appropriate fillers. Incorporation of fillers leads to increased modulus. Consequently, the increase of stiffness leads to a decrease of mechanical response of FTP composites because of the hindrance of chains motion induced by the presence of POSS particles. Yet, covalent grafting of POSS is found to play a critical role on the enhancement of mechanical properties of the composites. The maximum tensile and elongation at break are obtained for FTA with 5 phr of filler and seem to be correlated to a trade-off between cross-linking and grafting density. Furthermore, storage modulus E’ is strongly enhanced in the rubbery plateau region up to 4.0 MPa at 200 °C with 20 phr loading (+210% compared with FR). Thus, POSS-A appears as a promising reinforcing agent in fluoroelastomers for high temperature applications.Three POSS nanofillers have been incorporated in a FKM matrix. The nanocomposites were obtained as thin films. SEM/TEM and EDX imaging reveal a relatively proper dispersion state with the presence of micron-sized POSS domains that are smaller than aggregates that are attributed to the cross-linking system. The influence of POSS peripheric substituents and POSS content on thermal and thermomechanical properties has been studied. Although POSS fillers have little influence on the glass transition temperature, they are found to interfere with the vulcanization process. In particular, DSC measurements show that POSS-P hampers the cross-linking reaction, whereas the appearance of a new exothermic peak at lower temperature along with increased heat of reaction are indicative of the covalent grafting of POSS-A onto the FKM network. Both FExperiments are under way to further improve the dispersion prior to film deposition. To highlight a more pronounced impact of POSS ability to increase the thermal properties, tensile tests after thermal aging at high temperature and kinetics modelling of degradation are also in progress. Works are in progress to optimize the thermal and mechanical properties of composites FKM/POSS-A bearing various numbers of acrylate functional groups to study more deeply the effect of the grafting versus crosslinking reactions between POSS and FKM matrix.