Enhanced Flame Retardancy of Rigid Polyurethane Foams by Polyacrylamide/MXene Hydrogel Nanocomposite Coating.

Rigid polyurethane foam (RPUF) has been widely used in many fields, but its high flammability and frequent release of large amounts of toxic smoke during combustion limit its application. Hydrogel coatings, as a kind of environmentally friendly material, contain large amounts of water, which is beneficial to flame retardance of RPUF. MXene, as a two-dimensional inorganic nanomaterial, possesses a large specific surface area and good thermal stability, performing well in smoke suppression and as a physical barrier for flammable gas products and heat. Herein, to address the fire hazards of RPUF, MXene nanosheets were first grafted with double bonds, and then introduced into a polyacrylamide hydrogel system by radical polymerization to prepare MXene-based hydrogel coating (PAAm-MXene). The flame-retardant RPUF (coated RPUF) was prepared by painting the PAAm-MXene coating onto RPUF surface. The dispersion of modified MXene nanosheets (m-MXene) in hydrogels is improved compared with pristine MXene, and the addition of m-MXene contributes to the thermal stability enhancement of PAAm-MXene. Cone calorimetry, water retention test, and open flame combustion test were used to study the flame retardancy, smoke suppression, and water retention of flame-retardant RPUF. The coated RPUF exhibited significant flame retardancy, including reduced peak heat release rate (pHRR) at a maximum by 25.8%, and total heat release rate (THR) at a maximum by 24.6%, and total smoke production at a maximum by 38.9%. The results show that both MXene and m-MXene can improve the flame retardancy, smoke suppression, and water retention of hydrogels, but m-MXene has a better smoke suppression effect than MXene. That can be ascribed to the better dispersion of m-MXene than pristine MXene. The detailed performance improvement mechanisms are proposed. This work will not only improve the flame retardancy of RPUF, but also promotes the exploration of new flame-retardant strategies for RPUF.

Experimental Study on Thermal Runaway Process of 18650 Lithium-Ion Battery under Different Discharge Currents.

Lithium-ion batteries (LIBs) subjected to external heat may be prone to failure and cause catastrophic safety issues. In this work, experiments were conducted to investigate the influence of discharge current on the thermal runaway process under thermal abuse. The calibrated external heat source (20 W) and discharge currents from 1 to 6 A were employed to match the thermal abuse conditions in an operational state. The results indicated that the key parameters during the failure process, such as the total mass loss, the onset temperatures of safety venting and thermal runaway, and the peak temperature, are ultimately determined by the capacity inside the battery, and the discharge current can hardly change it. However, discharge currents can produce extra energy to accelerate the thermal runaway process. Compared with the battery in an open circuit, the onset time of thermal runaway was reduced by 7.4% at 6 A discharge. To quantify the effect of discharge current, the total heat generation by discharge current was calculated. The results show that a heat generation of 1.6 kJ was produced when the battery was discharged at 6 A, which could heat the cell to 34 °C (neglect of heat loss). This study simulates the failure process of the LIB in the operational state, which is expected to help the safety application of LIB and improve the reliability of the battery management system.

Gumi Bao decoction regulates bone metabolism-related mRNA expression in glucocorticoid-induced osteoporosis in rats.

BACKGROUND: Gumi Bao decoction is effective for the treatment of osteoporosis, but the theoretical and scientific basis is unknown. This study aimed to observe the effect of Gumi Bao decoction on Dickkopf-related protein 1 (DKK1) mRNA, runt-related transcription factor 2 (Runx2) mRNA, and cathepsin K (CTSK) mRNA in glucocorticoid-induced osteoporosis (GIOP) in rats and to investigate the underlying mechanism. METHODS: Sixty Sprague-Dawley (SD) rats were weighed and randomly divided into six groups: the normal control group (NC group), the methylprednisolone group (Met group), the Fosamax group, the low-dose Gumi Bao Decoction group (GBDL group), the medium-dose Gumi Bao Decoction group (GBDM group), and the high-dose Gumi Bao Decoction group (GBDH group). The basic physiological conditions of the rats and the bone morphology of the fourth lumbar vertebra and the left femur of three rats in each group were observed, and the mRNA expressions of bone tissue-related genes were detected. RESULTS: After administration, DKK1 mRNA expression was significantly up-regulated in the Met group compared to the NC group (P<0.001). Meanwhile, DKK1 mRNA was significantly down-regulated in the Fosamax group compared with the Met group (P<0.001). There was a significant difference in the down-regulation of DKK1 mRNA between the GBDM and GBDH groups (P<0.001). Runx2 mRNA was considerably down-regulated in the Met group compared with the NC group (P<0.001). Runx2 mRNA was up-regulated in the GBDM group, and the GBDH group was significantly different compared to the Met group (P<0.001). CTSK mRNA was significantly up-regulated in the Met group compared to the NC group (P<0.001). Compared with the Met group, CTSK mRNA expression was significantly down-regulated in the Fosamax group (P<0.001), as well as in the GBDL, GBDM, and GBDH groups (P<0.001). At 200× and 400×, there were significantly fewer osteoblasts and osteoclasts in the Met group than in the Fosamax, GBDM, and GBDH groups. CONCLUSIONS: The imbalance of bone homeostasis of GIOP is caused by an increase in bone resorption and decreased osteogenesis. Gumi Bao could regulate bone metabolism through the action of DKK1 via the Wnt/ß-catenin signaling pathway, up-regulating Runx2 mRNA and down-regulating CTSK mRNA.

A comprehensive investigation on the thermal and toxic hazards of large format lithium-ion batteries with LiFePO4 cathode.

Toxic gases released from lithium-ion battery (LIB) fires pose a very large threat to human health, yet they are poorly studied, and the knowledge of LIB fire toxicity is limited. In this paper, the thermal and toxic hazards resulting from the thermally-induced failure of a 68 Ah pouch LIB are systematically investigated by means of the Fourier transform infrared spectroscopy (FTIR) and 1/2 ISO full scale test room. The LIBs with higher state of charge (SOC) are found to have greater fire risks in terms of their burning behavior, normalized heat release rate, and fire radiation, as well as the concentration of toxic gases. Specifically, the thermal hazards are evaluated by combining the effects of convective and radiative heat. The major toxic gases detected from the online analysis are CO, HF, SO2, NO2, NO and HCl. Furthermore, Fractional Effective Dose (FED) and Fractional Effective Concentration (FEC) models are used to quantitatively assess the overall gas toxicity. Results show that the effects of irritant gases are much more significant than those of asphyxiant gases. HF and SO2 have much greater toxicity than the other fire gases. The maximum FEC value is approaching the critical threshold in such fire scenarios.

[Determination of acrylamide in coffee by ultra performance liquid chromatography-atmospheric pressure chemical ionization tandem mass spectrometry].

A method using ultra high performance liquid chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry (UHPLC-APCI-MS/MS) was developed for the determination of acrylamide in coffee. The coffee samples spiked with 13C3-acrylamide as the internal standard were extracted with methanol, and cleaned using HLB solid phase extraction (SPE) cartridges. The liquid chromatography separation was performed on a Brownlee validated AQ C18 column with isocratic elution. Methanol and 0.1% (volume percentage) formic acid aqueous solution were used as the mobile phase. Identification of acrylamide was achieved by APCI-MS/MS with multiple reaction monitoring (MRM) in the positive mode. The quantification analysis was performed by the internal standard method. The calibration curve showed good linearity with a correlation coefficient of 0.999 in the range of 0.5-100.0 µg/L. The limit of detection (LOD) was 5.0 µg/kg. The limit of quantification (LOQ) was 10.0 µg/kg. Recovery of acrylamide from coffee sample was evaluated at concentrations of 100.0, 200.0 and 1000.0 µg/kg. The average recoveries of acrylamide were between 94.6%-115.0% with relative standard derivations (RSDs) in the range of 2.8%-3.6% (n=6). This simple, accurate and sensitive method was proven to be suitable for the determination of acrylamide in coffee.

Experimental Study of Fire Hazards of Thermal-Insulation Material in Diesel Locomotive: Aluminum-Polyurethane.

This work investigated experimentally and theoretically the fire hazards of thermal-insulation materials used in diesel locomotives under different radiation heat fluxes. Based on the experimental results, the critical heat flux for ignition was determined to be 6.15 kW/m² and 16.39 kW/m² for pure polyurethane and aluminum-polyurethane respectively. A theoretical model was established for both to predict the fire behaviors under different circumstances. The fire behavior of the materials was evaluated based on the flashover and the total heat release rate (HRR). The fire hazards levels were classified based on different experimental results. It was found that the fire resistance performance of aluminum-polyurethane is much better than that of pure-polyurethane under various external heat fluxes. The concentration of toxic pyrolysis volatiles generated from aluminum-polyurethane materials is much higher than that of pure polyurethane materials, especially when the heat flux is below 50 kW/m². The hazard index HI during peak width time was proposed based on the comprehensive impact of time and concentrations. The predicted HI in this model coincides with the existed N-gas and FED models which are generally used to evaluate the fire gas hazard in previous researches. The integrated model named HNF was proposed as well to estimate the fire hazards of materials by interpolation and weighted average calculation.

Prediction of Three-Dimensional Downward Flame Spread Characteristics over Poly(methyl methacrylate) Slabs in Different Pressure Environments.

The present study is aimed at predicting downward flame spread characteristics over poly(methyl methacrylate) (PMMA) with different sample dimensions in different pressure environments. Three-dimensional (3-D) downward flame spread experiments on free PMMA slabs were conducted at five locations with different altitudes, which provide different pressures. Pressure effects on the flame spread rate, profile of pyrolysis front and flame height were analyzed at all altitudes. The flame spread rate in the steady-state stage was calculated based on the balance on the fuel surface and fuel properties. Results show that flame spread rate increases exponentially with pressure, and the exponent of pressure further shows an increasing trend with the thickness of the sample. The angle of the pyrolysis front emerged on sample residue in the width direction, which indicates a steady-burning stage, varies clearly with sample thicknesses and ambient pressures. A global non-dimensional equation was proposed to predict the variation tendency of the angle of the pyrolysis front with pressure and was found to fit well with the measured results. In addition, the dependence of average flame height on mass burning rate, sample dimension and pressure was proposed based on laminar diffusion flame theory. The fitted exponent of experimental data is 1.11, which is close to the theoretical value.

Experimental and Numerical Study on Effect of Sample Orientation on Auto-Ignition and Piloted Ignition of Poly(methyl methacrylate).

In this work, the effect of seven different sample orientations from 0° to 90° on pilot and non-pilot ignition of PMMA (poly(methyl methacrylate)) exposed to radiation has been studied with experimental and numerical methods. Some new and significant conclusions are drawn from the study, including a U-shape curve of ignition time and critical mass flux as sample angle increases for pilot ignition conditions. However, in auto-ignition, the ignition time and critical mass flux increases with sample angle α. Furthermore, a computational fluid dynamic model have been built based on the Fire Dynamics Simulator (FDS6) code to investigate the mechanisms controlling the dependence on sample orientation of the ignition of PMMA under external radiant heating. The results of theoretical analysis and modeling results indicate the decrease of total incident heat flux at sample surface plays the dominant role during the ignition processes of auto-ignition, but the volatiles gas flow has greater influence for piloted ignition conditions.

Experimental Studies on the Flammability and Fire Hazards of Photovoltaic Modules.

Many of the photovoltaic (PV) systems on buildings are of sufficiently high voltages, with potential to cause or promote fires. However, research about photovoltaic fires is insufficient. This paper focuses on the flammability and fire hazards of photovoltaic modules. Bench-scale experiments based on polycrystalline silicon PV modules have been conducted using a cone calorimeter. Several parameters including ignition time (tig), mass loss, heat release rate (HRR), carbon monoxide (CO) and carbon dioxide (CO2) concentration, were investigated. The fire behaviours, fire hazards and toxicity of gases released by PV modules are assessed based on experimental results. The results show that PV modules under tests are inflammable with the critical heat flux of 26 kW/m². This work will lead to better understanding on photovoltaic fires and how to help authorities determine the appropriate fire safety provisions for controlling photovoltaic fires.

[Determination of spinosyns A and D residues in food by high performance liquid chromatography-tandem mass spectrometry].

A high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/ MS) method was established for the determination of spinosyns A and D residues in foodstuffs. The food samples were extracted with acetonitrile-water (50:50, v/v), and then purified by an HLB solid phase extraction (SPE) column. The analytes were determined by HPLC-MS/MS and quantified by external standard method. The mass spectrometric detection was operated with electrospray in positive ionization mode and the spinosyns A and D were identified in multiple reaction monitoring (MRM) mode. The linear range of the method was 1-20 microg/L, with the correlation coefficient (r2) of 0.999 9. No significant matrix effect was found for spiked samples. The recoveries of spinosyns A and D spiked in food were 76.2%-114.0% at the spiked levels of 1-10 microg/kg. The relative standard deviations (RSDs) were less than 10%. The limits of detection (LODs) and quantification (LOQs) were 0.2 microg/kg and 0.5 microg/kg for spinosyn A, 0.5 microg/kg and 1.0 microg/kg for spinosyn D, respectively. The proposed procedure was applied to the analysis of 969 real samples from Xiamen, Fujian Province (China), of which 15 positive samples were found. The results showed that the proposed method is sensitive and accurate for the determination of spinosyns A and D in foodstuffs.

Gene expression alterations by conditional knockout of androgen receptor in adult Sertoli cells of Utp14b jsd/jsd (jsd) mice.

Spermatogenesis is dependent primarily on testosterone action on the Sertoli cells, but the molecular mechanisms have not been identified. Attempts to identify testosterone-regulated target genes in Sertoli cells have used microarray analysis of gene expression in mice lacking the androgen receptor (AR) in Sertoli cells (SCARKO) and wild-type mice, but the analyses have been complicated both by alteration of germ cell composition of the testis when pubertal or adult mice were used and by differences in Sertoli-cell gene expression from the expression in adults when prepubertal mice were used. To overcome these limitations and identify AR-regulated genes in adult Sertoli cells, we compared gene expression in adult jsd (Utp14b jsd/jsd, juvenile spermatogonial depletion) mouse testes and with that in SCARKO-jsd mouse testes, since their cellular compositions are essentially identical, consisting of only type A spermatogonia and somatic cells. Microarray analysis identified 157 genes as downregulated and 197 genes as upregulated in the SCARKO-jsd mice compared to jsd mice. Some of the AR-regulated genes identified in the previous studies, including Rhox5, Drd4, and Fhod3, were also AR regulated in the jsd testes, but others, such as proteases and components of junctional complexes, were not AR regulated in our model. Surprisingly, a set of germ cell­specific genes preferentially expressed in differentiated spermatogonia and meiotic cells, including Meig1, Sycp3, and Ddx4, were all upregulated about 2-fold in SCARKO-jsd testes. AR-regulated genes in Sertoli cells must therefore be involved in the regulation of spermatogonial differentiation, although there was no significant differentiation to spermatocytes in SCARKO-jsd mice. Further gene ontogeny analysis revealed sets of genes whose changes in expression may be involved in the dislocation of Sertoli cell nuclei in SCARKO-jsd testes.

Gene expression alterations by conditional knockout of androgen receptor in adult sertoli cells of Utp14b(jsd/jsd) (jsd) mice.

Spermatogenesis is dependent primarily on testosterone action on the Sertoli cells, but the molecular mechanisms have not been identified. Attempts to identify testosterone-regulated target genes in Sertoli cells have used microarray analysis of gene expression in mice lacking the androgen receptor (AR) in Sertoli cells (SCARKO) and wild-type mice, but the analyses have been complicated both by alteration of germ cell composition of the testis when pubertal or adult mice were used and by differences in Sertoli-cell gene expression from the expression in adults when prepubertal mice were used. To overcome these limitations and identify AR-regulated genes in adult Sertoli cells, we compared gene expression in adult jsd (Utp14b(jsd/jsd), juvenile spermatogonial depletion) mouse testes and with that in SCARKO-jsd mouse testes, since their cellular compositions are essentially identical, consisting of only type A spermatogonia and somatic cells. Microarray analysis identified 157 genes as downregulated and 197 genes as upregulated in the SCARKO-jsd mice compared to jsd mice. Some of the AR-regulated genes identified in the previous studies, including Rhox5, Drd4, and Fhod3, were also AR regulated in the jsd testes, but others, such as proteases and components of junctional complexes, were not AR regulated in our model. Surprisingly, a set of germ cell-specific genes preferentially expressed in differentiated spermatogonia and meiotic cells, including Meig1, Sycp3, and Ddx4, were all upregulated about 2-fold in SCARKO-jsd testes. AR-regulated genes in Sertoli cells must therefore be involved in the regulation of spermatogonial differentiation, although there was no significant differentiation from spermatocytes in SCARKO-jsd mice. Further gene ontogeny analysis revealed sets of genes whose changes in expression may be involved in the dislocation of Sertoli cell nuclei in SCARKO-jsd testes.

Global gene expression in the human fetal testis and ovary.

This study describes a temporal profile of gene expression from normal human fetal testes and ovaries. Gonads from 34 fetuses between 9 wk and 20 wk of gestation were obtained from the Department of Pathology and the Birth Defects Research Laboratory at the University of Washington. Relative transcript levels were determined using the Affymetrix Human Genome U133A Plus 2.0 arrays. Sex determination occurs in the human gonad at approximately 6 wk of gestation with development of the testis driven by expression of SRY. In this study, SRY transcript was present and elevated at 9 wk of gestation in the testis but was absent in the ovary. The transcript levels of other testis-specific factors SOX9 and AMH and the steroidogenic genes CYP17A1, CYP11A1, STAR, and HSD17B3 were all significantly higher in the testis. In contrast, transcripts known to be involved in meiosis, including STRA8, SPO11, SYCP3, TEX11, TEX14, and STAG3, showed highest expression in the fetal ovary beginning at Week 12. These gene expression profiles will be a resource for understanding and defining normal gonad development and provide the opportunity to dissect abnormal development.

Differential gene expression in the testes of different murine strains under normal and hyperthermic conditions.

Cryptorchidism and scrotal heating result in abnormal spermatogenesis, but the mechanism(s) prescribing this temperature sensitivity are unknown. It was previously reported that the AKR/N or MRL/MpJ-+/+ mouse testis is more heat-resistant than the testis from the C57BL/6 strain. We have attempted to probe into the mechanism(s) involved in heat sensitivity by examining global gene expression profiles of normal and heat-treated testes from C57BL/6, AKR/N, and MRL/MpJ-+/+ mice by microarray analysis. In the normal C57BL/6 testis, 415 and 416 transcripts were differentially expressed (at least 2-fold higher or lower) when compared with the normal AKR/N and MRL/MpJ-+/+ testis, respectively. The AKR/N and MRL/MpJ-+/+ strains revealed 268 differentially expressed transcripts between them. There were 231 transcripts differentially expressed between C57BL/6 and 2 purported heat-resistant strains, AKR/N and MRL/MpJ-+/+. Next, the testes of C57BL/6 and AKR/N mice were exposed to 43 degrees C for 15 minutes and harvested at different time points for terminal deoxynucleotidyl transferase dUTP nick end labeling (TUNEL) studies and microarrays. An increase of TUNEL-positive germ cell numbers was significant 8 hours after heat exposure in the C57BL/6 mouse. However, this increase was not observed in the AKR/N mouse until 10 hours after heat exposure. All tubules showed germ cell loss and disruption in C57BL/6 testis 24 hours after heat shock. In contrast, although a number of seminiferous tubules showed an abnormal morphology 24 hours post-heat shock in the AKR/N mouse, many tubules still retained a normal structure. Numerous transcripts exhibited differential regulation between the 2 strains within 24 hours after heat exposure. The differentially expressed transcripts in the testes 8 hours after heat exposure were targeted to identify the genes involved in the initial response rather than those attributable to germ cell loss. Twenty transcripts were significantly down-regulated and 19 genes were up-regulated by hyperthermia in C57BL/6 and did not show a parallel change in the AKR/N testis. Conversely, heat shock resulted in 30 up-regulated transcripts and 31 down-regulated transcripts in AKR/N that were not similarly regulated in C57BL/6. A number of genes shared similar differential expression patterns and differential regulation by hyperthermia in both strains of mice. Taken together, the results of the present study indicate that the diverse genetic backgrounds in the 3 strains lead to major differences in normal testis gene expression profiles, whereas the differences in heat shock responses involve a significantly smaller number of genes. The data generated may provide insights regarding gene networks and pathways involved in heat stress and their relationship to spermatogenesis.