α-calcium sulfate hemihydrate (α-HH) is known to be suitable for application as bone void filler. High percentage of α-HH is obviously needed for medical applications, especially for implantation. Three commerciall...α-calcium sulfate hemihydrate (α-HH) is known to be suitable for application as bone void filler. High percentage of α-HH is obviously needed for medical applications, especially for implantation. Three commercially available calcium sulfate dihydrates (DH, CaSO4·2H2O) with different sizes and surface morphologies were used as starting materials to synthesize high percentage α-HH via a hydrothermal method. The median particle sizes of the three types of DH were 946.7 μm, 162.4 μm and 62.4 μm, respectively. They were named as DH-L, DH-M and DH-S in this paper. The particle size distribution, morphology and phase composition of the raw materials were evaluated before synthesis. SEM results revealed that DH-L consisted of irregular large particles, while DH-M and DH-S were composed of plate-like particles with some small ones. High percentage HH can be obtained with proper synthesis parameters by hydrothermal method, specifically, 105 °C/90 min for DH-L (achieving 98.8% HH), 105°C/30 min for DH-M (achieving 96.7% HH) and 100°C/45 min for DH-S (achieving 98.4% HH). All the synthesized HH were hexagonal columns, demonstrating that they were α-phase HH. The particle size and morphology of starting material (DH) have significant influences on not only the rate of phase transition but also the morphology of the synthesized α-HH. Calcium sulfate dihydrate cements were prepared by the synthesized α-HH. The highest compressive strength of calcium sulfate dihydrate cement was 17.2 MPa. The results show that the preparation of high percentage α-HH is feasible via a hydrothermal method and the process can be further scaled up to industrial scale production.展开更多
Calcium sulfate hemihydrate whiskers were synthesized successfully via one-step hydrothermal crystallization method using phosphogypsum at 130 °C for 240 min with an initial slurry mass fraction of 2.5 wt%. The p...Calcium sulfate hemihydrate whiskers were synthesized successfully via one-step hydrothermal crystallization method using phosphogypsum at 130 °C for 240 min with an initial slurry mass fraction of 2.5 wt%. The phase compositions, microstructures, thermal properties and molecular structures of asprepared samples were analyzed by XRD, ESEM, EDS, TG-DTA, and FT-IR. The influence of raw materials' ball-milling time on the morphologies of whiskers was investigated. The effects of impurities on crystallization morphologies and length to diameter ratio(L/D) of calcium sulfate hemihydrate whiskers were studied. The results indicated that the calcium sulfate dihydrate crystalline could be translated directly into fibrous calcium sulfate hemihydrate whiskers. It was beneficial to form fine fiber structure when the ball-milling time of the raw material was 15 min. Aspect ratio of calcium sulfate hemihydrate whiskers decreased with increasing content of impurities. Moreover, the relative growth mechanism of whisker crystals via one-step hydrothermal crystallization method was discussed in detail.展开更多
The inhibition and its mechanism of sodium tripolyphosphate (STP) composited with super plasticizers (SPs) on hydration of α-calcium sulfate hemihydrate were studied by setting time, strength, hydration heat, X-ray d...The inhibition and its mechanism of sodium tripolyphosphate (STP) composited with super plasticizers (SPs) on hydration of α-calcium sulfate hemihydrate were studied by setting time, strength, hydration heat, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), electronic probe micro analysis (EPMA), scanning electron microscopy (SEM) and differential scanning calorimeter (DSC) measurements. The experimental results show that compared with STP addition, compositing STP with polycarboxylate (PC) plasticizer, the final setting time is prolonged from 0.5h to 2hs. While formulating STP with naphthalene-based plasticizer (NAP) or sulfonate melamine formaldehyde plasticizer (SMF), the final setting time is reduced to quarter of an hour. Similar changes can also be found in the rate of exothermic hydration and hydration degree. Formulating STP with suitable addition of PC can enhance the strength, while compositing STP and NAP or SMF weakens the strength. Besides, adding STP or STP and SMF, obvious movement (more than 1ev) of binding energy of Ca2p1/2 and Ca2p3/2 is detected. Compared with STP addition, content of the characteristic element (P) of STP is cut down form 1.1% to 0.49% by compositing STP with SMF. Furthermore, as hydration age increases, hydration inhibition in the presence of admixtures weakens and even disappears within 56 h.展开更多
Objective:The as-providedα-calcium sulfate hemihydrate bone repair material exhibits superior degradation properties and osteogenic property to the traditional calcium sulfate bone repair materials. Its effects on th...Objective:The as-providedα-calcium sulfate hemihydrate bone repair material exhibits superior degradation properties and osteogenic property to the traditional calcium sulfate bone repair materials. Its effects on the blood and the biocompatibility were studied to ensure its safety for the bone implantation application.Method: The hemolytic tests were conducted to evaluate the blood compatibility of theα-calcium sulfate hemihydrate. The extracts ofα-calcium sulfate hemihydrate with different concentration reacted with 2% rabbit red blood cell suspension. The existence and morphology of the red blood were observed through naked eye observation and microscope observation. The hemolytic ratios were calculated through the absorbances using a ultraviolet spectrophotometer.Result:It was observed by naked eye that the red blood accumulated at the bottom of the test tubes and the upper liquids were clear, colorless and transparent in the experimental sample. The microscope observation exhibited that the cells of the experimental samples had the normal morphology, no deformed and broken blood sell existed. The hemolytic ratios of the experimental sample were all less than 5%. The hemolytic ratios were increased with the increase of the concentration of the extracts. Conclusions: The hemolytic ratios of the medical -calcium sulfate hemihydrate accorded with the standard ISO/TR7405-1984(E). It could be concluded the material would not cause acute hemolysis. The osteogenic property exhibited dose dependence.展开更多
Objective:To prepare a bone repair material with certain mechanical strength and biological activity,this paper used calcium sulfate hemihydrate(CSH)powder compounded with calcium hydroxide(Ca(OH)2)powder to prepare a...Objective:To prepare a bone repair material with certain mechanical strength and biological activity,this paper used calcium sulfate hemihydrate(CSH)powder compounded with calcium hydroxide(Ca(OH)2)powder to prepare a bone repair scaffold material for physicochemical property characterization and testing.Methods:The physical and chemical properties and characterization of the dried and cured bone repair materials were determined by Fourier infrared spectroscopy(FT-IR),X-ray diffraction(XRD),and scanning electron microscopy;Universal material testing machine to determine the mechanical and mechanical strength of composite materials.Results:XRD showed that the structure of the composite material phase at 5%concentration was calcium sulfate hemihydrate and calcium hydroxide after hydration.The FT-IR and XRD analyses were consistent.Scanning electron microscopy(SEM)results showed that calcium hydroxide was uniformly dispersed in the hemihydrate calcium sulfate material.0%,1%,5%,and 10%specimen groups had compressive strengths of 3.86±3.1,5.27±1.28,8.22±0.96,and 14.4±3.28 MPa.10%addition of calcium hydroxide significantly improved the mechanical strength of the composites,but also reduced the the porosity of the material.Conclusion:With the addition of calcium hydroxide,the CSH-Ca(OH)2 composite was improved in terms of mechanical material and is expected to be a new type of bone repair material.展开更多
Alpha-calcium sulfate hemihydrate (α-HH) has been prepared from flue gas desulfurization (FGD) gypsum with salt solution method under atmospheric pressure. X-ray diffraction (XRD),thermogra-vimetry and differential s...Alpha-calcium sulfate hemihydrate (α-HH) has been prepared from flue gas desulfurization (FGD) gypsum with salt solution method under atmospheric pressure. X-ray diffraction (XRD),thermogra-vimetry and differential scanning calorimetry (TG-DSC),optical micrograph,X-ray photoelectron spec-troscopy (XPS),energy dispersive spectrometry (EDS),and scanning electron microscopy (SEM) have been employed to characterize the α-HH crystals,based on which the formation and growth mecha-nisms of the α-HH crystals have been discussed. The results show that FGD gypsum can be success-fully transformed into high purity α-HH in salt solution under mild conditions,and that a dissolu-tion-recrystallization route is most probably adopted by this transition. The growth of α-HH crystals in salt solution demonstrates a preferred direction along [001] and results in a bundle-of-sheets or bun-dle-of-raphide texture. The characteristics revealed in this study can help to understand and control the growth of the α-HH crystal from solution.展开更多
Calcium sulfate hemihydrate(CSH) whiskers were synthesized by phase transition in CaCl_2 solution under atmospheric pressure.Analytical-grade calcium sulfate dihydrate(AR CSD) was used as the raw material for the synt...Calcium sulfate hemihydrate(CSH) whiskers were synthesized by phase transition in CaCl_2 solution under atmospheric pressure.Analytical-grade calcium sulfate dihydrate(AR CSD) was used as the raw material for the synthesis of CSH whiskers,according to orthogonal experiments.The effects of reaction temperature,AR CSD content,H_2SO_4 content,and reaction time were investigated,and the crystallization conditions were optimized.The as-prepared CSH whiskers displayed a regular morphology and a highly uniform size,with an aspect ratio of 105.A simulation system was also established by blending various sulfates with AR CSD,to evaluate the effects of impurities in flue gas desulfurization(FGD) gypsum.The main aim was to prepare CSH whiskers directly from FGD gypsum,without any purification,using the optimized conditions.This is a facile potential alternative process for large-scale production of CSH whiskers using abundant FGD gypsum as source materials.展开更多
This work investigates durability of cement-free mortars with a binder comprised of ground granulated blast furnace slag (GGBFS) activated by high-calcium fly ash (HCFA) and sodium carbonate (Na<sub>2</sub>...This work investigates durability of cement-free mortars with a binder comprised of ground granulated blast furnace slag (GGBFS) activated by high-calcium fly ash (HCFA) and sodium carbonate (Na<sub>2</sub>CO<sub>3</sub>): the soundness, sulfate resistance, alkali-silica reactivity and efflorescence factors are considered. Results of tests show that such mortars are resistant to alkali-silica expansion. Mortars are also sulfate-resistant when the amount of HCFA in the complex binder is within a limit of 10 wt%. The fineness of fly ash determines its’ ability to activate GGBFS hydration, and influence soundness of the binder, early strength development, sulfate resistance and efflorescence behavior. The present article is a continuation of authors’ work, previously published in MSA, Vol. 14, 240-254.展开更多
The mining industry often uses shotcrete for ground stabilization. However, cracking within shotcrete is commonly observed, which delays production schedules and increases maintenance costs. A possible crack reduction...The mining industry often uses shotcrete for ground stabilization. However, cracking within shotcrete is commonly observed, which delays production schedules and increases maintenance costs. A possible crack reduction method is using expansive shotcrete mixture consisting of calcium sulfoaluminate cement(CSA), ordinary Portland cement(OPC), and calcium sulfate(CS) to reduce shrinkage. Furthermore, fibers can be added to the mixture to restrain expansion and impede cracking. The objective of this paper is to study the effects of nylon fiber, glass fiber, and steel fiber on an expansive shotcrete mixture that can better resist cracking. In this study, parameters such as density, water absorption, volume of permeable voids, unconfined compressive strength(UCS), splitting tensile strength(STS), and volume change of fiber-added expansive mixtures were determined at different time periods(i.e. the strengths on the 28 th day, and the volume changes on the 1 st, 7 th, 14 th, 21 st, and 28 th days). The results show that addition of fibers can improve mixture durability, in the form of decreased water absorption and reduced permeable pore space content. Moreover, the expansion of the CSA-OPC-CS mixture was restrained up to50% by glass fiber, up to 43% by nylon fiber, and up to 28% by steel fiber. The results show that the STS was improved by 57% with glass fiber addition, 43% with steel fiber addition, and 38% with nylon fiber addition. The UCS was also increased by 31% after steel fiber addition, 26% after nylon fiber addition, and16% after glass fiber addition. These results suggest that fiber additions to the expansive shotcrete mixtures can improve durability and strengths while controlling expansion.展开更多
In this paper,the solid waste desulfurization gypsum produced by coal-fired power plants was used as a raw material to prepare calcium sulfate whiskers with high application prospects.Calcium sulfate whiskers with uni...In this paper,the solid waste desulfurization gypsum produced by coal-fired power plants was used as a raw material to prepare calcium sulfate whiskers with high application prospects.Calcium sulfate whiskers with uniform morphology and high aspect ratio can be prepared by hydrothermal method in sulfuric acid solution.A new process of desulfurization gypsum activated by high-energy grinding to reduce the reaction temperature and sulfuric acid concentration was developed.Through the comparison of product morphology,the best grinding time was determined to be 3.5 h.The mechanism of desulfurization gypsum through physical–chemical coupling to reduce energy consumption was clarified.The activation of desulfurization gypsum by grinding and the acidic environment provided by the sulfuric acid solution made the calcium sulfate solution reached rapid saturation and accelerated the nucleation rate.By calculating the conversion and crystallization rate of calcium sulfate whiskers,it was found that there were obvious"autocatalytic"kinetic characteristics during the crystallization process.展开更多
The thermodynamic stability of sulfate ions on synthesized calcium aluminosilicate hydrate (C-A-S-H) microstructure with different Ca/Si ratios and Al/Si ratios was investigated by XRD, SEM-EDS, 29Si and 27A1 nuclear ...The thermodynamic stability of sulfate ions on synthesized calcium aluminosilicate hydrate (C-A-S-H) microstructure with different Ca/Si ratios and Al/Si ratios was investigated by XRD, SEM-EDS, 29Si and 27A1 nuclear magnetic resonance (NMR) and thermodynamic modeling. The results indicate that sulfate attack leads to both decalcification and dealumination for C-A-S-H gels, and the amount of corrosion products (gypsum and ettringite) decreased gradually with decreasing Ca/Si ratios of C-A-S-H. Sulfate ions can also promote the polymerization degree of C-A-S-H gels, improving its resistance to sulfate attack. Moreover, the 4-coordination aluminum (Al[4]) in C-A-S-H, 5-coordination aluminum (Al[5]), 6-ccordination aluminum (A1[6J) in TAH (third aluminum hydrate) and Al[6] in monosulfate or C-A-H (calcium aluminate hydrate) can be transformed into Al[6] in ettringite by sulfate attack. Furthermore, through thermodynamic calculation, the decrease of Ca/Si ratios and increase of Al/Si ratios can improve the thermodynamic stability of C-A-S-H gels under sulfate attack, which agrees well with the experiment results.展开更多
Plenty of flue gas desulfurization(FGD) gypsum generated from coal-fired power plants for sulfur dioxide sequestration caused many environmental issues. Preparing calcium sulfate whisker(CSW) from FGD gypsum by hydrot...Plenty of flue gas desulfurization(FGD) gypsum generated from coal-fired power plants for sulfur dioxide sequestration caused many environmental issues. Preparing calcium sulfate whisker(CSW) from FGD gypsum by hydrothermal synthesis is considered to be a promising approach to solve this troublesome problem and utilize calcium sulfate in a high-value-added way. The effects of particle size of FGD gypsum, slurry concentration,and additives on CSW were investigated in this work. The results indicated that fine particle size of FGD gypsum and moderately high slurry concentration were beneficial for crystal nucleation and growth. Three additives of magnesium chloride, citric acid, and sodium dodecyl benzene sulfonate(SDBS) were employed in this study. It was found that mean length and aspect ratio of CSW were both decreased by the usage of magnesium chloride,while a small quantity of citric acid or SDBS could improve the CSW morphology. When multi-additives of citric acid-SDBS were employed, the mean length and aspect ratio increased more than 20%. Moreover, surface morphology of CSW went better, and the particle size and crystal shape became more uniform.展开更多
Hollow calcium carbonate(CaCO3) microspheres were prepared in aqueous solution with the presence of polyoxyethylene(20) sorbitan monolaurate(Tween20) and sodium dodecyl sulfate(SDS).The microspheres were characterized...Hollow calcium carbonate(CaCO3) microspheres were prepared in aqueous solution with the presence of polyoxyethylene(20) sorbitan monolaurate(Tween20) and sodium dodecyl sulfate(SDS).The microspheres were characterized with X-ray diffraction(XRD),scanning electron microscopy(SEM) and transmission electron microscope(TEM).The X-ray diffraction data showed that the hollow CaCO3 microsphere consisted of calcite crystals.The influence of Tween20 and SDS concentrations on the morphology of CaCO3 crystals was investigated.The results suggested that the"core-shell model"of Tween20/SDS micelle aggregated as templates,which could control the growth of hollow CaCO3 microspheres.The interaction between mixed surfactants and calcium ions played a critical role in organizing calcium carbonate in microscopic level.展开更多
The influences of magnesium and ferric ions in their different ratios on the rate of gypsum crystallization were studied under the conditions similar to those of wet flue-gas desulfurization(WFGD). The results show th...The influences of magnesium and ferric ions in their different ratios on the rate of gypsum crystallization were studied under the conditions similar to those of wet flue-gas desulfurization(WFGD). The results show that addition of both Mg2+ and Fe3+ increased induction time and decreased the growth efficiency up to 50% compared with the baseline(without impurities) depending on the concentration and the type of impurity. The effects of Mg2+ and Fe3+ on the surface energy and the rate of nucleation were estimated by employing the classical nucleation theory. The surface energy decreased by 8% and 14% with the addition of 0.02 mol/L magnesium or ferric ions, respectively, compared to the baseline. Mg2+ and Fe3+ made the growth rate of the (020), (021) and (040) faces of gypsum crystal a much greater reduction, which leads to the formation of needle crystals compared to the baseline which favors the formation of plate or flakes. Furthermore, an edge detection program was developed to quantify the effects of impurities on the filtration rate of gypsum product. The results show that the inhibition efficiency of the presence of 0.02 mol/L Mg2+ and Fe3+ on the filtration rate of gypsum crystal ranges from 22% to 39%.展开更多
The influence of sulfated polysaccharide (SPS) isolated from marine algae Sargassum fusiforme on the morphology and phase compositions of urinary crystal calcium oxalate was investigated in vitro by means of scanning ...The influence of sulfated polysaccharide (SPS) isolated from marine algae Sargassum fusiforme on the morphology and phase compositions of urinary crystal calcium oxalate was investigated in vitro by means of scanning electron microscopy and X-ray diffraction. SPS maybe is a potential inhibitor to CaOxa urinary stones by inhibiting the growth of calcium oxalate monohydrate (COM), preventing the aggregation of COM, and inducing the formation of calcium oxalate dihydrate (COD) crystals.展开更多
1 Introduction Calcium sulfate deposition is one of the most important and serious problems faced by heat transfer equipment during operation(Pavlos et al.,1999;Liu et al.,1996).The crystallization of calcium sulfate ...1 Introduction Calcium sulfate deposition is one of the most important and serious problems faced by heat transfer equipment during operation(Pavlos et al.,1999;Liu et al.,1996).The crystallization of calcium sulfate is known as a展开更多
1 Introduction There exist calcium and sulfate ions outside sodium chloride in solution mining for calcium sulfate brine.The calcium and sulfate ions not only affect the purity of the vacuum salt products,but also inc...1 Introduction There exist calcium and sulfate ions outside sodium chloride in solution mining for calcium sulfate brine.The calcium and sulfate ions not only affect the purity of the vacuum salt products,but also increase the scaling of vacuum evaporation tanks and brine reusing pipes.Additives have certain impacts on the crystallization dynamics(Randolph et al.,1971).The展开更多
In order to eliminate the effect of calcite associated with scheelite on the scheelite flotation, hydrochloric acid was used to dissolve the calcite, and the soaking solution was used to prepare CaSO_4 whiskers by hyd...In order to eliminate the effect of calcite associated with scheelite on the scheelite flotation, hydrochloric acid was used to dissolve the calcite, and the soaking solution was used to prepare CaSO_4 whiskers by hydrothermal reaction with sulfuric acid at ambient pressure. First, the condition experiments of preparing CaSO_4 whiskers by using CaCl_2 and H_2SO_4 were carried out to optimize reaction parameters of the crystallization process. The optimal conditions were: at 102 ℃ reaction temperature, 0,5 mol/L reactant concentration and 60 min reaction time. Then based on the condition experiments and considering keeping acid concentration stable for achieving HCl recycling, Calcium sulfate whiskers with the average diameter of 1.41 μm and the average aspect ratio of 109 were prepared by the soaking solution after evaporating to half of its volume and 1.0 mol/L H_2SO_4 at 102 ℃ for 60 min: After ion exchange processing,the filtrate could be used as HCl in the process of HCl dissolution.展开更多
Multilevel lumbar fusion usually requires a large quantity of iliac crest bone graft but the supply is usually insufficient, so an alternative bone graft substitute for autograft is needed. This prospective study inve...Multilevel lumbar fusion usually requires a large quantity of iliac crest bone graft but the supply is usually insufficient, so an alternative bone graft substitute for autograft is needed. This prospective study investigated the efficacy of calcium sulfate by comparing the fusion rates between the experimental material (calcium sulfate pellets with bone chips from laminectomy) and autologous iliac bone graft in long segment (three-or four-level) lumbar and lumbosacral posterolateral fusion. Forty-five patients with degenerative scoliosis or spondylolisthesis received multilevel spine fusion and decompression. The experimental material of calcium sulfate pellets with decompression bone chips was placed on the experimental side and the iliac crest bone graft was placed on the control side. The fusion status was assessed radiographically at three-month intervals, and solid fusion was defined as a clear continuous intertransverse bony bridge at all levels. The average follow-up period was 34.4 months. Twenty-nine (64.4%) patients showed solid fusion on the experimental side and 39 (86.7%) patients on the control side. The overall fusion rate was 86.7%. A statistically significant relation was found between the two sides with the Kappa coefficient of agreement of 0.436. Compared to the control side, the fusion rate of experimental side is significantly reduced (p = 0.014). The fusion ability of autograft is higher than the experimental material in multilevel lumbar posterolateral fusion. However, the overall fusion rate of calcium sulfate pellets is improved, compared with previously reported rates, which suggested that such material may be considered as an acceptable bone graft extender.展开更多
基金financial support from the Swedish Innovation Agency(VINNOVA)and China Scholarship Council(CSC).
文摘α-calcium sulfate hemihydrate (α-HH) is known to be suitable for application as bone void filler. High percentage of α-HH is obviously needed for medical applications, especially for implantation. Three commercially available calcium sulfate dihydrates (DH, CaSO4·2H2O) with different sizes and surface morphologies were used as starting materials to synthesize high percentage α-HH via a hydrothermal method. The median particle sizes of the three types of DH were 946.7 μm, 162.4 μm and 62.4 μm, respectively. They were named as DH-L, DH-M and DH-S in this paper. The particle size distribution, morphology and phase composition of the raw materials were evaluated before synthesis. SEM results revealed that DH-L consisted of irregular large particles, while DH-M and DH-S were composed of plate-like particles with some small ones. High percentage HH can be obtained with proper synthesis parameters by hydrothermal method, specifically, 105 °C/90 min for DH-L (achieving 98.8% HH), 105°C/30 min for DH-M (achieving 96.7% HH) and 100°C/45 min for DH-S (achieving 98.4% HH). All the synthesized HH were hexagonal columns, demonstrating that they were α-phase HH. The particle size and morphology of starting material (DH) have significant influences on not only the rate of phase transition but also the morphology of the synthesized α-HH. Calcium sulfate dihydrate cements were prepared by the synthesized α-HH. The highest compressive strength of calcium sulfate dihydrate cement was 17.2 MPa. The results show that the preparation of high percentage α-HH is feasible via a hydrothermal method and the process can be further scaled up to industrial scale production.
基金Funded by the National High-tech Research and Development Program of China(2011AA06A106)
文摘Calcium sulfate hemihydrate whiskers were synthesized successfully via one-step hydrothermal crystallization method using phosphogypsum at 130 °C for 240 min with an initial slurry mass fraction of 2.5 wt%. The phase compositions, microstructures, thermal properties and molecular structures of asprepared samples were analyzed by XRD, ESEM, EDS, TG-DTA, and FT-IR. The influence of raw materials' ball-milling time on the morphologies of whiskers was investigated. The effects of impurities on crystallization morphologies and length to diameter ratio(L/D) of calcium sulfate hemihydrate whiskers were studied. The results indicated that the calcium sulfate dihydrate crystalline could be translated directly into fibrous calcium sulfate hemihydrate whiskers. It was beneficial to form fine fiber structure when the ball-milling time of the raw material was 15 min. Aspect ratio of calcium sulfate hemihydrate whiskers decreased with increasing content of impurities. Moreover, the relative growth mechanism of whisker crystals via one-step hydrothermal crystallization method was discussed in detail.
基金Funded by the Major State Basic Research Development Program of China (973 Program) (No. 2009CB623104)the National Technology R&D Program for the 11th Five-year Plan (No. 2006BAJ05B03)
文摘The inhibition and its mechanism of sodium tripolyphosphate (STP) composited with super plasticizers (SPs) on hydration of α-calcium sulfate hemihydrate were studied by setting time, strength, hydration heat, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), electronic probe micro analysis (EPMA), scanning electron microscopy (SEM) and differential scanning calorimeter (DSC) measurements. The experimental results show that compared with STP addition, compositing STP with polycarboxylate (PC) plasticizer, the final setting time is prolonged from 0.5h to 2hs. While formulating STP with naphthalene-based plasticizer (NAP) or sulfonate melamine formaldehyde plasticizer (SMF), the final setting time is reduced to quarter of an hour. Similar changes can also be found in the rate of exothermic hydration and hydration degree. Formulating STP with suitable addition of PC can enhance the strength, while compositing STP and NAP or SMF weakens the strength. Besides, adding STP or STP and SMF, obvious movement (more than 1ev) of binding energy of Ca2p1/2 and Ca2p3/2 is detected. Compared with STP addition, content of the characteristic element (P) of STP is cut down form 1.1% to 0.49% by compositing STP with SMF. Furthermore, as hydration age increases, hydration inhibition in the presence of admixtures weakens and even disappears within 56 h.
文摘Objective:The as-providedα-calcium sulfate hemihydrate bone repair material exhibits superior degradation properties and osteogenic property to the traditional calcium sulfate bone repair materials. Its effects on the blood and the biocompatibility were studied to ensure its safety for the bone implantation application.Method: The hemolytic tests were conducted to evaluate the blood compatibility of theα-calcium sulfate hemihydrate. The extracts ofα-calcium sulfate hemihydrate with different concentration reacted with 2% rabbit red blood cell suspension. The existence and morphology of the red blood were observed through naked eye observation and microscope observation. The hemolytic ratios were calculated through the absorbances using a ultraviolet spectrophotometer.Result:It was observed by naked eye that the red blood accumulated at the bottom of the test tubes and the upper liquids were clear, colorless and transparent in the experimental sample. The microscope observation exhibited that the cells of the experimental samples had the normal morphology, no deformed and broken blood sell existed. The hemolytic ratios of the experimental sample were all less than 5%. The hemolytic ratios were increased with the increase of the concentration of the extracts. Conclusions: The hemolytic ratios of the medical -calcium sulfate hemihydrate accorded with the standard ISO/TR7405-1984(E). It could be concluded the material would not cause acute hemolysis. The osteogenic property exhibited dose dependence.
基金National Natural Science Foundation of China(No.82060347)Postgraduate innovation research project of Hainan Medical College(No.HYYS2020-38)。
文摘Objective:To prepare a bone repair material with certain mechanical strength and biological activity,this paper used calcium sulfate hemihydrate(CSH)powder compounded with calcium hydroxide(Ca(OH)2)powder to prepare a bone repair scaffold material for physicochemical property characterization and testing.Methods:The physical and chemical properties and characterization of the dried and cured bone repair materials were determined by Fourier infrared spectroscopy(FT-IR),X-ray diffraction(XRD),and scanning electron microscopy;Universal material testing machine to determine the mechanical and mechanical strength of composite materials.Results:XRD showed that the structure of the composite material phase at 5%concentration was calcium sulfate hemihydrate and calcium hydroxide after hydration.The FT-IR and XRD analyses were consistent.Scanning electron microscopy(SEM)results showed that calcium hydroxide was uniformly dispersed in the hemihydrate calcium sulfate material.0%,1%,5%,and 10%specimen groups had compressive strengths of 3.86±3.1,5.27±1.28,8.22±0.96,and 14.4±3.28 MPa.10%addition of calcium hydroxide significantly improved the mechanical strength of the composites,but also reduced the the porosity of the material.Conclusion:With the addition of calcium hydroxide,the CSH-Ca(OH)2 composite was improved in terms of mechanical material and is expected to be a new type of bone repair material.
基金Supported by the National High-Tech Research & Development Program of China (Grant No. 2006AA06Z385)New Century Excellent Talents in University (Grant No. NCET-04-0549)the Project of Science and Technology Plan of Zhejiang Province (Grant No. 2007C23055)
文摘Alpha-calcium sulfate hemihydrate (α-HH) has been prepared from flue gas desulfurization (FGD) gypsum with salt solution method under atmospheric pressure. X-ray diffraction (XRD),thermogra-vimetry and differential scanning calorimetry (TG-DSC),optical micrograph,X-ray photoelectron spec-troscopy (XPS),energy dispersive spectrometry (EDS),and scanning electron microscopy (SEM) have been employed to characterize the α-HH crystals,based on which the formation and growth mecha-nisms of the α-HH crystals have been discussed. The results show that FGD gypsum can be success-fully transformed into high purity α-HH in salt solution under mild conditions,and that a dissolu-tion-recrystallization route is most probably adopted by this transition. The growth of α-HH crystals in salt solution demonstrates a preferred direction along [001] and results in a bundle-of-sheets or bun-dle-of-raphide texture. The characteristics revealed in this study can help to understand and control the growth of the α-HH crystal from solution.
基金financially supported by the Shanghai Foundation of Excellent Young University Teachersthe Science and Technology Commission of Shanghai Municipality(13ZR1415100,13JC1402700,14195800600)the Science and Technology Development Fund of Pudong New Area(PKJ2012-C05)
文摘Calcium sulfate hemihydrate(CSH) whiskers were synthesized by phase transition in CaCl_2 solution under atmospheric pressure.Analytical-grade calcium sulfate dihydrate(AR CSD) was used as the raw material for the synthesis of CSH whiskers,according to orthogonal experiments.The effects of reaction temperature,AR CSD content,H_2SO_4 content,and reaction time were investigated,and the crystallization conditions were optimized.The as-prepared CSH whiskers displayed a regular morphology and a highly uniform size,with an aspect ratio of 105.A simulation system was also established by blending various sulfates with AR CSD,to evaluate the effects of impurities in flue gas desulfurization(FGD) gypsum.The main aim was to prepare CSH whiskers directly from FGD gypsum,without any purification,using the optimized conditions.This is a facile potential alternative process for large-scale production of CSH whiskers using abundant FGD gypsum as source materials.
文摘This work investigates durability of cement-free mortars with a binder comprised of ground granulated blast furnace slag (GGBFS) activated by high-calcium fly ash (HCFA) and sodium carbonate (Na<sub>2</sub>CO<sub>3</sub>): the soundness, sulfate resistance, alkali-silica reactivity and efflorescence factors are considered. Results of tests show that such mortars are resistant to alkali-silica expansion. Mortars are also sulfate-resistant when the amount of HCFA in the complex binder is within a limit of 10 wt%. The fineness of fly ash determines its’ ability to activate GGBFS hydration, and influence soundness of the binder, early strength development, sulfate resistance and efflorescence behavior. The present article is a continuation of authors’ work, previously published in MSA, Vol. 14, 240-254.
基金financial support from Natural Sciences and Engineering ResearchCouncil(NSERC)(NSERC EGP 501335-16) along with the donated CSA cement
文摘The mining industry often uses shotcrete for ground stabilization. However, cracking within shotcrete is commonly observed, which delays production schedules and increases maintenance costs. A possible crack reduction method is using expansive shotcrete mixture consisting of calcium sulfoaluminate cement(CSA), ordinary Portland cement(OPC), and calcium sulfate(CS) to reduce shrinkage. Furthermore, fibers can be added to the mixture to restrain expansion and impede cracking. The objective of this paper is to study the effects of nylon fiber, glass fiber, and steel fiber on an expansive shotcrete mixture that can better resist cracking. In this study, parameters such as density, water absorption, volume of permeable voids, unconfined compressive strength(UCS), splitting tensile strength(STS), and volume change of fiber-added expansive mixtures were determined at different time periods(i.e. the strengths on the 28 th day, and the volume changes on the 1 st, 7 th, 14 th, 21 st, and 28 th days). The results show that addition of fibers can improve mixture durability, in the form of decreased water absorption and reduced permeable pore space content. Moreover, the expansion of the CSA-OPC-CS mixture was restrained up to50% by glass fiber, up to 43% by nylon fiber, and up to 28% by steel fiber. The results show that the STS was improved by 57% with glass fiber addition, 43% with steel fiber addition, and 38% with nylon fiber addition. The UCS was also increased by 31% after steel fiber addition, 26% after nylon fiber addition, and16% after glass fiber addition. These results suggest that fiber additions to the expansive shotcrete mixtures can improve durability and strengths while controlling expansion.
基金supported by the State Key Laboratory of Mineral Processing Science and Technology Open Fund(BGRIMM-KJSKL-2017-16)Liaoning Provincial Department of Education Youth Project(LJ2017QL028)Coal Resource Safety Mining and Clean Utilization Engineering Research Center Open Fund(LNTU15KF18)。
文摘In this paper,the solid waste desulfurization gypsum produced by coal-fired power plants was used as a raw material to prepare calcium sulfate whiskers with high application prospects.Calcium sulfate whiskers with uniform morphology and high aspect ratio can be prepared by hydrothermal method in sulfuric acid solution.A new process of desulfurization gypsum activated by high-energy grinding to reduce the reaction temperature and sulfuric acid concentration was developed.Through the comparison of product morphology,the best grinding time was determined to be 3.5 h.The mechanism of desulfurization gypsum through physical–chemical coupling to reduce energy consumption was clarified.The activation of desulfurization gypsum by grinding and the acidic environment provided by the sulfuric acid solution made the calcium sulfate solution reached rapid saturation and accelerated the nucleation rate.By calculating the conversion and crystallization rate of calcium sulfate whiskers,it was found that there were obvious"autocatalytic"kinetic characteristics during the crystallization process.
基金Funded by Anhui Key Laboratory of Advanced Building Materials,Anhui Jianzhu University(No.JZCL201602KF)Major State Basic Research Development Program of China(973 Program)(No.2015CB655101)+2 种基金State Key Laboratory of High Performance Civil Engineering Materials(No.2015CEM005)Natural Science Foundation of Hebei Province(No.E2016209283)Hubei Key Laboratory of Roadway Bridge and Structure Engineering(Wuhan University of Technology)(No.DQZDJJ201504)
文摘The thermodynamic stability of sulfate ions on synthesized calcium aluminosilicate hydrate (C-A-S-H) microstructure with different Ca/Si ratios and Al/Si ratios was investigated by XRD, SEM-EDS, 29Si and 27A1 nuclear magnetic resonance (NMR) and thermodynamic modeling. The results indicate that sulfate attack leads to both decalcification and dealumination for C-A-S-H gels, and the amount of corrosion products (gypsum and ettringite) decreased gradually with decreasing Ca/Si ratios of C-A-S-H. Sulfate ions can also promote the polymerization degree of C-A-S-H gels, improving its resistance to sulfate attack. Moreover, the 4-coordination aluminum (Al[4]) in C-A-S-H, 5-coordination aluminum (Al[5]), 6-ccordination aluminum (A1[6J) in TAH (third aluminum hydrate) and Al[6] in monosulfate or C-A-H (calcium aluminate hydrate) can be transformed into Al[6] in ettringite by sulfate attack. Furthermore, through thermodynamic calculation, the decrease of Ca/Si ratios and increase of Al/Si ratios can improve the thermodynamic stability of C-A-S-H gels under sulfate attack, which agrees well with the experiment results.
基金Supported by National Science Foundation of China(51374059,51304042)the Fundamental Research Funds for the Central Universities of China(N130402020)
文摘Plenty of flue gas desulfurization(FGD) gypsum generated from coal-fired power plants for sulfur dioxide sequestration caused many environmental issues. Preparing calcium sulfate whisker(CSW) from FGD gypsum by hydrothermal synthesis is considered to be a promising approach to solve this troublesome problem and utilize calcium sulfate in a high-value-added way. The effects of particle size of FGD gypsum, slurry concentration,and additives on CSW were investigated in this work. The results indicated that fine particle size of FGD gypsum and moderately high slurry concentration were beneficial for crystal nucleation and growth. Three additives of magnesium chloride, citric acid, and sodium dodecyl benzene sulfonate(SDBS) were employed in this study. It was found that mean length and aspect ratio of CSW were both decreased by the usage of magnesium chloride,while a small quantity of citric acid or SDBS could improve the CSW morphology. When multi-additives of citric acid-SDBS were employed, the mean length and aspect ratio increased more than 20%. Moreover, surface morphology of CSW went better, and the particle size and crystal shape became more uniform.
基金Supported by the Beijing Natural Science Foundation(2082021)the National Science & Technology Pillar Program in the 12th Five-Year Plan Period (2011BAE06B06-2)
文摘Hollow calcium carbonate(CaCO3) microspheres were prepared in aqueous solution with the presence of polyoxyethylene(20) sorbitan monolaurate(Tween20) and sodium dodecyl sulfate(SDS).The microspheres were characterized with X-ray diffraction(XRD),scanning electron microscopy(SEM) and transmission electron microscope(TEM).The X-ray diffraction data showed that the hollow CaCO3 microsphere consisted of calcite crystals.The influence of Tween20 and SDS concentrations on the morphology of CaCO3 crystals was investigated.The results suggested that the"core-shell model"of Tween20/SDS micelle aggregated as templates,which could control the growth of hollow CaCO3 microspheres.The interaction between mixed surfactants and calcium ions played a critical role in organizing calcium carbonate in microscopic level.
基金Supported by the State 11.5 Support Plan(No.2006BAA01B04)the New Century Excellent Talent Support Plan of China (No.NCET-06-0513)
文摘The influences of magnesium and ferric ions in their different ratios on the rate of gypsum crystallization were studied under the conditions similar to those of wet flue-gas desulfurization(WFGD). The results show that addition of both Mg2+ and Fe3+ increased induction time and decreased the growth efficiency up to 50% compared with the baseline(without impurities) depending on the concentration and the type of impurity. The effects of Mg2+ and Fe3+ on the surface energy and the rate of nucleation were estimated by employing the classical nucleation theory. The surface energy decreased by 8% and 14% with the addition of 0.02 mol/L magnesium or ferric ions, respectively, compared to the baseline. Mg2+ and Fe3+ made the growth rate of the (020), (021) and (040) faces of gypsum crystal a much greater reduction, which leads to the formation of needle crystals compared to the baseline which favors the formation of plate or flakes. Furthermore, an edge detection program was developed to quantify the effects of impurities on the filtration rate of gypsum product. The results show that the inhibition efficiency of the presence of 0.02 mol/L Mg2+ and Fe3+ on the filtration rate of gypsum crystal ranges from 22% to 39%.
基金granted by the National Natural Science Foundation of China(20471024)the Project-sponsored by SRF for ROCS,SEMthe Key project of Natural Science Foundation of China(20031010).
文摘The influence of sulfated polysaccharide (SPS) isolated from marine algae Sargassum fusiforme on the morphology and phase compositions of urinary crystal calcium oxalate was investigated in vitro by means of scanning electron microscopy and X-ray diffraction. SPS maybe is a potential inhibitor to CaOxa urinary stones by inhibiting the growth of calcium oxalate monohydrate (COM), preventing the aggregation of COM, and inducing the formation of calcium oxalate dihydrate (COD) crystals.
基金financial support of National Nature Science Foundation (21376178)TIDA giant growth plan (2011-XJR13020)+3 种基金Tianjin Science and technology support program (12ZCDZSF06900)Tianjin University of Science and Technology fund for scientific research (20120119)Tianjin education commission program (20130509)Research fund for the doctoral program of higher education of China(20131208120001)
文摘1 Introduction Calcium sulfate deposition is one of the most important and serious problems faced by heat transfer equipment during operation(Pavlos et al.,1999;Liu et al.,1996).The crystallization of calcium sulfate is known as a
基金financial support of National Nature Science Foundation (21376178)TIDA giant growth plan (2011-XJR13020)+3 种基金Tianjin Science and technology support program (12ZCDZSF06900)Tianjin University of Science and Technology fund for scientific research (20120119)Tianjin education commission program (20130509)Research fund for the doctoral program of higher education of China (20131208120001)
文摘1 Introduction There exist calcium and sulfate ions outside sodium chloride in solution mining for calcium sulfate brine.The calcium and sulfate ions not only affect the purity of the vacuum salt products,but also increase the scaling of vacuum evaporation tanks and brine reusing pipes.Additives have certain impacts on the crystallization dynamics(Randolph et al.,1971).The
基金provided by the National Key Technology R&D Programs from the Ministry of Science and Technology of China(No.2012BAB07B05)the Program of Introducing Talents of Discipline to Universities(Supported by the 111 Project,B14034)the Fundamental Research Funds for the Central Universities of Central South University(No.2016zzts104)
文摘In order to eliminate the effect of calcite associated with scheelite on the scheelite flotation, hydrochloric acid was used to dissolve the calcite, and the soaking solution was used to prepare CaSO_4 whiskers by hydrothermal reaction with sulfuric acid at ambient pressure. First, the condition experiments of preparing CaSO_4 whiskers by using CaCl_2 and H_2SO_4 were carried out to optimize reaction parameters of the crystallization process. The optimal conditions were: at 102 ℃ reaction temperature, 0,5 mol/L reactant concentration and 60 min reaction time. Then based on the condition experiments and considering keeping acid concentration stable for achieving HCl recycling, Calcium sulfate whiskers with the average diameter of 1.41 μm and the average aspect ratio of 109 were prepared by the soaking solution after evaporating to half of its volume and 1.0 mol/L H_2SO_4 at 102 ℃ for 60 min: After ion exchange processing,the filtrate could be used as HCl in the process of HCl dissolution.
文摘Multilevel lumbar fusion usually requires a large quantity of iliac crest bone graft but the supply is usually insufficient, so an alternative bone graft substitute for autograft is needed. This prospective study investigated the efficacy of calcium sulfate by comparing the fusion rates between the experimental material (calcium sulfate pellets with bone chips from laminectomy) and autologous iliac bone graft in long segment (three-or four-level) lumbar and lumbosacral posterolateral fusion. Forty-five patients with degenerative scoliosis or spondylolisthesis received multilevel spine fusion and decompression. The experimental material of calcium sulfate pellets with decompression bone chips was placed on the experimental side and the iliac crest bone graft was placed on the control side. The fusion status was assessed radiographically at three-month intervals, and solid fusion was defined as a clear continuous intertransverse bony bridge at all levels. The average follow-up period was 34.4 months. Twenty-nine (64.4%) patients showed solid fusion on the experimental side and 39 (86.7%) patients on the control side. The overall fusion rate was 86.7%. A statistically significant relation was found between the two sides with the Kappa coefficient of agreement of 0.436. Compared to the control side, the fusion rate of experimental side is significantly reduced (p = 0.014). The fusion ability of autograft is higher than the experimental material in multilevel lumbar posterolateral fusion. However, the overall fusion rate of calcium sulfate pellets is improved, compared with previously reported rates, which suggested that such material may be considered as an acceptable bone graft extender.
