工艺参数对选择性激光烧结PS/SBS/纳米CaCO3制件弯曲强度影响

针对聚苯乙烯(PS)粉末选择性激光烧结(SLS)成型件强度较低的问题,采用机械混合法制备了PS/苯乙烯–丁二烯–苯乙烯嵌段共聚物(SBS)/纳米CaCO₃复合粉末,通过单因素实验分析了SLS工艺参数对成型件弯曲强度的影响,并通过正交试验和极差分析获得了最优工艺参数组合。实验结果表明,烧结件的弯曲强度随着激光功率的增大而升高,随着扫描速度、扫描间距和分层厚度的增大而降低;激光功率对PS/SBS/纳米CaCO₃复合粉末烧结件弯曲强度的影响最大,分层厚度对弯曲强度的影响最小,扫描速度和扫描间距的影响介于两者之间;最佳工艺参数组合为:激光功率27 W,扫描速度1300 mm/s,扫描间距0.24 mm,单层厚度0.22 mm。在此工艺参数组合下PS/SBS/纳米CaCO₃复合粉末烧结件的弯曲强度为13.38 MPa;改性纳米CaCO₃与PS和SBS的相容性较好,能有效起到增强的作用。     

滑石、CaCO3、BaSO4填充PP复合材料力学性能及界面相互作用对比

以3种白色矿物粉体［颗粒状CaCO₃、BaSO₄,片层状滑石（talc）］为填料,聚丙烯（PP）为基体树脂,通过熔融共混法制备PP复合材料,研究3种矿物粉体在不同含量时对PP复合材料的力学性能、流动性能与断裂形貌的影响规律,并采用Turcasanyi半经验公式计算了矿物填料与PP复合材料力学性能界面相互作用。结果表明,3种矿物粉体的加入均降低了PP的拉伸强度,PP/talc复合材料的拉伸强度明显高于PP/CaCO₃ 与PP/BaSO₄,且talc的加入明显增强了PP的拉伸模量与弯曲模量;CaCO₃ 与BaSO₄的加入使复合材料弯曲强度降低,talc的加入使复合材料弯曲强度提高;CaCO₃对PP断裂伸长率与悬臂梁缺口冲击强度的提升最为明显;talc的加入使复合材料流动性能得到提高,而颗粒状的CaCO₃与BaSO₄的加入对加工性能影响较小;CaCO₃ 与BaSO₄在PP中均存在一定团聚现象,且与PP相容性较差,存在明显界面缺陷;talc与PP间界面较模糊,二者之间有较强的黏结作用。     

Powder Processing for the Fabrication of Si3N4 Ceramics: I, Influence of Spray-Dried Granule Strength on Pore Size Distribution in Green Compacts

The effect of spray-dried granule strength on the micro-structure of green compacts obtained by isostatic pressing was quantitatively analyzed. The fracture strength of single granules of Si₃N₄ powder made with ultrafine A1₂O₃ and Y₂O₃ powders was measured directly by diametral compression. It was found that fracture strength increased notably with the increasing relative density of the granule and the decreasing size of agglomerates in suspension before spray-drying. Even when green bodies were prepared at an isostatic pressure of 200 MPa, intergranular pores, which negatively affected densification of the sintered bodies, occurred between unfractured granules. The volume and size of these pores in the green compacts increased with the increasing fracture strength of the granules. In the case of closely packed granules, an isostatic pressure of 800 MPa was required to completely collapse the intergranular pores. A simple equation was derived to calculate the isostatic pressure necessary for complete collapse of intergranular pores in the green compacts, and it was determined that granule strength must be kept as low as possible to obtain uniform green compacts.     

Preparation and Microstructure of a ZrB2–SiC Composite Fabricated by the Spark Plasma Sintering–Reactive Synthesis (SPS–RS) Method

A mixture of Zr, B₄C, and Si powders was adopted to synthesize a ZrB₂–SiC composite using the spark plasma sintering–reactive synthesis (SPS–RS) method. SPS treatments were carried out in the temperature range of 1350°–1500°C under a varying pressure of 20–65 MPa with a 3-min holding time. A dense (∼98.5%) ZrB₂–SiC composite was successfully fabricated at 1450°C for 3 min under 30 MPa. The microstructure of the composite was investigated. The in situ formed ZrB₂ and SiC phases dispersed homogeneously on the whole. The grain size of ZrB₂ and SiC was <5 and 1 μm, respectively. A number of in situ formed ultrafine SiC particles were observed entrapped in the ZrB₂ grains.     

Ti/Zr复合纳滤膜的制备及其性能

通过聚合溶胶路线制备出稳定的Ti/Zr(摩尔比=1:1)复合溶胶。采用浸浆法,在平均孔径为5～6 nm的片状a-Al₂O₃/g-Al₂O₃载体上制备出完整无缺陷的Ti/Zr复合纳滤膜。详细考察了焙烧温度对Ti/Zr粉体的影响,并考察了Ti/Zr复合纳滤膜的性能。结果表明:在较高烧成温度下(500℃),Ti/Zr粉体依然呈无定形态且保持微孔结构。在400℃烧成温度下制备出孔径为1.49 nm的Ti/Zr复合纳滤膜,该膜的截留分子量(MWCO)为880,纯水通量为4.3 L·m^-2·h^-1·MPa^-1。在pH=6,压力0.8 MPa的条件下,该膜对0.005 mol·L^-1的MgCl₂、CaCl₂的截留率分别为85%和78%。     

The effect of powder size on induction behaviour and binder distribution during high shear melt agglomeration of calcium carbonate

Growth mechanisms in high shear mixer granulation were observed over a wide range of particle size and liquid-to-solid (L/S) ratio. The materials used were calcium carbonate (CaCO₃; size fractions in the range 1.5 to 85 μm) with a binder of polyethylene glycol 6000 (PEG 6k). The binder, solid at room temperature, was added by the “melt-in” method. A 10 L vertical-axis granulator was used, with a chopper and a four-bladed impeller.

The mean granule size and granule size distribution were measured at regular intervals during the agglomeration process by careful sampling and sieving. The uniformity of binder distribution among the granules was also measured.

The growth behaviours of each grade of primary particles were classified and compared. An induction type mechanism was observed with an initial period of slow growth in mean particle size that lasted 2 to 3 min (the induction period). This was followed by a short rapid growth phase lasting 1 to 2 min. The final stage was a plateau of more or less zero growth. Interestingly, the end of the induction period and the onset of rapid growth corresponded to a change in the granule size distribution from bimodal to monomodal and a similar change in the distribution of binder. Induction period growth rate tended to be lower for granules of finer particles, but these grew more rapidly during the rapid growth stage and produced larger granules than the coarser primary particles.

The liquid-to-solid (L/S) ratio had a significant effect on the growth rate during the rapid growth stage but a minor effect on the granule size distribution and binder distribution. Primary particle size had a significant effect on the final average size of granules, the growth rate during the rapid growth stage and the distribution of granule size and binder.     

改性聚环氧琥珀酸对纳米碳酸钙分散性的研究

为避免纳米碳酸钙在水中团聚,采用可生物降解的改性聚环氧琥珀酸作为分散剂。由于改性聚环氧琥珀酸结构单元中有强极性磺酸基团,增强了分散液粒子之间的静电斥力。与聚环氧琥珀酸相比,改性聚环氧琥珀酸作分散剂时纳米碳酸钙悬浊液的稳定性更好,分散液粒子的粒径更小,流动性更好。将三聚磷酸钠作协同分散剂与其配合使用后,可显著提高改性聚环氧琥珀酸对纳米碳酸钙的分散效果。     

Fabrication of Machinable Silicon Carbide-Boron Nitride Ceramic Nanocomposites

SiC/BN nanocomposite powders with the microstructure of micrometer-sized SiC particles coated with nanometer-sized BN particles were prepared via a chemical reaction, which used a mixture of boric acid (H₃BO₃) and urea (CO(NH₂)₂) as reactants coated on the surface of the SiC particles to react under a nitrogen-gas atmosphere. The results of XRD, TEM, and SAED studies showed that the coating layer (BN) was composed mostly of amorphous and nanometer-sized BN particles at the reaction temperature of 850°C. When the nanocomposite powders were hot-pressed at 1850°C, machinable SiC/BN ceramic nanocomposites with fine grain size and homogeneous microstructure were fabricated. The composite that contained 20 wt% BN exhibited high strength (the three-point bending strength was 588.4 ± 26.8 MPa) and excellent machinability.     

用于选择性激光烧结成型的聚酰胺6/硫酸钙复合粉体的制备及性能研究

采用溶液沉淀法制备了聚酰胺6/硫酸钙（PA6/CaSO₄）复合粉体,通过扫描电子显微镜（SEM）、差示扫描量热仪（DSC）、激光粒度分布仪和Ｘ射线衍射仪（XRD）对复合粉体的微观形貌、热性能、粒度分布、晶体结构和流动性进行了表征。结果表明,随着CaSO₄的加入,PA6/CaSO₄复合粉体由松散的球形结构转变为密实的球形结构;CaSO₄的加入能够提高PA6/CaSO₄复合粉体的结晶度并拓宽其烧结温度窗口,在CaSO₄含量为5 %（质量分数,下同）时,结晶度和烧结温度窗口均达到最大值,分别为61.84 %和18.95 ℃;PA6/CaSO₄复合粉体的粒径随CaSO₄含量的增加呈现先减后增的趋势,休止角先减后增,堆积密度先增后减;当CaSO₄含量为3 %~5 %时,PA6/CaSO₄复合粉体的流动性能最佳,最适用于选择性激光烧结。     

Features of corrosion resistance of AlN–SiC ceramics in air up to 1600°C

The kinetics and mechanism of (80% AlN + 20% SiC) and (50% AlN + 50% SiC) powders and ceramics oxidation in air up to 1600°C were studied with the aid of TG, DTA, XRD, EPMA, SEM and metallographic analysis methods. The ceramics samples were obtained by hot pressing fine-dispersion AlN and SiC powders with an average particle size of 1 μm at 1800°C for 2 h. This ensures a fine-grain material structure with a uniform distribution of phase components. It was shown that in a nonisothermal regime, a three-stage oxidation mechanism takes place. It was established that the scale formed consists of three oxide layers. In the inner layer, Al₁₀N₈O₂ oxynitride and β-SiO₂ (cristobalite) phases were observed; in the intermediate layer, β-SiAlON was found for samples with a relatively low SiC content whereas -Al₂O₃ was present in samples with a greater SiC content. The outer layer contains 3Al₂O₃.2SiO₂ (mullite) as a main phase, the latter ensuring highly protective properties of the scale. The materials investigated can be considered as having extremely high resistance to corrosion up to 1550°C.     

Combustion Synthesis of Silicon Carbide in Nitrogen Atmosphere

Fine SiC powders were synthesized by burning the mixed reactionts Si and C in a nitrogen atmosphere of 3 to 10 MPa. The exothermic synthesis reaction propagated spontaneously after igniting the reactants at room temperature. The SiC powders obtained had a uniform size distribution of about 0.2 μm. The combustion velocity was 0.8 to 1.5 mm / s. The maximum temperature measured at the reaction was 2500 K, which was higher than the adiabatic combustion temperature of SiC, but slightly lower than the decomposition temperature of Si₃N₄ under nitrogen pressure.     

聚乙烯/纳米硫酸钙粉体复合软包装应用性能研究

采用含有51 %的纳米硫酸钙（CaSO₄）与聚乙烯（PE）为主要原料,通过熔融共挤制备了一种绿色低碳可降解的新型环保复合薄膜,并与同等碳酸钙（CaCO₃）含量的PE/CaCO₃复合薄膜比较,研究高填充无机纳米聚烯烃复合软包装材料的应用性能。采用拉力试验机、高温凝胶色谱仪、氙灯日晒老化试验箱、总有机碳（TOC）分析仪等设备对其物理性能、卫生性能、降解性能、碳含量进行测试分析。结果表明,PE/CaSO₄复合薄膜的拉伸强度、断裂伸长率优于同等含量的PE/CaCO₃复合薄膜,总迁移量（水、4 %乙酸、20 %乙醇、95 %乙醇、异辛烷）、高锰酸钾消耗量、重金属未超出国家标准的限量要求,在加速老化条件下,其拉伸性能和重均分子量均能达到光降解塑料的要求,且其碳含量远较其他塑料薄膜要低。     

Spray-dried ceramic powders: A quantitative correlation between slurry characteristics and shapes of the granules

The characteristics and consequently the properties of ceramic coatings performed using plasma spraying means depend not only on the operating conditions but also on the powder feedstock. Oxide powders are commonly prepared in one stage or in a combination of stages of fusing, crushing, agglomerating and sintering. The spray drying process (which corresponds to the agglomerating route) is a technique in which small constituent particles dispersed in water (which is called slurry) are sprayed in hot air and granulated thanks to a binder (latex or PVA). Spray drying is carried out for a variety of reasons, two major motivations being the production of composite and shape controlled powders for thermal spray applications. The aim of the present work was to establish a correlation between the slurry formulation and the characteristics of the spray dried granules for two oxide ceramics: Al₂O₃ and Y₂O₃-ZrO₂. Detailed studies on the dispersion and stability of the slurries were performed using sedimentation tests, electrophoretic mobility measurements as well as adsorption isotherms experiments. Then, a drying experimental test based on the drying of a suspended droplet was developed to assess the drying mechanisms, identify the correlation between the slurry characteristics and the morphology of the dried granules and finally to predict the shapes of the spray-dried powders. It was shown that there is a qualitative relation between the sedimentation behaviour (as measured by the sediment ratio) and the granule shape (solid or hollow) and a quantitative relation between the thickness of the shell (for hollow granule) and the state of dispersion and the nature of the binder used. Finally, several powder batches were prepared in the spray-dryer which confirm the reliability of the drying simulation test.     

衣康酸共聚物合成工艺的优化及其阻垢性能研究

以衣康酸(IA)、烯丙氧基羟丙基磺酸钠(AHPS)、烯丙基聚氧乙烯醚(APEG)为单体,通过自由基聚合的方式,合成出IA-AHPS-APEG三元共聚物。利用中心复合设计法建立了数学模型,结合静态阻碳酸钙垢测试,对聚合反应的引发剂用量、反应温度和反应时间进行了优化。通过FT-IR技术分析了聚合物IA-AHPS-APEG的分子结构,利用TG、SEM和XRD等技术分析了碳酸钙垢和硫酸钙垢的形貌和晶体结构变化,探究了聚合物IA-AHPS-APEG的阻垢机理。结果表明,优化后的IA-AHPS-APEG可以抑制碳酸钙和硫酸钙晶体的正常生长,并使碳酸钙晶体发生晶格畸变,其对碳酸钙的阻垢率最高可达93.2%,对硫酸钙的阻垢率接近100%。     

Reactive Hot Pressing of ZrB2–SiC Composites

A ZrB₂–SiC composite was prepared from a mixture of zirconium, silicon, and B₄C via reactive hot pressing. The three-point bending strength was 506 ± 43 MPa, and the fracture toughness was 4.0 MPa·m^1/2. The microstructure of the composite was observed via scanning electron microscopy; the in-situ -formed ZrB₂ and SiC were found in agglomerates with a size that was in the particle-size ranges of the zirconium and silicon starting powders, respectively. A model of the microstructure formation mechanism of the composite was proposed, to explain the features of the phase distributions. It is considered that, in the reactive hot-pressing process, the B and C atoms in B₄C will diffuse into the Zr and Si sites and form ZrB₂ and SiC in situ , respectively. Because the diffusion of Zr and Si atoms is slow, the microstructure (phase distributions) of the obtained composite shows the features of the zirconium and silicon starting powders.     

Controlling the morphology of ceramic and composite powders obtained via spray drying – A review

Spray drying is one of the most convenient methods for drying suspensions (slurries) and for granulation of materials. Spray dried powders have good flowability, narrow size distribution and controllable morphology. Morphology of powder particles (also called granules or microspheres) strongly affects the use and handling of powders. This review discusses the latest research on parameters that affect morphology and size of granules obtained by spray drying: atomization parameters, properties of sprayed slurry, mass transfer etc. The formation of hollow and dense granules is extensively reviewed. Granule size is affected by droplet size, slurry concentration and initial particle size. Morphology mostly depends on size distribution of initial ceramic particles, agglomeration tendency in the slurry and mechanical strength of the shell of a granule during the drying process compared to capillary force of the suspension liquid. Polymer additives (e.g. binders and lubricants) change the properties of granule shell and the evaporation of moisture; thus, polymer additives significantly affect morphology.     

多孔Al2O3/SiC、MoSi2/SiC复合材料的制备及吸波性能

以Si、Al₂O₃、MoSi₂微粉和生物竹材为原料,采用包埋烧结法分别制备出SiC多孔材料、Al₂O₃/SiC、MoSi₂/SiC复合材料。采用XRD、SEM及波导法测试其物相组成、显微结构及吸波性能。结果表明：MoSi₂/SiC复合材料的厚度为2 mm时有明显的吸波特性,有效吸收带宽在X波段的9.65~12.4 GHz频率范围内达2.75 GHz,且最低反射损耗为-38.27 dB。Al₂O₃/SiC复合材料孔道内的Al₂O₃与SiC晶须交缠,形成大量电偶极矩,产生介电损耗;MoSi₂/SiC复合材料除介电损耗外还存在电阻损耗,使得复合材料电磁损耗增加,是较有前途的结构功能吸波材料。     

On agglomeration phenomena in ball mills: application to the synthesis of composite materials

Composites of poly(vinyl acetate) filled with calcium carbonate (CaCO₃) have been synthesized in a ball mill. The different steps in fragmentation and agglomeration phenomena have been identified. The materials have first been ground separately to characterize their behaviour in the mill. Then, they were ground together. It has been shown that small CaCO₃ fragments cover PVA particles, limiting for a first time the agglomeration of these and permitting their size reduction. Then, when PVA fragments are small enough, a competition between size reduction and agglomeration occurs, which favours the dispersion of CaCO₃ in the matrix. It has also been observed that the presence of the filler does not modify significantly the molecular mobility of PVA.     

油酸修饰纳米CaCO3对PP结晶行为和力学性能的影响

Oleic acid (OA)-modified CaCO3 nanoparticles were prepared using surface modification method. Infrared spectroscopy (IR) was used to investigate the structure of the modified CaCO3 nanoparticles, and the result showed that OA attached to the surface of CaCO3 nanoparticles with the ionic bond. Effect of OA concentration on the dispersion stability of CaCO3 in heptane was also studied, and the result indicated that modified CaCO3 nanoparticles dispersed in heptane more stably than unmodified ones. The optimal proportion of OA to CaCO3 was established. The effect of modified CaCO3 nanoparticles on crystallization behavior of polypropylene (PP) was studied by means of DSC. It was found that CaCO3 significantly increased the crystallization temperature, crystal-lization degree and crystallization rate of PP, and the addition of modified CaCO3 nanoparticles can lead to the for-mation of β-crystal PP. Effect of the modified CaCO3 content on mechanical properties of PP/CaCO3 nanocompo-sites was also studied. The results showed that the modified CaCO3 can effectively improve the mechanical proper-ties of PP. In comparison with PP, the impact strength of PP/CaCO3 nanocomposites increased by about 65% and the flexural strength increased by about 20%.     

Kinetics of property change associated with atmospheric humidity changes in alumina powder granules with PVA binder

A microcompression testing machine was used on single Al₂O₃ powder granules to study their stress–strain behavior as a function of relative humidity. The test granules were prepared by spray-drying slurries containing 3 mass% poly(vinyl alcohol) and Al₂O₃ powder. The stress–strain curves and granule strength were determined at regular time intervals, after step changes in atmospheric humidity. When stress was applied, deformation increased rapidly with the stress. This stress corresponded to the fracture strength of the granule. In a dry atmosphere, the granules deformed linearly with increasing stress, and a rapid change in strain was noted above a certain critical value of increased stress. In a wet atmosphere, the granules deformed continuously at lower stress. The mechanical properties of the granules changed rapidly with time when the atmospheric relative humidity was changed. Within 3 min of exposure to a new atmosphere, the mechanical properties of the granules reached equilibrium values. The change in properties with humidity was controlled by moisture diffusion in the granules and was reversible.