CN117285335B - 高温相变储能陶瓷材料及其制备方法 - Google Patents
高温相变储能陶瓷材料及其制备方法 Download PDFInfo
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- CN117285335B CN117285335B CN202311577978.XA CN202311577978A CN117285335B CN 117285335 B CN117285335 B CN 117285335B CN 202311577978 A CN202311577978 A CN 202311577978A CN 117285335 B CN117285335 B CN 117285335B
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- 238000004146 energy storage Methods 0.000 title claims abstract description 68
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 89
- 235000015895 biscuits Nutrition 0.000 claims abstract description 56
- 150000003839 salts Chemical class 0.000 claims abstract description 48
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000002156 mixing Methods 0.000 claims abstract description 36
- 239000002002 slurry Substances 0.000 claims abstract description 34
- 239000003094 microcapsule Substances 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 29
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000006004 Quartz sand Substances 0.000 claims abstract description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 21
- 238000005245 sintering Methods 0.000 claims abstract description 20
- 239000000725 suspension Substances 0.000 claims abstract description 20
- 229910052674 natrolite Inorganic materials 0.000 claims abstract description 19
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000741 silica gel Substances 0.000 claims abstract description 14
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- 239000000395 magnesium oxide Substances 0.000 claims abstract description 13
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- 238000007598 dipping method Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 29
- 239000002994 raw material Substances 0.000 claims description 26
- 230000008859 change Effects 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000010433 feldspar Substances 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
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- 239000001095 magnesium carbonate Substances 0.000 description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 3
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
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- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
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- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
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- QCQCHGYLTSGIGX-GHXANHINSA-N 4-[[(3ar,5ar,5br,7ar,9s,11ar,11br,13as)-5a,5b,8,8,11a-pentamethyl-3a-[(5-methylpyridine-3-carbonyl)amino]-2-oxo-1-propan-2-yl-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3h-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxobutanoic acid Chemical compound N([C@@]12CC[C@@]3(C)[C@]4(C)CC[C@H]5C(C)(C)[C@@H](OC(=O)CC(C)(C)C(O)=O)CC[C@]5(C)[C@H]4CC[C@@H]3C1=C(C(C2)=O)C(C)C)C(=O)C1=CN=CC(C)=C1 QCQCHGYLTSGIGX-GHXANHINSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 241000264877 Hippospongia communis Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
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- 239000004568 cement Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
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- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
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- SSOLNOMRVKKSON-UHFFFAOYSA-N proguanil Chemical compound CC(C)\N=C(/N)N=C(N)NC1=CC=C(Cl)C=C1 SSOLNOMRVKKSON-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明属于储能陶瓷材料技术领域,具体涉及高温相变储能陶瓷材料及其制备方法。所述的高温相变储能陶瓷材料的制备方法,包括以下步骤:将氧化铝粉、钠长石粉、石英砂粉、Cr2O3和/或铬铁矿粉干混,将Al(H2PO4)3溶液和氢氧化铝粉湿混,将上述混料和预处理后的原盐混合,经模压成型、干燥、烧结,得到微胶囊素坯;将电熔镁砂粉、Al(H2PO4)3溶液、钠长石粉、石英砂粉、无机硅胶溶液、粘结剂混合均匀,得到料浆悬浮液,喷涂或浸渍在微胶囊素坯表面,然后干燥、烧结,得到高温相变储能陶瓷材料。所制备的高温相变储能陶瓷材料,与其它无机盐相比,显热潜热量大,热传导性能好,可以以最大程度储能蓄热。
Description
技术领域
本发明属于储能陶瓷材料技术领域,具体涉及高温相变储能陶瓷材料及其制备方法。
背景技术
储能(蓄热)技术是余热回收利用、分布式能源等技术的关键环节。钢铁、冶金、水泥等行业的工业窑炉的余热,是一种典型的二次能源,工业窑炉能耗巨大,余热产生量也巨大,若能回收这些余热,不仅可以节约能源,还可以减少污染。一般采用耐火材料或陶瓷材料作为蓄热载体,利用其耐高温性进行显热蓄热。
目前,高温窑炉蓄热室的结构和蓄热用材料由耐火砖转变为蓄热球或蜂窝体,但这些改变仅仅局限在结构上,而材料本质没有变化。工业窑炉余热资源利用的难点在于其温度跨度大、空间分布广,且存在时间上和数量上的波动性。余热传递和存储技术的落后已成为限制工业余热利用的关键性因素之一,而储能技术正是将非稳态热量整流成稳态热量的技术,即将非稳态热量用储能材料将其存储,等到需要热量时,再可控和稳定地利用非稳态余热,它克服了钢铁工业许多余热间隙性的难点,并有效地解决了热量供需不匹配的矛盾关系。因此,将储能技术应用于工业窑炉余热利用领域,对具有非稳态余热资源的高品质回收利用具有重大意义。
储能(蓄热)技术主要包括显热储能、相变(潜热)储能、热化学/吸附储能技术等。其中,热化学储能的储能密度最大,但距离工业应用尚有很多问题亟待解决,并具有一定的危险性;显热储能技术是目前市场中应用最为成熟的储能技术(如镁砖),但显热储能材料的蓄热密度偏低,容易导致储能***体积庞大、成本过高;相变(潜热)储能主要是依靠相变材料在相变过程中吸收和释放热量的特性来进行蓄热和放热,其在一定程度上综合了热化学储能密度高和显热储能工艺简单成熟的优点。
无机盐类相变储能材料,主要包括各类硝酸盐、碳酸盐、氟盐、盐酸盐及其混合物。工业生产中通常使用其混合物作为储能材料,通过选择混合盐中不同组分的配比来调整其熔点,以适应不同场景下的工作温度或寻求更高的相变潜热。常用无机盐混合物的熔点一般在150-900℃,甚至可达更高温度,主要应用于中高温储能领域。熔融盐类潜热(相变)储能材料是由多种酸根与碱性金属复合组成,其中常见的有氯化盐(盐酸盐)、氟化盐、硝酸盐、碳酸盐、硫酸盐等,常见的碱金属有锂、钠、钾、镁等。复合形成的熔融盐类相变储能材料种类广泛,且相较于有机类相变储能材料,其蓄热密度高,对温度变化响应速度更快。
但是,盐酸盐发生相变过程时会有大量的熔融盐产生,其流出会对容器和设备造成很强的腐蚀。
发明内容
针对现有技术的不足,本发明的目的是:提供一种高温相变储能陶瓷材料,与其它无机盐相比,显热潜热量大,热传导性能好,可以以最大程度储能蓄热;本发明还提供其制备方法,原材料与制作成本低,制备工艺简单可行,适合大规模工业生产与应用。
本发明所述的高温相变储能陶瓷材料的制备方法,包括以下步骤:
(1)素坯原料混合:将氧化铝粉、钠长石粉、石英砂粉、Cr2O3和/或铬铁矿粉进行干混,得到混合干料;将Al(H2PO4)3溶液和氢氧化铝粉进行湿混,硬化,得到混合湿料;然后将上述混合干料、混合湿料混合,并加入预处理后的原盐,混合均匀后得到素坯浆料;
(2)微胶囊素坯制备:将素坯浆料经模压成型,然后干燥、烧结、冷却,得到微胶囊素坯;
(3)素坯封装:将电熔镁砂粉、Al(H2PO4)3溶液、钠长石粉、石英砂粉、无机硅胶溶液、粘结剂混合均匀,得到料浆悬浮液,喷涂或浸渍在微胶囊素坯表面,然后干燥、烧结、冷却,得到高温相变储能陶瓷材料。本发明所采用的粉料粒度均在200-400目之间,优选为300目。
步骤(1)中,以质量份数计,各原料的用量如下:
氧化铝粉 100份,
预处理后的原盐 70-90份,
Al(H2PO4)3溶液 20-30份,
氢氧化铝粉 4-8份,
钠长石粉 5-10份,
石英砂粉 5-10份,
Cr2O3和/或铬铁矿粉 15-20份。
其中,氧化铝粉的氧化铝含量≥99%。
钠长石粉一种常见的长石矿物,钠长石的化学分子式为Na2O·Al2O3·6SiO2,其理论化学组成为:Na2O11.8%,Al2O319.4%,SiO268.8%。
石英砂粉的主要矿物成分是SiO2。
铬铁矿粉的主要成分为铁、镁和铬的氧化物。高温相变储能陶瓷材料在使用过程中,原盐会频繁处于熔融状态,可能会分解产生氯气或氯化氢气体,加入的Cr2O3或铬铁矿粉起到酸性抑制剂的作用,防止产生过量的氯气或氯化氢气体。
Al(H2PO4)3溶液的浓度为40-60wt.%;无机硅胶溶液的浓度为30-40wt.%。
Al(H2PO4)3溶液的pH值≥2.0,浓度在40-60wt.%之间为宜,优选为50wt.%。本发明将Al(H2PO4)3溶液和氢氧化铝粉进行湿混时,可以加入适量水进行稀释,水的加入量优选为Al(H2PO4)3溶液的0.2-1倍。湿混后的得到混料pH值为中性,采用酸性的Al(H2PO4)3溶液(pH≥2.0)加入适量的氢氧化铝粉,可以加快微胶囊素坯的硬化时间,其中Al(H2PO4)3溶液pH≥2.0,过低的酸性会导致制成的微胶囊素坯强度过低。
原盐的主要化学成分含量为:NaCl≥95wt.%、Ca2+≤0.2wt.%、Mg2+≤0.1wt.%、SO4 2-≤0.5wt.%、H2O≤2wt.%、水不溶物≤0.2wt.%。
优选的,所述原盐的预处理方法为:将原盐经球磨机干磨0.5-2h,过200-400目筛,再在380-400℃温度下保温1-3h,即得预处理后的原盐。对原盐进行预处理,一方面使原盐粒径与氧化铝粉粒径保持一致,另一方面可以去除原盐内含的自由水、结晶水、一些有机物杂质,可以省去球磨、干燥环节。
步骤(1)中,将Al(H2PO4)3溶液和氢氧化铝粉进行湿混后,硬化4-6h。
步骤(2)中,模压成型时,将素坯浆料在4h之内压制成型;所采用的模具可以为标准试样模具、方形砖模具、孔型砖模具等;压力机操作时,加压次数3次,加压速度为“一轻、二重、慢提起”。
步骤(2)中,干燥时,在100-120℃保温3-4h,优选的,在0.5-1h时间内由室温匀速升至100-120℃。
步骤(2)中,烧结时,在740-760℃保温0.5-2h,优选的,在5-6h时间内匀速升至740-760℃。烧结时需要控制适宜的升温速率,若升温过快,素坯极易开裂。
步骤(2)中,冷却时,自然条件下冷却至室温。
步骤(3)中,以质量份数计,各原料的用量如下:
电熔镁砂粉 100份,
Al(H2PO4)3溶液 40-50份,
钠长石粉 10-15份,
石英砂粉 6-10份,
无机硅胶溶液 10-16份,
粘结剂 10-16份。
其中,电熔镁砂粉为死烧细粉,选取电熔镁砂的目的,一是改善粘结性能;二是因为镁砂具有较高的导热系数,一般为40-60W·m-1·K-1,加入镁砂以后,能够明显增加成品陶瓷材料的导热性能。如果选择轻烧氧化镁(≤1350℃烧结),硬化速度过快,一般几秒内硬化,不易控制料浆和涂覆性能。
Al(H2PO4)3溶液的pH值≥2.0,浓度在40-60wt.%之间为宜,优选为50wt.%。
钠长石粉一种常见的长石矿物,钠长石的化学分子式为Na2O·Al2O3·6SiO2,其理论化学组成为:Na2O11.8%,Al2O319.4%,SiO268.8%。
石英砂粉的主要矿物成分是SiO2。
无机硅胶溶液的浓度为30-40wt.%,优选为35wt.%。无机硅胶平均孔径为2-3nm,比表面积为650-800m3/g,添加无机硅胶可以改善粘结性能。
粘结剂为羧甲基纤维素钠(CMC)、羧甲基纤维素钠、甲基纤维素、聚乙烯醇、聚丙烯酸中的一种或多种。粘结剂25℃粘度为10000-20000Pa•s。
步骤(3)中,当采用喷涂方式将料浆悬浮液喷涂在微胶囊素坯表面时,一般采用喷枪喷涂;当采用浸渍方式将料浆悬浮液浸渍在微胶囊素坯表面时,一般浸渍1-5s。
步骤(3)中,干燥时,在100-120℃保温3-4h,优选的,在0.5-1h时间内由室温匀速升至100-120℃。
步骤(3)中,烧结时,在820-850℃保温0.5-2h,优选的,在5-6h时间内匀速升至820-850℃。烧结时需要控制适宜的升温速率,要求不得高于120℃/h,若升温过快(大于200℃/h),封装层容易开裂。
步骤(3)中,冷却时,自然条件下冷却至室温。
本发明在微胶囊素坯烧结过程中,会有少量有机物或结晶水以气体的方式溢出,这是为了排除有机物和陶瓷胶囊内残存的结晶水,而最终制备的高温相变储能陶瓷材料,在今后的使用中,因为进行了封装,一些残存或原盐融化产生的一些气体,因毛细管的作用,会依附在微胶囊内壁,并不会有气体溢出成品陶瓷砖外。
本发明还提供上述制备方法所制备的高温相变储能陶瓷材料,熔点为800-805℃(差示扫描量热仪DSC测试),体积密度为2.0-2.2g/cm3(GB/T2997-2015),常温耐压强度≥17MPa(GB/T5072-2008),800℃×0.5h条件下高温抗折强度≥0.48MPa(GB/T3002-2017),导热系数≥40W·m-1·K-1。
盐酸盐具有相变潜热大,发生相变时的温度变化小且易于控制等优点,但在盐酸盐发生相变过程时会有大量的熔融盐产生,其流出会对容器和设备造成很强的腐蚀。氧化铝陶瓷材料本身具有高抗压强度和良好的致密度,且其耐高温和化学稳定性良好,其性质正好可以弥补熔融盐作为相变材料存在的缺陷。高温相变储热(蓄热)氧化铝陶瓷材料由氧化铝陶瓷基体材料和盐酸盐相变材料复合而成,在进行高温烧结的过程中陶瓷材料表面会形成致密的微观网络结构,其产生的毛细作用力可以将在高温熔融盐吸附在氧化铝陶瓷基体内。
此外,在金属冶炼过程中的高温服役环境温度控制领域,封装后的高温相变储能材料具有蓄热性能且在蓄热过程中可以保持温度基本不变。将封装后的高温相变蓄热材料代替或者部分代替常规的普通耐火材料永久层,利用高温吸收的热量补充低温时所需的热量,可以起到一定的温控作用,使得整个冶炼过程处于相对平稳的温度环境。
与现有技术相比,本发明的有益效果如下:
(1)本发明在陶瓷材料表面进行封装,与其它无机盐相比,盐酸盐的高温显热潜热量大,热传导性能好,外表面的陶瓷膜层封装材料耐强碱酸腐蚀性好,冷热循环过程中不开裂,原盐的摩尔百分数达到60%,可以以最大程度储能蓄热;
(2)本发明制得的高温相变储能陶瓷材料,体积密度为2.0-2.2g/cm3,常温耐压强度≥17MPa,800℃×0.5h条件下高温抗折强度≥0.48MPa,导热系数≥40W·m-1·K-1;
(3)本发明的原材料与制作成本低,制备工艺简单可行,适合大规模工业生产与应用。
附图说明
图1为本发明实施例1所制备的高温相变储能陶瓷材料的微观形貌图;
图2为本发明实施例1所制备的高温相变储能陶瓷材料的差示扫描量热仪DSC测试图。
具体实施方式
下面结合实施例对本发明作进一步说明,实施例中所使用的原料,如无特别说明,均为市售常规原料;实施例中所使用的工艺方法,如无特别说明,均为本领域常规方法。
实施例中,所采用的原盐满足以下要求:NaCl≥95wt.%、Ca2+≤0.2wt.%、Mg2+≤0.1wt.%、SO4 2-≤0.5wt.%、H2O≤2wt.%、水不溶物≤0.2wt.%。
实施例中,所采用的粉料粒度均在200-400目之间。
实施例中,高温相变储能陶瓷材料的熔点采用差示扫描量热仪DSC测试,温度范围30-900℃,升温速率10℃/min;体积密度依据标准GB/T2997-2015进行测试,常温耐压强度依据标准GB/T5072-2008进行测试,800℃×0.5h条件下高温抗折强度依据标准GB/T3002-2017进行测试。
实施例1
一种高温相变储能陶瓷材料,制备方法如下:
(1)素坯原料混合:
将原盐经球磨机干磨1h,过300目筛,再在390℃温度下保温2h,得到预处理后的原盐;
称取以下质量份数的原料:氧化铝粉100份,预处理后的原盐80份,Al(H2PO4)3溶液(浓度50wt.%)25份,氢氧化铝粉6份,钠长石粉8份,石英砂粉7份,Cr2O3粉18份;
将称取的氧化铝粉、钠长石粉、石英砂粉、Cr2O3粉进行干混,得到混合干料;
将称取的Al(H2PO4)3溶液,加入0.5倍的水稀释,并加入氢氧化铝粉混合,置于通风良好处,硬化5h,得到混合湿料;
将上述混合干料、混合湿料进行混合,再加入预处理后的原盐,混合均匀后得到素坯浆料。
(2)微胶囊素坯制备:
采用标准试样模具(直径50mm,高50mm,依据GB/T5072-2008),将素坯浆料在压力机上半干压制成型,0.5h由室温匀速升至120℃,然后保温3h,进行干燥;6h由室温匀速升至750℃,然后保温1h,进行烧结;之后自然匀速冷却到室温,制得到微胶囊素坯。
(3)素坯封装:
称取以下质量份数的原料:电熔镁砂粉100份,Al(H2PO4)3溶液45份,钠长石粉12份,石英砂粉8份,无机硅胶溶液(浓度35wt.%)12份,粘结剂14份;
将上述原料混合均匀,得到料浆悬浮液,喷涂在微胶囊素坯表面,将喷涂料浆悬浮液后的微胶囊素坯0.5h由室温匀速升至120℃,然后保温3h,进行干燥;6h由室温匀速升至830℃,然后保温1h,进行烧结,之后自然匀速冷却到室温,制得高温相变储能陶瓷材料。
所制备的高温相变储能陶瓷材料的微观形貌图如图1,差示扫描量热仪DSC测试结果如图2。经测试,高温相变储能陶瓷材料熔点为802.9℃,体积密度为2.09g/cm3,常温耐压强度18.4MPa,800℃×0.5h条件下高温抗折强度0.49MPa,导热系数41.4W·m-1·K-1。
实施例2
一种高温相变储能陶瓷材料,制备方法如下:
(1)素坯原料混合:
将原盐经球磨机干磨2h,过400目筛,再在380℃温度下保温1h,得到预处理后的原盐;
称取以下质量份数的原料:氧化铝粉100份,预处理后的原盐70份,Al(H2PO4)3溶液(浓度40wt.%)30份,氢氧化铝粉8份,钠长石粉10份,石英砂粉5份,Cr2O3粉15份;
将称取的氧化铝粉、钠长石粉、石英砂粉、Cr2O3粉进行干混,得到混合干料;
将称取的Al(H2PO4)3溶液,加入0.5倍的水稀释,并加入氢氧化铝粉混合,置于通风良好处,硬化6h,得到混合湿料;
将上述混合干料、混合湿料进行混合,再加入预处理后的原盐,混合均匀后得到素坯浆料。
(2)微胶囊素坯制备:
采用标准试样模具(200mm×53mm×35mm),将素坯浆料在160吨压力机上半干压制成型,1h由室温匀速升至190℃,然后保温4h,进行干燥;5h由室温匀速升至740℃,然后保温2h,进行烧结;之后自然匀速冷却到室温,制得到微胶囊素坯。
(3)素坯封装:
称取以下质量份数的原料:电熔镁砂粉100份,Al(H2PO4)3溶液(浓度40wt.%)50份,钠长石粉10份,石英砂粉10份,无机硅胶溶液(浓度40wt.%)10份,甲基纤维素16份;
将上述原料混合均匀,得到料浆悬浮液,喷涂在微胶囊素坯表面,将喷涂料浆悬浮液后的微胶囊素坯1h由室温匀速升至190℃,然后保温4h,进行干燥;5h由室温匀速升至820℃,然后保温2h,进行烧结,之后自然匀速冷却到室温,制得高温相变储能陶瓷材料。
经测试,高温相变储能陶瓷材料熔点为803.2℃,体积密度为2.18g/cm3,常温耐压强度18.6MPa,800℃×0.5h条件下高温抗折强度0.52MPa,导热系数40.2W·m-1·K-1。
实施例3
一种高温相变储能陶瓷材料,制备方法如下:
(1)素坯原料混合:
将原盐经球磨机干磨0.5h,过200目筛,再在400℃温度下保温3h,得到预处理后的原盐;
称取以下质量份数的原料:氧化铝粉100份,预处理后的原盐90份,Al(H2PO4)3溶液(浓度60wt.%)20份,氢氧化铝粉4份,钠长石粉5份,石英砂粉10份,铬铁矿粉18份;
将称取的氧化铝粉、钠长石粉、石英砂粉、铬铁矿粉进行干混,得到混合干料;
将称取的Al(H2PO4)3溶液,加入0.2倍的水稀释,并加入氢氧化铝粉混合,置于通风良好处,硬化4h,得到混合湿料;
将上述混合干料、混合湿料进行混合,再加入预处理后的原盐,混合均匀后得到素坯浆料。
(2)微胶囊素坯制备:
采用标准试样模具(220mm×80mm×65mm),将素坯浆料在400吨压力机上半干压制成型,0.5h由室温匀速升至120℃,然后保温3h,进行干燥;6h由室温匀速升至760℃,然后保温0.5h,进行烧结;之后自然匀速冷却到室温,制得到微胶囊素坯。
(3)素坯封装:
称取以下质量份数的原料:电熔镁砂粉100份,Al(H2PO4)3溶液(浓度60wt.%)45份,钠长石粉12份,石英砂粉8份,无机硅胶溶液(浓度30wt.%)14份,聚丙烯酸13份;
将上述原料混合均匀,得到料浆悬浮液,喷涂在微胶囊素坯表面,将喷涂料浆悬浮液后的微胶囊素坯0.5h由室温匀速升至120℃,然后保温3h,进行干燥;6h由室温匀速升至850℃,然后保温0.5h,进行烧结,之后自然匀速冷却到室温,制得高温相变储能陶瓷材料。
经测试,高温相变储能陶瓷材料熔点为804.5℃,体积密度为2.15g/cm3,常温耐压强度18.1MPa,800℃×0.5h条件下高温抗折强度0.50MPa,导热系数42.0W·m-1·K-1。
实施例4
一种高温相变储能陶瓷材料,制备方法如下:
(1)素坯原料混合:
将原盐经球磨机干磨1h,过300目筛,再在390℃温度下保温2h,得到预处理后的原盐;
称取以下质量份数的原料:氧化铝粉100份,预处理后的原盐85份,Al(H2PO4)3溶液(浓度50wt.%)25份,氢氧化铝粉5份,钠长石粉8份,石英砂粉8份,铬铁矿粉20份;
将称取的氧化铝粉、钠长石粉、石英砂粉、铬铁矿粉进行干混,得到混合干料;
将称取的Al(H2PO4)3溶液,加入1倍的水稀释,并加入氢氧化铝粉混合,置于通风良好处,硬化5h,得到混合湿料;
将上述混合干料、混合湿料进行混合,再加入预处理后的原盐,混合均匀后得到素坯浆料。
(2)微胶囊素坯制备:
采用标准试样模具(220mm×200mm×76mm,20孔型砖),将素坯浆料在400吨压力机上半干压制成型,0.5h由室温匀速升至120℃,然后保温3h,进行干燥;6h由室温匀速升至750℃,然后保温1h,进行烧结;之后自然匀速冷却到室温,制得到微胶囊素坯。
(3)素坯封装:
称取以下质量份数的原料:电熔镁砂粉100份,Al(H2PO4)3溶液(浓度50wt.%)40份,钠长石粉15份,石英砂粉6份,无机硅胶溶液(浓度35wt.%)16份,聚乙烯醇10份;
将上述原料混合均匀,得到料浆悬浮液,喷涂在微胶囊素坯表面,将喷涂料浆悬浮液后的微胶囊素坯0.5h由室温匀速升至120℃,然后保温3h,进行干燥;6h由室温匀速升至830℃,然后保温1h,进行烧结,之后自然匀速冷却到室温,制得高温相变储能陶瓷材料。
经测试,高温相变储能陶瓷材料熔点为800.6℃,体积密度为2.01g/cm3,常温耐压强度17.8MPa,800℃×0.5h条件下高温抗折强度0.48MPa,导热系数42.3W·m-1·K-1。
Claims (10)
1.一种高温相变储能陶瓷材料的制备方法,其特征在于:包括以下步骤:
(1)素坯原料混合:将氧化铝粉、钠长石粉、石英砂粉、Cr2O3和/或铬铁矿粉进行干混,得到混合干料;将Al(H2PO4)3溶液和氢氧化铝粉进行湿混,硬化,得到混合湿料;然后将上述混合干料、混合湿料混合,并加入预处理后的原盐,混合均匀后得到素坯浆料;
(2)微胶囊素坯制备:将素坯浆料经模压成型,然后干燥、烧结、冷却,得到微胶囊素坯;
(3)素坯封装:将电熔镁砂粉、Al(H2PO4)3溶液、钠长石粉、石英砂粉、无机硅胶溶液、粘结剂混合均匀,得到料浆悬浮液,喷涂或浸渍在微胶囊素坯表面,然后干燥、烧结、冷却,得到高温相变储能陶瓷材料。
2.根据权利要求1所述的高温相变储能陶瓷材料的制备方法,其特征在于:Al(H2PO4)3溶液的浓度为40-60wt.%;无机硅胶溶液的浓度为30-40wt.%。
3.根据权利要求2所述的高温相变储能陶瓷材料的制备方法,其特征在于:步骤(1)中,以质量份数计,各原料的用量如下:
氧化铝粉 100份,
预处理后的原盐 70-90份,
Al(H2PO4)3溶液 20-30份,
氢氧化铝粉 4-8份,
钠长石粉 5-10份,
石英砂粉 5-10份,
Cr2O3和/或铬铁矿粉 15-20份。
4.根据权利要求3所述的高温相变储能陶瓷材料的制备方法,其特征在于:原盐的主要化学成分含量为:NaCl≥95wt.%、Ca2+≤0.2wt.%、Mg2+≤0.1wt.%、SO4 2-≤0.5wt.%、H2O≤2wt.%、水不溶物≤0.2wt.%。
5.根据权利要求4所述的高温相变储能陶瓷材料的制备方法,其特征在于:所述原盐的预处理方法为:将原盐经球磨机干磨0.5-2h,过200-400目筛,再在380-400℃温度下保温1-3h,即得预处理后的原盐。
6.根据权利要求1所述的高温相变储能陶瓷材料的制备方法,其特征在于:步骤(1)中,将Al(H2PO4)3溶液和氢氧化铝粉进行湿混后,硬化4-6h。
7.根据权利要求1所述的高温相变储能陶瓷材料的制备方法,其特征在于:步骤(2)中,干燥时,在100-120℃保温3-4h,在0.5-1h时间内由室温匀速升至100-120℃;
烧结时,在740-760℃保温0.5-2h,在5-6h时间内匀速升至740-760℃。
8.根据权利要求2所述的高温相变储能陶瓷材料的制备方法,其特征在于:步骤(3)中,以质量份数计,各原料的用量如下:
电熔镁砂粉 100份,
Al(H2PO4)3溶液 40-50份,
钠长石粉 10-15份,
石英砂粉 6-10份,
无机硅胶溶液 10-16份,
粘结剂 10-16份。
9.根据权利要求1所述的高温相变储能陶瓷材料的制备方法,其特征在于:步骤(3)中,干燥时,在100-120℃保温3-4h,在0.5-1h时间内由室温匀速升至100-120℃;
烧结时,在820-850℃保温0.5-2h,在5-6h时间内匀速升至820-850℃。
10.一种由权利要求1-9任一项所述的制备方法制备得到的高温相变储能陶瓷材料,其特征在于:熔点为800-805℃,体积密度为2.0-2.2g/cm3,常温耐压强度≥17MPa,800℃×0.5h条件下高温抗折强度≥0.48MPa,导热系数≥40W·m-1·K-1。
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