Preparation and properties of hydroxyapatite aerogel composite phase change materials
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摘要: 以相變材料為核心的潛熱儲存技術，對加快新能源開發和提高能源利用率起著關鍵性作用。以油酸鈣為前驅體，通過水熱法合成了具有自支撐網絡結構的羥基磷灰石（HAP）氣凝膠，并采用浸漬法制備出自支撐羥基磷灰石復合相變材料。通過掃描電鏡、傅里葉紅外光譜、X射線衍射、熱重法、差示掃描量熱法等手段對所制備復合相變材料的形貌、穩定性、熱性能等進行了表征及測試。實驗結果表明，負載石蠟或十八醇的羥基磷灰石氣凝膠復合相變材料均具有良好的熱性能，質量分數60%石蠟@HAP氣凝膠復合相變材料的熔融焓和凝固焓測量值分別為85.10和85.30 J·g?1，結晶度為81.50%；質量分數60%十八醇@HAP氣凝膠復合相變材料的熔融焓和凝固焓測量值為113.78和112.25 J·g?1，結晶度為86.20%，且具有很好的熱穩定性和化學穩定性。此外，羥基磷灰石氣凝膠載體材料阻燃性好，無腐蝕且安全環保，有效拓展了相變材料在智能保溫紡織物和建筑材料等領域的實際應用。Abstract: To address energy shortage and environmental pollution, scientists are working to develop methods for the production, conversion, and storage of new energy sources. The development of thermal energy storage (TES) is considered to be one of the most effective energy conservation and environmental protection strategies for utilizing various renewable energy sources. Energy storage technology can solve the contradiction between energy supply and demand in time and space and also improve energy efficiency. Currently, TES includes mainly sensible heat storage, latent heat storage, and thermochemical energy storage. The latent heat TES based on phase change materials (PCMs) is an efficient technology that is being actively pursued owing to high storage density in a small temperature region, which is essential for accelerating new energy development and improving energy efficiency. In this paper, hydroxyapatite aerogels with self-supporting network structure were prepared via a hydrothermal method using calcium oleate as a precursor. Self-supporting hydroxyapatite-based composite phase change materials were synthesized using the impregnation method. The morphology and thermal properties of the prepared composite phase change materials were characterized and tested by scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetry, and differential scanning calorimetry. The experimental results show that the composite phase change materials of hydroxyapatite aerogels loaded with octadecanol or paraffin have good thermal properties. The measured values of melting enthalpy and solidified enthalpy of the 60% paraffin@HAP composite phase change materials are 85.10 and 85.30 J·g?1, respectively, and its crystallinity is 81.50%. The measured values of melting enthalpy and solidified enthalpy of the 60% octadecanol@HAP composite phase change material are 113.78 and 112.25 J·g?1, respectively, and its crystallinity is 86.20%. In addition, the composite has good thermal and chemical stability. Furthermore, the hydroxyapatite substrate has the advantages of good flame retardancy, corrosion-free characteristics, safety, and environmental protection, which effectively expands the practical application of phase change materials in the field of intelligent thermal insulation textiles and building materials.
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Key words:
- phase change materials /
- hydroxyapatite /
- paraffin /
- octadecanol /
- latent heat /
- fire resistance
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圖 1 HAP納米線形成機理示意圖
Figure 1. Schematic illustration of the formation mechanism of HAP nanowires
圖 2 材料掃描圖.（a） HAP氣凝膠；（b） 60%石蠟@HAP氣凝膠復合相變材料；（c） 60%十八醇@HAP氣凝膠復合相變材料
Figure 2. SEM images of studied materials: (a) HAP aerogels; (b) 60% paraffin@HAP aerogels composite PCMs; (c) 60% octadecanol@HAP aerogels composite PCMs
圖 3 HAP氣凝膠的數碼照片.（a） HAP氣凝膠冷凍干燥前；（b） HAP氣凝膠冷凍干燥后；（c） 蒲公英頂部的HAP氣凝膠；（d）HAP氣凝膠燃燒前；（e） HAP氣凝膠燃燒中；（f） HAP氣凝膠燃燒后
Figure 3. Digital images of HAP aerogels: (a) HAP aerogels before freeze-dried; (b) HAP aerogels after freeze-dried; (c) HAP aerogels on top of the dandelion; (d) HAP aerogels before combustion; (e) HAP aerogels in combustion; (f) HAP aerogels after combustion
圖 4 不同材料紅外光譜圖.（a） 石蠟、HAP氣凝膠及復合相變材料；（b） 十八醇、HAP氣凝膠及復合相變材料
Figure 4. FTIR spectra of different materials: (a) paraffin, HAP aerogels and composite PCMs; (b) octadecanol, HAP aerogels and composite PCMs
圖 5 材料X射線衍射圖.（a） 石蠟、HAP氣凝膠及復合相變材料；（b） 十八醇、HAP氣凝膠及復合相變材料
Figure 5. X-ray diffraction patterns: (a) paraffin, HAP aerogels and composite PCMs; (b) octadecanol, HAP aerogels and composite PCMs
圖 6 熱重曲線. （a）石蠟、HAP氣凝膠及復合相變材料；（b）十八醇、HAP氣凝膠及復合相變材料
Figure 6. Thermogravimetric curves: (a) paraffin, HAP aerogels and composite PCMs; (b) octadecanol, HAP aerogels and composite PCMs
圖 7 復合相變材料差示掃描量熱分析曲線.（a） 石蠟及復合相變材料；（b） 十八醇及復合相變材料；（c） 石蠟復合相變材料循環20次前后；（d） 十八醇復合相變材料循環20次前后
Figure 7. DSC curves of composite PCMs: (a) paraffin and composite PCMs; (b) octadecanol and composite PCMs; (c) paraffin composite before and after 20 times cycling; (d) octadecanol composite before and after 20 times thermal cycling
圖 8 60%石蠟@HAP氣凝膠和60%十八醇@HAP氣凝膠復合相變材料泄漏測試
Figure 8. Leakage test of 60% paraffin@HAP aerogels and 60% octadecanol@aerogels of composite PCMs
表 1 HAP氣凝膠相變復合材料的熱性能
Table 1. Thermal properties of HAP aerogel composite PCMs
相變材料 負載量/% Tm/℃ Tf/℃ $\Delta {H_{\rm{m}}}$/（J·g?1） $\Delta {H_{\rm{f}}}$/（J·g?1） 石蠟 100 61.73 55.97 176.97 174.45 石蠟@HAP 60 57.68 47.81 85.10 85.30 十八醇 100 63.98 52.59 221.01 218.75 十八醇@HAP 60 61.40 53.03 113.78 112.25 
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表 2 60%石蠟@HAP復合相變材料和文獻中石蠟復合相變材料的熱性能對比
Table 2. Thermal performance comparison of 60% paraffin@HAP composite PCMs and paraffin composite PCMs in literature
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