Journal of Textile Research ›› 2026, Vol. 47 ›› Issue (1): 11-19.doi: 10.13475/j.fzxb.20250404001

• Fiber Materials • Previous Articles     Next Articles

Preparation and properties of calcium alginate freeze dried three-dimensional porous materials

YU Qiuyu1,2, WU Jiang3,4(), TAN Yanjun1,2, SHAN Wenxi3,4, DENG Yuntao1,2, LI Zongquan1,2   

  1. 1. College of Textile Science and Engineering, Xi'an Polytechnic University, Xi'an, Shaanxi 710048, China
    2. Shaanxi Province Functional Materials Dyeing and Finishing Innovation Engineering Research Center, Xi'an Polytechnic University, Xi'an, Shaanxi 710048, China
    3. National Center for Clinical Medical Research of Oral Diseases, Stomatological Hospital of Air Force Military Medical University, Xi'an, Shaanxi 710038, China
    4. National Key Laboratory of Reconstruction and Regeneration of Oral and Maxillofacial System, Stomatological Hospital of Air Force Military Medical University, Xi'an, Shaanxi 710038, China
  • Received:2025-04-22 Revised:2025-11-05 Online:2026-01-15 Published:2026-01-15
  • Contact: WU Jiang E-mail:wujiang@fmmu.edu.cn

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Abstract:

Objective This study aims to use sodium alginate to prepare a three-dimensional porous material with stable structure and excellent liquid absorption performance so as to solve problems such as poor liquid absorption performance and complex preparation process for conventional medical dressings (such as cotton yarn). During the preparation process, the porous structure of the calcium alginate material is uneven, which causes low absorption to liquid and poor structural stability, limiting its application in the field of medical dressings.

Method This study transformed sodium alginate (SA) colloidal crystals into three-dimensional porous materials with uniform pores through stepwise cooling and freeze drying techniques. On this basis, the preparation process of calcium alginate (CA) three-dimensional porous materials was optimized by the Box-Behnken response surface method, and the influence of SA mass fraction, CaCl2 mass fraction and treatment time on the liquid absorption performance of the material was studied. The optimal preparation process was obtained, and physical and chemical properties of the CA three-dimensional porous material were characterized.

Results During the preparation process, the method of stepwise cooling (freezing from -5 ℃ to -10 ℃ for 6 h, and finally freezing at -20 ℃ for 12 h) was found effective in solving the bulging and streak problems of SA colloid during the freezing process. This stepwise freezing process ensured uniform heat transfer from the inside to the outside of the SA crystal, making a smooth surface of the final prepared SA crystal. The further optimized freeze drying time was 36 h, not only ensuring uniformity of pore size, but also imparting excellent physical and chemical properties to the SA three-dimensional porous freeze dried material. The preparation process of CA three-dimensional porous materials was optimized by the Box-Behnken response surface method. The prepared CA three-dimensional porous materials showed excellent performance under the conditions of SA mass fraction of 1.75%, CaCl2 mass fraction of 3.5%, and the freeze drying time of 9 h. Its liquid absorption rate was as high as 3 064%, showing a high liquid absorption capacity. In a wet state, the material's tensile breaking strength was 0.42 MPa, the elongation of breaking was 45%, and the compression rebound rate was 100%, showing good liquid absorption performance and structural stability, which meets the requirements of medical dressings. Fourier infrared spectroscopy (FT-IR) analysis showed that the absorption peak of CA at 3 367 cm-1 was enhanced, indicating that Ca2+ reacted chemically with SA. Energy spectrum analysis (ESC) showed that the calcium content in CA increased by 8.08% compared with SA, and the sodium content decreased by 8.25% compared with SA, further confirming the replacement reaction between Ca2+ and SA. Scanning electron microscopy (SEM) observations indicated that CA three-dimensional porous material had a uniform network interpenetrating porous structure inside, which helps improve the material's liquid absorption performance and mechanical stability. Thermogravimetric analysis (TG) showed that the thermal decomposition temperature of CA was 70 ℃ higher than that of SA, demonstrating better thermal stability, which indicated that the introduction of Ca2+ enhanced the structural stability of the material.

Conclusion A CA three-dimensional porous material with uniform pores, stable structure and excellent liquid absorption performance was successfully prepared by stepwise freezing process and response surface optimization method. This material has significant advantages in liquid absorption, mechanical properties and thermal stability, meets the standard requirements of medical dressings, and has broad application prospects. The research results provide important theoretical basis and technical support for the development of new high-performance medical dressings, and also lay the foundation for the further application of calcium alginate materials in the field of biomedical science.

Key words: calcium alginate, sodium alginate, freeze drying technology, three-dimensional porous material, response surface experiment, medical dressing

CLC Number: 

  • TS959.9

Fig.1

Stepwise freezing process"

Fig.2

Preparation process of CA three-dimensional porous material"

Fig.3

Viscosities of SA colloids with different mass fractions"

Fig.4

Freeze-forming effect of SA colloids with different mass fractions"

Fig.5

Schematic diagram of freezing process. (a) Conventional freezing process -20 ℃/24 h; (b) Conventional freezing process -10 ℃/24 h; (c) Stepwise freezing process -5 ℃/6 h (Step 1); (d) Stepwise freezing process -10 ℃/6 h (Step 2); (e) Stepwise freezing process -20 ℃/12 h (Step 3)"

Fig.6

Forming effects of SA freeze dried materials of different freeze-drying time periods"

Fig.7

SEM images of freeze dried materials with different SA mass fractions"

Tab.1

Response surface experimental factors and horizontal coding table"

水平 A B C
CaCl2质量分数/% 时间/h SA质量分数/%
-1 0.20 8 1.25
0 0.30 10 1.75
1 0.40 12 2.25

Tab.2

Response surface experimental design and results"

实验编号 A/% B/h C/% 吸液率R/%
1 0.20 8 1.75 2 670
2 0.40 8 1.75 1 769
3 0.20 12 1.75 1 653
4 0.40 12 1.75 2 117
5 0.20 9 1.25 2 428
6 0.40 9 1.25 1 404
7 0.20 9 2.25 1 616
8 0.40 9 2.25 1 088
9 0.30 8 1.25 2 606
10 0.30 12 1.25 2 517
11 0.30 8 2.25 1 960
12 0.30 12 2.25 1 888
13 0.30 10 1.75 3 399
14 0.30 10 1.75 2 767
15 0.30 10 1.75 3 076
16 0.30 10 1.75 3 294
17 0.30 10 1.75 3 083

Tab.3

Regression analysis of variance"

方差来源 平方和 自由度 均方 F值 P值 显著性
模型 725.61 9 80.62 13.26 0.001 3 **
A 49.65 1 49.65 8.16 0.024 4 *
B 8.69 1 8.69 1.43 0.270 8 —
C 72.18 1 72.18 11.87 0.010 8 *
AB 46.85 1 46.85 7.70 0.027 5 *
AC 6.15 1 6.15 1.01 0.348 1 —
BC 0.722 1 7.22 1.18 0.973 5 —
A2 296.85 1 296.85 48.81 0.000 2 **
B2 22.45 1 22.45 3.69 0.096 2 —
C2 177.98 1 177.98 29.26 0.001 0 **
残差 42.57 7 6.08 — — —
失拟项 18.98 3 6.33 1.07 0.455 0 —
纯误差 23.60 4 5.90 — — —
总差 768.18 16 — — — —

Fig.8

Response surface diagram, contour map of CA three-dimensional porous material. (a) Interaction effect of CaCl2 mass fraction and time on liquid absorption rate; (b) Interaction effect of SA mass fraction and time on liquid absorption rate; (c) Interaction effect of CaCl2 mass fraction and SA mass fraction on liquid absorption rate"

Fig.9

Fitted line between predicted values and actual values"

Fig.10

SEM images of cross-section of CA three-dimensional porous materials"

Tab.4

Mass percentage of SA and CA elements"

材料 质量分数/%
C O Na Cl Ca
SA 41.79 31.68 16.94 5.17 4.45
CA 43.38 28.95 8.69 6.63 12.53

Fig.11

Infrared spectra of SA and CA three-dimensional porous materials"

Fig.12

Thermogravimetric curves of SA and CA materials"

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