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Preparation and properties of PLCL/OM-Laponite materials with potential applications in orthopedic bandage

  • Yan Ren , Yonggang Lin , Yabei Ding , Ruimin Tang , Minglong Yuan , Hongli Li EMAIL logo and Yongming Chuan EMAIL logo
Published/Copyright: January 29, 2025
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Journal of Polymer Engineering
From the journal Journal of Polymer Engineering Volume 45 Issue 2

Abstract

Poly(l-lactide-co-caprolactone) (PLCL) is the polymeric material with good biodegradability and biocompatible properties, but it is insufficient in strength properties that the pure PLCL is performed as orthopedic bandage. The PLCL has been blended with the laponite which is modified by cetyltrimethylammonium bromide (CTAB) to prepare composited bandage splines. The organic-modified laponite (OM-laponite) results of Fourier transform infrared (FTIR) and thermogravimetry analysis (TG) indicate that the laponite was successfully grafted with CTAB and the thermal stability was improved with increasing CTAB. The mechanical properties reveal that elongation at break strengthen with the increasing OM-laponite. When the content of OM-laponite is 2.0 %, the elongation at break and tensile strength of composited spline are superior to the medical orthopedic bandage. The results of thermal stability show that it was helpful to improve the crystallization properties of PLCL with the addition of OM-laponite. The water contact angle results demonstrate that the hydrophilicity is enhanced and is beneficial to cell adhesion. The results of cell experiment illustrate that the composite materials have a certain effect on cell proliferation when the content of OM-laponite is less than 2 %. Compared with the medical orthopedic bandage, it is satisfied with the application requirements.

Keywords: organic modification; Laponite; PLCL; orthopedic bandage

1 Introduction

According to statistics, there are millions of patients diagnosed with bone defects each year, and the number is gradually increasing. Thus, it is particularly important to address the problem of bone defects. 1 , 2 , 3 With scientific developments, biodegradable polymer materials have become an important part of bone tissue engineering research. 4 , 5 , 6

PLCL, a copolymer of lactide (LA) and caprolactone (CL), has the high strength of polylactic acid and the toughness of polycaprolactone, as well as good biodegradability and biocompatibility. 7 Moran et al. 8 used PLCL to prepare expandable balloon implants for the treatment of rotator cuff injuries and tissue separation. Ramot et al. 9 synthesized a new fibrous dural graft from poly(levulinic acid-caprolactone acid) and poly(dextrolactide-caprolactone acid) and the implanted graft was completely absorbed after 12 months, with the remaining macrophages morphologically resembling the anti-inflammatory M2-like phenotype, which aided tissue healing, indicating that PLCL-based grafts are safe and effective for repairing rabbit dura mater. Wenshuai Liu et al. 10 poly(l-lactide-co-ε-caprolactone) (PLCL) copolymers were examined to modulate the elasticity of PLLA with the random presence of CL units in PLLA. They performed platelet adhesion test and hemolysis test, as well as in vivo implantation and biocompatibility. The results showed that PLCL scaffolds have good platelet and endotheliocyte adhesion ability and no obvious hemolysis was observed. In vivo subcutaneous implantation of PLCL scaffolds demonstrated superior biocompatibility.

Ning et al. 11 used electrospinning method to prepare a series of poly(l-lactide-co-ε-caprolactone) (PLCL)/acellular dermal matrix (ADM) nanofiber scaffolds with different proportions, injectable gelatin methacryloyl (GelMA) hydrogel loaded with PLCL/ADM short nanofibers (GelMA-Fibers) was constructed as a transplantation vector of ADSCs. It was demonstrated that GelMA-fibers could effectively promote the proliferation of ADSCs in vitro. Most importantly, GelMA-fibers increased the survival rate of ADSCs transplantation and decreased their apoptosis rate within 14 d.

Regarding bone tissue engineering, in addition to having the advantages of being degradable, nontoxic and harmless, and inducing bone regeneration, the given material must also have good tensile strength and toughness to meet the demand as a bone repair material. Low molecular weight PLCL has weak mechanical strength and is mostly used as a drug carrier, vascular scaffold or nerve scaffold, etc. 12 , 13 For example, Zhang et al. 14 used PLCL (Mw = 50,000 g/mol) prepared nerve conduits loaded with different masses of methylcobalamin and demonstrated that the loaded MB could be continuously released for at least 21 days and could effectively promote the elongation and proliferation of bone marrow MSCs and the proliferation of N2a cells in vitro. However, both PLA and PCL are hydrophobic polyesters, which have limitations in terms of biomaterial and cytocompatibility. 15

Inorganic nanoparticles, such as montmorillonite and hydroxyapatite, are compounded with organic polymer materials, and their nano-properties are used to enhance the mechanical properties of polymer materials. 16 , 17 Jingshui Xu et al. 18 enhanced thermoplastic polyurethane elastomer (TPU) by using a small amount of 4,4′–methylenediphenyl diisocyanate (MDI) modified native clay (MDI-MMT) as a filler. The results showed that compared with pure TPU, TPU/MDI-MMT nanocomposites exhibited better mechanical properties, including Young’s modulus, tensile strength and elongation at break. In addition to sufficient mechanical strength, bone repair materials must also have certain comprehensive mechanical properties. Therefore, the aim of study was to identify a bone repair material that improves bone regeneration properties. 19

Laponite is synthetic lithium alginate. Its chemical structure is as follows: 20 Na+0.7[(Si8Mg5.5Li0.3)O20(OH)4]−0.7. This special structure gives laponite unique properties, such as a certain degree of hydrophilicity, large surface activity, high cation exchange capacity, an interlayer surface with unusual water content characteristics, and the ability to strongly modify the flow properties of liquids. 21 , 22 Laponite has excellent biological properties and has been widely studied for biomedical applications, including wound healing, drug delivery, 3D bioprinting, and tissue regeneration engineering. Gaspar 23 and Cai et al. 24 introduced laponite into different hydrogels, and both found the laponite greatly improved the hydrogel. Zhang et al. 25 developed injectable RGD-alginate/laponite (RGD-Alg/Lap) hydrogel microspheres that regenerated in vivo myeloid tissue with abundant microvasculature by sustained release of VEGF through laponite. Gonzaga et al. 26 used the lyophilization method to prepare chitosan/clay nanometer dressing composite scaffolds, demonstrating that the presence of laponite clay on the scaffold was essential to obtain a material with superior properties. However, the application was limited by the relatively poor hydrophobicity of laponite and the reagglomeration of dispersed lamellae when blended with polymers; nevertheless, the addition of laponite can lead to an improvement in the strength and toughness of PLCL, making it a good additive for bone repair materials.

Therefore, in this study, the PLCL material was modified by blending organized laponite to improve the cytocompatibility of PLCL and expand its application potential. The PLCL/OM-laponite was also processed into sheets using screw extrusion molding technology to characterize its mechanical properties, biocompatibility and thermal stability, and to analyze its potential application prospects.

2 Materials and methods

2.1 Materials

L-Lactide (L-LA), Dutch Prak Company; ε-caprolactone (ε-CL), China Petrochemical Group Asset Management Co., Ltd. Baling Petrochemical Branch; stannic octoate, Shanghai Aladdin Biochemical Technology Co., Ltd.; Dichloromethane and anhydrous ethanol, were purchased from Chengdu Cologne Chemicals Co., Ltd.; Laponite, Rockwood, USA; CTAB, Silver nitrate, Chengdu Kelon Chemical Reagent Company; Orthopedic fixture sample, Chinese People’s Liberation Army (PLA) Joint Logistics and Security Forces Hospital 920; Mouse mononuclear macrophage leukemia cell code RAW264.7, item number CL-0190 Procell.

2.2 Methods

2.2.1 The organic modification of Laponite (OM-Laponite)

A quantity of laponite was added to a reactor containing ethanol/water (1/1 by mass), and dissolved with sufficient stirring. Then, cetyltrimethylammonium bromide was added, heated to approximately 80 °C and stirred at reflux for 4–5 h. The solid was separated from the liquid and washed with a mixed ethanol/water (1/1 by mass) dispersant. The wash solution was tested with AgNO3 solution until there were no Br-ions (no precipitate). Modified organolithium alginate containing long chain alkanes was obtained by drying under vacuum.

2.2.2 Preparation of PLCL

Lactide and caprolactone were added according to the mass ratio of 7:3, 8:2 and 9:1 and stir in the oil bath to heat up to 100 °C to melt lactide. After the solution is clarified, high-purity nitrogen is replaced three times. Under the protection of nitrogen, stannous octoate was added as catalyst according to 5/1,000 of the total feeding amount. It was heated to 150 °C and reacted for 6–8 h under nitrogen protection to form a viscous state. After the reaction was completed, the heating was stopped to cool it naturally to room temperature, and the product was dissolved in dichloromethane. After dissolution, the polymer was poured into excess ethanol. The solid was precipitated by rapid stirring and then filtered and dried under vacuum to obtain PLCL.

2.2.3 Preparation of PLCL/OM-laponite materials

The three proportions of PLCL and OM-laponite were dried separately in a vacuum oven at 60 °C for 48 h. The PLCL copolymer materials were blended with OM-laponite according to the proportions in Table 1 and mixed well to prepare the PLCL/OM-laponite composites. The material was processed and molded by screw extrusion technology before being charged from the inlet of the torque rheometer (XXS-300, Shanghai Science and Technology Innovation Group). The screw extruded material melt was pressed out and cooled by the three-roller machine (LXY-80X150, Shanghai Science and Technology Innovation Group) to obtain sheets with a thickness of 1.0 mm, which were prepared for testing.

Table 1:

PLCL/OM-Laponite material ratio.

Sample PLCL copolymerization ratio PLCL (g) OM-Laponite (g) Content of OM-Laponite
A 9:1 100 0 0
A1 9:1 99 1.0 1.0 %
A2 9:1 98 2.0 2.0 %
A3 9:1 97 3.0 3.0 %
B 8:2 100 0 0
B1 8:2 99 1.0 1.0 %
B2 8:2 98 2.0 2.0 %
B3 8:2 97 3.0 3.0 %
C 7:3 100 0 0
C1 7:3 99 1.0 1.0 %
C2 7:3 98 2.0 2.0 %
C3 7:3 97 3.0 3.0 %

2.2.4 Fourier transform infrared (FTIR) testing

The organic-modified laponite powders, PLCL copolymer materials and the PLCL/OM-laponite materials were dried at 50 °C for 3 h. The samples were mixed and ground with the dried potassium bromide powder at a ratio of 1:100 and then pressed into shape using a tablet press. Detection was carried out using the Nicolet IS10 FTIR spectrometer. The test range was from 500 to 4,000 cm−1.

2.2.5 Thermogravimetric (TG) testing

Thermogravimetric analysis of the organic-modified laponite powders, PLCL copolymer materials and PLCL/OM-laponite materials were carried out using an STA449 simultaneous thermogravimetric analyzer (NETZSCN, Germany) with an initial temperature of 25 °C and a sample mass between 5 and 10 mg, ramped up at 10 °C/min under N2 protection and tested in the temperature range 25–800 °C.

2.2.6 DSC testing

Five to ten milligrams of product were weighed and sealed in an aluminum crucible. The temperature range was −30 to 300 °C by differential scanning calorimetry (DSC 214, NETZSCN, Germany) with a set nitrogen rate of 40 mL/min, a purge gas rate of 60 mL/min and a temperature rise rate of 5 °C/min.

2.2.7 Mechanical property testing

The composite sheets were cut to a suitable shape and size. Then, the mechanical properties of the samples were measured on a CMT4104 microcomputer controlled electronic universal testing machine at room temperature to obtain the tensile strength and elongation at break of the material sheets. The tensile rate was 50 mm/min.

2.2.8 Scanning electron microscopy (SEM) testing

The morphological characteristics of the PLCL copolymer materials and PLCL/OM-laponite composites were observed by field emission scanning electron microscopy (SEM). Vacuum dried sheets were prepared for inspection by quenching and cooling in liquid nitrogen, and the sections were sprayed with gold. An S-3400 N electron scanning microscope (Hitachi, Japan) was used to observe the cross-sectional surfaces of the composite sheets.

2.2.9 Contact angle testing

Contact angle measurements were carried out on an OCA20 optical video contact angle meter (DataPhysics, Germany) at 25 °C. PLCL copolymer materials and PLCL/OM-laponite sheets were laid flat on the sample table and then distilled water was dropped onto the surface of the sheets by microinjection. The injection volume was approximately 3.0–5.0 μL. The contact angles were measured separately, and the average value was taken as the contact angle for this sample water.

2.2.10 Cytotoxicity testing

RAW264.7 cells in logarithmic growth phase were taken and gently placed in the culture flask until the cells fell off. All the cells in the culture flask were transferred into a 15 mL centrifuge tube and centrifuged at 250×g for 5 min. The supernatant was removed, and the appropriate amount of medium was added to make a single cell suspension. The cell density was adjusted to 5 × 104/mL and 100 μL/well was seeded in 96-well plates (edge holes were filled with sterile PBS), and cultured at 37 °C and 5 % CO2. After the cells were adherent, PLCL (9/1), PLCL (8/2) and PLCL (7/3) were set up in the zero-adjustment group, the control group and the material group, with four replicates in each group, and the corresponding concentration gradient drugs were added according to the experimental scheme. After 24 h of drug action, the supernatant was taken. The serum-free medium was diluted 1:10 with CCK8 reagent, and 110 μL/well of diluted CCK8 working solution was added. Then, the plate was gently shaken several times and incubation was continued for 2 h at 37 °C with 5 % CO2 at a constant temperature. The absorbance of each well was measured at 450 nm.

2.2.11 Degradability testing

In vitro degradation tests were carried out with constant temperature shaking. A buffer solution of 0.01 mol/L PBS was prepared. The PLCL copolymer materials and PLCL/OM-laponite plates were then cut to the appropriate size, weighed, placed in a glass vial containing PBS buffer solution and then placed in a constant temperature shaking chamber set at 37 °C with an oscillation rate of 100 r/min. The samples were washed, dried and weighed at 5 days(d), 15 d, 30 d, 45 d, 60 d, 75 d and 90 d of degradation. The degradation rate was calculated using Formula (1).

(1) Degradation rate = W 1 − W 2 W 1 × 100   %

2.2.12 Statistical analysis

The experimental data were plotted using GraphPad Prism 5 software (GraphPad Software Inc., La Jolla, CA 92037, USA), and all data were analyzed using one-way ANOVA. The results were expressed as the mean ± standard deviation (× ± s). p < 0.05 was considered a statistically significant difference.

3 Results and discussion

3.1 FTIR

Figure 1a shows the infrared spectra of CTAB, laponite and modified OM-laponite. Laponite:CTAB = 1:0.3, laponite:CTAB = 1:0.2, laponite:CTAB = 1:0.1. The ratio is mole ratio. There were bending vibration peaks of silicon oxygen tetrahedron (Si–O) and magnesium (lithium) oxygen octahedron (Mg–O or Li–O) near 654 cm−1, the Si–O stretching vibration peak at 1,003 cm−1, and the–OH stretching vibration absorption peak at 3,500 cm−1. In addition, 1,468 cm−1 is the bending vibration peak of C–H in cetyltrimethylammonium bromide, and the stretching vibration peaks of C–H (–CH3 and –CH2) in cetyltrimethylammonium bromide are approximately 2,800–3,000 cm−1, the absorption peak of NH3 is 3,700 cm−1 and the absorption peak at 1,636 cm−1 is weakened, indicating that the organic quaternary ammonium cations have replaced the sodium ions in the laponite layer. The results are similar to those of montmorillonite modified by organic quaternary ammonium salts. With the increase in the modifier cetyltrimethylammonium bromide, the absorption peak of NH3 at 3,686 cm−1 was significantly enhanced.

Figure 1: FTIR test results. (a) FTIR spectra of organic-modified laponite powders, (b) PLCL copolymer materials and (c) PLCL/OM-laponite materials.
Figure 1:

FTIR test results. (a) FTIR spectra of organic-modified laponite powders, (b) PLCL copolymer materials and (c) PLCL/OM-laponite materials.

Figure 1b is the infrared spectra of PLCL copolymers with three ratios (lactide/ε-caprolactone = 9/1, lactide/ε-caprolactone = 8/2, lactide/ε-caprolactone = 7/3). Typical polyester absorption peaks appear in the figure. The three infrared absorption peak curves show that the stretching vibration peak of –OH in the polymer is at 3,500 cm−1, the bending vibration absorption peak of –CH3 is at 2,998 cm−1, the stretching vibration peak of–CH2–is at 2,946 cm−1, and the strong absorption peak at 1,757 cm−1 is the stretching vibration absorption peak of C=O. This is because both the ester group and the carboxyl group in the polymer contain C=O, the bending vibration absorption peak of –CH3 is at 1,455 cm−1, and the C–C bending vibration peak is at 1,384 cm−1. The–CH2–bending vibration peak is at 1,367 cm−1, and the C=O stretching vibration peaks of the ester group are at 1,131 cm−1 and 1,088.56 cm−1. It shows that lactide and caprolactone are successfully copolymerized at three ratios.

Figure 1c shows the infrared spectra of PLCL/OM-laponite blends with different proportions. The characteristic absorption peaks of PLCL appeared at 3,500 cm−1, 1,757 cm−1, 1,131 cm−1 and 1,088 cm−1. The stretching vibration absorption peak of –OH in PLCL and OM-laponite was at 3,500 cm−1, and the strong absorption peak at 1,757 cm−1 was the stretching vibration absorption peak of C=O. This is because both ester groups and carboxyl groups in the polymer contain C=O, and the C=O bending vibration peaks of ester groups were at 1,131 cm−1 and 1,088 cm−1. In addition, an obvious amino characteristic peak appeared at approximately 3,750 cm−1, and the Si–O-alkyl multiple-peak appeared at 1,046 cm−1, indicating that OM-laponite and PLCL can be well blended and modified.

3.2 TG

The results are shown in Figure 2a. The CTAB has only one stage of heat loss, and the decomposition temperature is 240–320 °C. The decomposition is rapid, mainly due to mass loss from molecular chain breaks. There is only one stage of lithium saponite pyrolysis, at approximately 100 °C. The weight loss at this stage is mainly due to the breaking of hydrogen bonds within and the lithium saponites. The weight loss of OM-laponite was divided into two stages. The weight loss in the 35–200 °C stage is due to the water loss caused by the fracture of intramolecular and intermolecular hydrogen bonds of OM-laponite. In the range of 250–430 °C, cleavage of the long chain aliphatic carbon chain occurs. The cleavage of laponite has only one stage, and the weight loss in this stage is mainly due to the mass loss caused by the breakage of hydrogen bonds within and between laponite molecules.

Figure 2: Remaining mass (TG) and differential (DTG) curves. (a) Remaining mass (TG) and differential (DTG) curves of the OM-laponite powders, (b) PLCL copolymer materials and (c–e) PLCL/OM-laponite materials: (c) PLCL (7/3)/OM-laponite-1–3 %, (d) PLCL (8/2)/OM-laponite-1–3 %, (e) PLCL (9/1)/OM-laponite-1–3 %.
Figure 2:

Remaining mass (TG) and differential (DTG) curves. (a) Remaining mass (TG) and differential (DTG) curves of the OM-laponite powders, (b) PLCL copolymer materials and (c–e) PLCL/OM-laponite materials: (c) PLCL (7/3)/OM-laponite-1–3 %, (d) PLCL (8/2)/OM-laponite-1–3 %, (e) PLCL (9/1)/OM-laponite-1–3 %.

Figure 2b shows the TG-DTG curves of PLCL copolymers at three ratios (PLCL 9/1, PLCL 8/2, PLCL 7/3). It can be seen from the diagram that in the range of 0–800 °C, the PLCL under the three copolymerization ratios has only one obvious thermal weight loss process, which is at the stage of 200–400 °C. The maximum thermal decomposition rate temperatures of the three proportions are PLCL 9/1 287.4 °C, 8/2 306.4 °C, 7/3 326.9 °C, respectively. This process is mainly the decomposition of PLCL macromolecular chains, and there is almost no residue. The weight loss of PLCL with three copolymerization ratios reached 100 %, which was due to the fact that the polymer PLCL contained only C, H and O elements. With the increase of lactide content, the thermal stability of PLCL also increased, which was due to the higher thermal stability of PLA than PCL.

Thermogravimetric analyses of PLCL (7/3)/OM-laponite, PLCL (8/2)/OM-laponite and PLCL (9/1)/OM-laponite materials are shown in Figure 2c and e, respectively. It can be seen from the figure that when the PLCL material was blended with OM-laponite, the thermal degradation temperature was slightly higher than that of pure PLCL. The material test temperature range is 25–800 °C, and several PLCL/OM-laponite materials have only one obvious mass loss stage, which is in the temperature range of 200–500 °C. The heat loss is mainly caused by the cracking of the PLCL macromolecular chain and the breaking of covalent bonds in OM-laponite molecules. Furthermore, it can be seen that in the three groups of PLCL (7/3)/OM-laponite, PLCL (8/2)/OM-laponite and PLCL (9/1)/OM-laponite, with increasing of OM-laponite content, the thermal decomposition temperature of PLCL/OM-laponite materials slightly shifts to high temperature, and the thermal stability increases with the increase of OM-laponite content. In the three groups of PLCL (7/3)/OM-laponite, with the increase of OM-laponite content from 1 to 3 %, the maximum thermal decomposition rate temperatures were 355 °C, 372.7 °C, 377.3 °C, respectively. In the three groups of PLCL (8/2)/OM-laponite, with the increase of OM-laponite content from 1 to 3 %, the maximum thermal decomposition rate temperatures were 352.3 °C, 354.5 °C, 365.7 °C, respectively. In the three groups of PLCL (9/1)/OM-laponite, as the content of OM-laponite increases from 1 to 3 %, the maximum thermal decomposition rate temperatures are 330.9 °C, 365 °C, 370.4 °C, respectively. This is mainly because OM-laponite in PLCL has higher rigidity and has a certain inhibitory effect on the activity of PLCL molecules, so the PLCL molecular chain has a higher decomposition temperature than the completely free molecular chain during thermal decomposition, thus delaying the thermal decomposition rate of the composite. In addition, when the materials undergo thermal degradation, the OM-laponite on the surface of the material can prevent the movement of small molecules within the PLCL to some extent due to the thermal decomposition of the PLCL molecular chains.

At the same time, there is an interfacial force between PLCL and OM-laponite, which can act as a physical crosslinking point in the material system, inhibiting the movement of molecular chains to a certain extent and improving the thermal stability of the materials.

3.3 DSC

Figure 3a–c show the DSC plots of the PLCL copolymer materials and PLCL/OM-laponite materials. The data in Table 2 show that the addition of lithium alginate increased the melting temperature of PLCL, and the melting temperatures of different proportions of PLCL were close to each other. When the content of OM-laponite increases from 1 to 2 %, the melting temperature of OM-laponite/PLCL composites increases. When the content of OM-laponite increases from 2 to 3 %, the melting temperature of OM-laponite/PLCL composites decreases. The former is because OM-laponite acts as a nucleating agent during the crystallization process, which makes PLCL easier to crystallize during melt cooling, accelerates the crystallization rate of PLA, and improves the thermal stability of the material. In addition, compared with pure PLCL, the melting temperature of PLCL/OM-laponite composites also increased. The reason for this may be due to the cross-linking effect of OM-laponite in PLCL. More cross-linking points restrict the movement of the polymer molecular chains. The addition of inorganic nanoparticles increased the crosslinking points of the materials, but the number of crosslinking points was reduced due to the aggregation of the particles in a certain content of the sample. When the addition amount is moderate, the degree of dispersion of the particles in the matrix increases, resulting in an increase in the number of potential nucleation points, resulting in a corresponding increase in the number of grains formed after the temperature change. With the increase of the addition amount of particles, the particles were agglomerated due to the high surface activity, which reduced the nucleation points. When the particle content was more than 3 %, the melting temperature of OM-laponite/PLCL began to decrease.

Figure 3: Thermal analysis of PLCL/OM-laponite: (a) PLCL (7/3)/OM-laponite-0–3 %, (b) PLCL (8/2)/OM-laponite-0–3 %, (c) PLCL (9/1)/OM-laponite-0–3 %.
Figure 3:

Thermal analysis of PLCL/OM-laponite: (a) PLCL (7/3)/OM-laponite-0–3 %, (b) PLCL (8/2)/OM-laponite-0–3 %, (c) PLCL (9/1)/OM-laponite-0–3 %.

Table 2:

Thermal analysis data.

OM-Laponite PLCL (7/3) (°C) PLCL (8/2) (°C) PLCL (9/1) (°C)
0 170.3 173.7 174.6
1.0 % 172.6 174.4 178.3
2.0 % 174.9 177.1 181.6
3.0 % 171.8 174.0 175.1

In addition, compared with pure PLCL, the melting temperature of OM-laponite/PLCL composites also increased. The reason may be due to the cross-linking effect of OM-Laponite particles in the PLCL matrix. The more cross-linking points, the less free volume of the polymer, and the higher degree of constraint on the movement of the molecular chain. The addition of inorganic nanoparticles increased the cross-linking points of the composites, but the agglomeration of particles in the samples with more than a certain content led to a decrease in the number of cross-linking points. This shows that OM-laponite not only acts as a nucleating agent in the crystallization process of PLCL, but also hinders the diffusion of molecular chains. In the OM-laponite/PLCL nanocomposite system, the nucleation effect is dominant when the content of OM-laponite is 1–2 %. Therefore, the melting temperature of OM-laponite/PLCL is better than that of PLCL. When the content of OM-laponite is 3 %, the improvement effect of OM-laponite on the thermal stability of PLCL decreases with the increase of OM-laponite content due to the increasing hindrance of molecular chain diffusion during the crystallization of PLCL.

3.4 Mechanical analysis

Figure 4 shows the mechanical properties of PLCL and PLCL/OM-laponite and orthopedic ligature samples.

Figure 4: Mechanical properties of PLCL and PLCL/OM-laponite and orthopedic ligature samples: (a) elongation at break, (b) elastic modulus, (c) tensile strength.
Figure 4:

Mechanical properties of PLCL and PLCL/OM-laponite and orthopedic ligature samples: (a) elongation at break, (b) elastic modulus, (c) tensile strength.

The tensile strength of most PLCL composites decreased with increasing OM-laponite content over the experimental range. When the content of OM-laponite was increased from 1.0 to 2.0 %, the tensile strength decreased. When the content of OM-laponite was increased from 2.0 to 3.0 %, there was no significant change in tensile strength. The addition of OM-laponite reduced the elastic modulus of PLCL composites. When the addition amount increased from 1 to 2 %, the elastic modulus showed a downward trend. When the addition amount increased from 2 to 3 %, the elastic modulus showed an upward trend, but the overall elastic modulus was lower than that of pure PLCL. The presence of lithium alginate may introduce microscopic defects in the polymer matrix, resulting in stress concentration, thereby reducing the overall modulus and strength. This is consistent with the common behavior of inorganic fillers in polymer matrix. For the decrease of strength, it may be due to the fact that the dispersion of lithium alginate is more uniform and the interface bonding is poor at low filler content, which makes the stress transfer uneven and leads to the decrease of strength. Additionally, as seen from the graph, the elongation at break of the PLCL/OM-Laponite composite only increases with increasing OM-Laponite content. The two materials PLCL (8/2) and PLCL (9/1) first increase and then decrease with increasing OM-laponite content. This is mainly because PLCL (7/3) itself is less stiff than PLCL (8/2) and PLCL (9/1). The addition of OM-laponite has little effect on the rigid structure of PLCL (7/3). For the other two materials it can be assumed that the interactions between the molecular chains can increase when OM-laponite is dispersed homogeneously. When the content of OM-laponite is too high, fractures occur due to agglomeration and the formation of stress concentration points. Moreover, the elongation at break of PLCL (7/3) is better than that of the orthopedic material.

Comparing PLCL/OM-laponite materials with existing samples for orthopedic applications, it was found that the tensile strength of PLCL (8/2)/OM-laponite and PLCL (9/1)/OM-laponite was higher than the tensile strength of the tip, middle and interface sections of the orthopedic ligature, and that its elongation at break was also at the same level as that of the orthopedic ligature samples. Furthermore, the tensile strength and elongation at break of PLCL (7/3)/OM-laponite meet the tensile performance requirements of existing bone fixation devices. Therefore, the PLCL/OM-laponite materials prepared in this experiment have potential applications in orthopedic clinics.

3.5 Scanning electron microscope analysis of PLCL/OM-laponite materials

The surface structure characteristics of the PLCL/OM-laponite materials were obtained by field emission scanning electron microscopy (SEM). Figure 5 shows PLCL (7/3)/OM-laponite, PLCL (8/2)/OM-laponite and PLCL (9/1)/OM-laponite. The SEM images of PLCL/OM-laponite sheets with 12 different blending ratios of OM-laponite contents of 1.0, 2.0 and 3.0 %. The surface of 12 kinds of composite materials is smooth, flat and crack-free. The cross section shows that there are no cracks and delamination in the composite material, and laponite is uniformly dispersed in the PLCL material. Therefore, the PLCL/OM-laponite materials prepared in this study have a relatively strong structure, which is conducive to their application in orthopedic materials.

Figure 5: SEM image of PLCL/OM-laponite sheet side: (a) PLCL (7/3)-flat, (a1) PLCL (7/3)-section. (b) PLCL (7/3)/OM-laponite-1.0 %-flat, (b1) PLCL (7/3)/OM-laponite-1.0 %-section. (c) PLCL (7/3)/OM-laponite-2.0 %-flat, (c1) PLCL (7/3)/OM-laponite-2.0 %-section. (d) PLCL (7/3)/OM-laponite-3.0 %-flat, (d1) PLCL (7/3)/OM-laponite-3.0 %-section. (e) PLCL (8/2)-flat; (e1) PLCL (8/2)-section. (f) PLCL (8/2)/OM-laponite-1.0 %-flat, (f1) PLCL (8/2)/OM-laponite-1.0 %-section. (g) PLCL (8/2)/OM--2.0 %-flat, (g1) PLCL (8/2)/OM-laponite-2.0 %-section. (h) PLCL (8/2)/OM-laponite-3.0 %-flat, (h1) PLCL (8/2)/OM-laponite-3.0 %-section. (i) PLCL (8/2)-flat, (i1) PLCL (8/2)-section. (j) PLCL (8/2)/OM-laponite-1.0 %-flat, (j1) PLCL (8/2)/OM-laponite-1.0 %-section. (k) PLCL (8/2)/OM-laponite-2.0 %-flat, (k1) PLCL (8/2)/OM-laponite-2.0 %-section. (l) PLCL (8/2)/OM-laponite-3.0 %-flat, (l1) PLCL (8/2)/OM-laponite-3.0 %-section.
Figure 5:

SEM image of PLCL/OM-laponite sheet side: (a) PLCL (7/3)-flat, (a1) PLCL (7/3)-section. (b) PLCL (7/3)/OM-laponite-1.0 %-flat, (b1) PLCL (7/3)/OM-laponite-1.0 %-section. (c) PLCL (7/3)/OM-laponite-2.0 %-flat, (c1) PLCL (7/3)/OM-laponite-2.0 %-section. (d) PLCL (7/3)/OM-laponite-3.0 %-flat, (d1) PLCL (7/3)/OM-laponite-3.0 %-section. (e) PLCL (8/2)-flat; (e1) PLCL (8/2)-section. (f) PLCL (8/2)/OM-laponite-1.0 %-flat, (f1) PLCL (8/2)/OM-laponite-1.0 %-section. (g) PLCL (8/2)/OM--2.0 %-flat, (g1) PLCL (8/2)/OM-laponite-2.0 %-section. (h) PLCL (8/2)/OM-laponite-3.0 %-flat, (h1) PLCL (8/2)/OM-laponite-3.0 %-section. (i) PLCL (8/2)-flat, (i1) PLCL (8/2)-section. (j) PLCL (8/2)/OM-laponite-1.0 %-flat, (j1) PLCL (8/2)/OM-laponite-1.0 %-section. (k) PLCL (8/2)/OM-laponite-2.0 %-flat, (k1) PLCL (8/2)/OM-laponite-2.0 %-section. (l) PLCL (8/2)/OM-laponite-3.0 %-flat, (l1) PLCL (8/2)/OM-laponite-3.0 %-section.

3.6 Contact angle analysis of PLCL/OM-laponite materials

The contact angle is the most commonly used method to measure surface wettability. 27 From Figure 6, it can be seen that the water contact angle of PLCL/OM-laponite materials decreases with increasing of OM-laponite content because OM-laponite materials are hydrophilic materials; its addition will increase the hydrophilicity of PLCL materials. At the same time, among the three PLCL materials, the most obvious improvement is PLCL (7/3), and the water contact angle of the other two PLCL materials also decreases, which is not as obvious as PLCL (7/3). This may be because among the three PLCL materials, PLCL (7/3) has the worst hydrophilicity. When hydrophilic materials are added, the hydrophilic sites increase significantly, so the water contact angle decreases significantly.

Figure 6: Contact angle of PLCL and PLCL/OM-laponite.
Figure 6:

Contact angle of PLCL and PLCL/OM-laponite.

3.7 Cytotoxicity analysis of PLCL/OM-laponite materials

Figure 7 shows the cell viability data of the PLCL/OM-laponite cytotoxicity test on macrophage leukemia cells. It can be seen from the figure that the cell viability of PLCL (8/2) materials containing OM-laponite (3.0 %) was 95.9 % at a cell concentration of 50 μg/mL, and the cell viability of PLCL (9/1) materials containing OM-laponite (1.0 %) was 97.8 %. Except that the cell viability of these two materials was less than 100 %, the cell viability of the other PLCL/OM-laponite materials was greater than 100 % at a concentration of 50 μg/mL, indicating that the prepared PLCL/OM-laponite materials were basically nontoxic to cells. In addition, it can be seen from the diagram that the high content of OM-laponite is not conducive to cell growth. Within the experimental range, when the content of OM-laponite is 2.0 %, the cell survival rate is the highest.

Figure 7: Cell viability of PLCL/OM-laponite materials.
Figure 7:

Cell viability of PLCL/OM-laponite materials.

3.8 Degradation analysis of PLCL/OM-laponite materials

Figure 8 shows the in vitro degradation test diagram of PLCL/OM-laponite materials. The in vitro degradation test was carried out for 60 days. Samples were taken on 0 d, 15 d, 30 d, 45 d and 60 d, and then dried and weighed. The results are shown in the diagram. The degradation rates of PLCL (7/3)/OM-laponite-1.0 %, PLCL (7/3)/OM-laponite-2.0 % and PLCL (7/3)/OM-laponite-3.0 % were 4.41, 1.57 and 1.11 %, respectively. The degradation rates of PLCL (8/2)/OM-laponite-1.0 %, OM- PLCL (8/2)/laponite-2.0 % and PLCL (8/2)/OM-laponite-3.0 % were 2.62, 2.04 and 1.29 %, respectively. The degradation rates of PLCL (9/1)/OM-laponite-1.0 %, PLCL (9/1)/OM-laponite-2.0 % and PLCL (9/1)/OM-laponite-3.0 % were 4.76, 2.14 and 1.27 %, respectively. The degradation rates of several PLCL/OM-laponite samples decreased with increasing OM-laponite content, which may be due to the stable crystal structure of OM-laponite.

Figure 8: Degradation results of PLCL/OM-laponite materials.
Figure 8:

Degradation results of PLCL/OM-laponite materials.

4 Conclusions

In this paper, laponite was modified by cetyltrimethylammonium bromide to prepare OM-laponite, which was blended with PLCL. The structure and properties of laponite after organic modification were analyzed by FTIR, TGA.

The results showed that cetyltrimethylammonium bromide was successfully grafted onto laponite. The thermal stability of OM-laponite was improved with increasing of CTAB. The addition of OM-laponite can improve the mechanical properties of PLCL to a certain extent, and the interaction between OM-laponite and PLCL is enhanced, when the content of OM-laponite is 2.0 %, the elongation at break and tensile strength of composited spline are superior to the medical orthopedic bandage. OM-laponite has a dual effect on the thermal stability of PLCL; on the one hand, it acts as a nucleating agent and inhibits the diffusion movement of the PLCL molecular chain to promote the thermal stability of PLCL. On the other hand, when the content of OM-laponite exceeds 2.0 %, it will agglomerate and reduce the thermal stability. The degradation rate of PLCL/OM-laponite composites decreased with increasing of OM-laponite content. The water contact angle results demonstrate that the hydrophilicity is enhanced and is beneficial to cell adhesion. The results of cell experiment illustrate that the composite materials have a certain effect on cell proliferation when the content of OM-laponite is less than 2 %. Most importantly, the material we prepared has a better tensile strength than existing orthopedic medical materials, which is promising for its potential application in orthopedic material applications.

Corresponding authors: Hongli Li and Yongming Chuan, National and Local Joint Engineering Research Center for Green Preparation Technology of Biobased Materials, Yunnan Minzu University, Kunming, 650500, China, E-mail: (H. Li), (Y. Chuan)

Funding source: Basic Research Project of Yunnan Province-general project

Award Identifier / Grant number: 202301AT070018

Funding source: Yunnan Minzu University 2023 Master’s Research Innovation Fund Project

Award Identifier / Grant number: 2023SKY030

Funding source: Yunnan Provincial High Level Talent Training Support Plan

Award Identifier / Grant number: YNWR-CYJS-2020-038

Funding source: Ten Thousand Talent Plans for Young Top-notch Talents of Yunnan Province

Award Identifier / Grant number: YNWR-QNBJ-2019-094

  1. Research ethics: Not applicable.

  2. Informed consent: Not applicable.

  3. Author contributions: Yan Ren: data curation, visualization, writing-original draft, formal analysis. Yonggang Lin: formal analysis, writing – review & editing. Yabei Ding: software, writing-review. Ruimin Tang: software, writing-review. Minglong Yuan: software, writing-review. Hongli Li: supervision, project administration, funding acquisition. Yongming Chuan: validation, writing – review & editing. The authors have accepted responsibility for the entire content of this manuscript and approved its submission.

  4. Use of Large Language Models, AI and Machine Learning Tools: None declared.

  5. Conflict of interest: The authors state no conflict of interest.

  6. Research funding: This work was supported by Yunnan Provincial High Level Talent Training Support Plan (YNWR-CYJS-2020-038), Basic Research Project of Yunnan Province-general project (202301AT070018), Ten Thousand Talent Plans for Young Top-notch Talents of Yunnan Province (YNWR-QNBJ-2019-094) and Yunnan Minzu University 2023 Master’s Research Innovation Fund Project (2023SKY030).

  7. Data availability: Data will be made available on request.

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Received: 2024-05-27
Accepted: 2024-10-27
Published Online: 2025-01-29
Published in Print: 2025-02-25

© 2024 Walter de Gruyter GmbH, Berlin/Boston

Articles in the same Issue

  1. Frontmatter
  2. Material Properties
  3. Synthesis and characterization of ASU-PPO based anion exchange membrane with PEG support for water electrolysis
  4. Experimental and numerical investigations on the mechanical properties of overmolded hybrid fiber reinforced thermoplastic composites
  5. Preparation and Assembly
  6. Reed fiber as a sustainable filler for tuning the biodegradability of polylactic acid composites
  7. Preparation of liquid metal/thermoplastic polyurethane composites with enhanced thermal conductivity via rolling regulation
  8. Lignin charcoal/preparation of chitosan composite membrane and H2S adsorption properties
  9. Synthesis and formulation of modified milk protein and its study as an adhesive for wood binding
  10. Preparation and properties of PLCL/OM-Laponite materials with potential applications in orthopedic bandage
  11. Engineering and Processing
  12. Probability evaluation of the ternary polymerization and reactivity ratio of bio-based PA5T/56
https://doi.org/10.1515/polyeng-2024-0099
Keywords for this article
organic modification; Laponite; PLCL; orthopedic bandage

Articles in the same Issue

  1. Frontmatter
  2. Material Properties
  3. Synthesis and characterization of ASU-PPO based anion exchange membrane with PEG support for water electrolysis
  4. Experimental and numerical investigations on the mechanical properties of overmolded hybrid fiber reinforced thermoplastic composites
  5. Preparation and Assembly
  6. Reed fiber as a sustainable filler for tuning the biodegradability of polylactic acid composites
  7. Preparation of liquid metal/thermoplastic polyurethane composites with enhanced thermal conductivity via rolling regulation
  8. Lignin charcoal/preparation of chitosan composite membrane and H2S adsorption properties
  9. Synthesis and formulation of modified milk protein and its study as an adhesive for wood binding
  10. Preparation and properties of PLCL/OM-Laponite materials with potential applications in orthopedic bandage
  11. Engineering and Processing
  12. Probability evaluation of the ternary polymerization and reactivity ratio of bio-based PA5T/56
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