Preparation and properties of nano-TiO2-modified photosensitive materials for 3D printing

Yingying Liu; Jin Chen; Lei Ning; Jianke Sun; Lu Liu; Kun Zhao

doi:10.1515/epoly-2022-0037

Article Open Access

Preparation and properties of nano-TiO₂-modified photosensitive materials for 3D printing

Yingying Liu , Jin Chen , Lei Ning , Jianke Sun , Lu Liu and Kun Zhao

Published/Copyright: August 18, 2022

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From the journal e-Polymers Volume 22 Issue 1

Abstract

The surface of nano-TiO₂ was modified by a silane coupling agent KH570, and the photosensitive resin was modified by blending the modified nano-TiO₂ with three-dimensional (3D) printing light-curing resin. The modified nano-TiO₂ powder was characterized by infrared spectrum, X-ray diffraction, contact angle test, and scanning electron microscope. The effects of different content of modified TiO₂ on the viscosity, curing shrinkage, tensile strength, elongation at break, hardness, thermal stability, and cross-section morphology of 3D printing photosensitive resin were studied. The results showed that the mechanical properties of epoxy resin were improved obviously after surface modification with a silane coupling agent. When the mass fraction of TiO₂ was 1.5%, the mechanical properties of the molded parts were the best. The tensile strength, impact strength, and elongation at break were increased by 51.1, 43.8, and 10.8%, respectively, and the hardness value was maintained at 81–83 HD. The addition of modified TiO₂ can improve the heat resistance of the epoxy resin. When the amount of TiO₂ is 1.5%, the T _50%, T _max, and carbon residue rate of the epoxy resin are increased by 3.44°C, 6.34°C, and 25.3%, respectively.

Keywords: modified nano-TiO2 ; 3D printing photosensitive resin; mechanical properties; enhanced phase shrinkage; epoxy resin

1 Introduction

Three-dimensional (3D) printing technology is a significant leap in the field of manufacturing technology in the world in the past 30 years. It has reached the high complexity and high precision structure that traditional manufacturing is difficult to achieve. It is a unique dieless manufacturing concept. Stereolithography apparatus (SLA, i.e., stereoscopic light-curing molding technology) is the most mature 3D printing technology with the highest molding accuracy (1,2,3). SLA takes liquid photosensitive resin as raw material, which is rapidly transformed from liquid resin to solid material under the action of ultraviolet light. This process is accompanied by the shrinkage of material volume. Excessive volume shrinkage will affect the molding accuracy, and at the same time, it will cause serious deformation of the molding parts. The material properties are affected, resulting in the actual strength of the photosensitive resin being only 1/10 to 1/100 of the theoretical strength (4). In order to reduce the serious influence caused by internal stress, inorganic fillers are usually added as rigid nodes between molecular chains. Common inorganic fillers include Al₂O₃ (5,6), TiO₂ (7,8,9,10,11), SiC (12), TiC (13), ZrC, and B₄C (14). TiO₂ is a common inorganic nano-filler, which has the advantages of non-toxic, large specific surface area, and good heat resistance. Compared with traditional fillers, nano-fillers can also improve the properties of polymer materials when the amount of nano-fillers is small (15,16,17,18,19). Nano titanium oxide is widely used in plastics, fine ceramics, composite materials, surface protection, aerospace industry, semiconductor, and other fields due to its good properties of high strength, high hardness, high resistivity, high-temperature resistance, and wear resistance (20,21,22). It is the most widely used material among oxides (23). With the increase in the volume fraction of nanoparticles, the strength of the composite increases, and the plastic toughness of the composite decreases (24). When the volume fraction exceeds 4%, the nanoparticles are easy to agglomerate, and no matter how much reinforcement is added, the mechanical properties of the composite will not be improved (25,26). Liu et al. (27) and Liu (28) used polyvinyl alcohol to encapsulate nanoparticles, and Liu Kai used polymer binder to encapsulate ceramic particles to improve the dispersion of nanoparticles, which is suitable for SLS (laser sintering technology) molding with short molding cycle, low molding accuracy, and poor green body density, but not for SLA molding with high accuracy requirements. Ning et al. (29) modified the nano powder with KH570 to obtain the composite resin with good dispersion. However, the mechanical properties and the influencing factors of SLA are not studied. In this article, silane coupling agent KH570 was used to modify the surface of TiO₂, and the modified nano-TiO₂ was mechanically blended with 3D printing photosensitive resin to modify the photosensitive resin. The effects of different content of modified TiO₂ on the viscosity, curing shrinkage, tensile strength, elongation at break, hardness, thermal stability, and cross-section morphology of 3D printing photosensitive resin were studied.

2 Materials and methods

2.1 Raw materials

Nano-TiO₂ (the particle size is 10 nanometers); 3100 a bisphenol A epoxy acrylate (EA); γ-methacryloxypropyl trimethoxysilane (KH570); 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO); 1,6-hexanediol diacrylate (HDDA); analytical pure absolute ethanol; and distilled water (self-made).

2.2 Surface modification of TiO₂

About 100 mL mixed solution of anhydrous ethanol and deionized water was prepared according to the ratio of 1:1.5 and added to a 250 mL three-port flask with a spherical condenser and stirrer; the pH of the solution was adjusted to 10 with ammonia water, 20 g dry nano-TiO₂ powder was weighed, added into a three-port flask, and stirred with a stirrer under the condition of 70°C constant temperature oil bath for 30 min, so that the powder can be evenly dispersed in the solution. After that, the mixed solutions of KH-570 and ethanol with different mass fractions (5, 10, 15, 20, and 25%) were added to three-port flasks. After the reaction at 70°C for 3 h, ultraviolet (UV) light was used to irradiate the reaction process. After the reaction, it was cooled to room temperature, filtered, washed, dried in a 100°C blow-drying oven, ground, sieved through 200 meshes, dried, and stored for standby. The mechanism of KH-570-modified TiO₂ is shown in Figure 1.

Figure 1

Mechanism of KH-570-modified nano-TiO₂.

2.3 Photosensitive resin molding

A certain amount of photoinitiator TPO was weighed and dissolved in the active diluent HDDA. It was stirred in a water bath at 40°C for 30 min to completely dissolve and then mixed with bisphenol A epoxy acrylic resin to obtain a mixed solution. The modified TiO₂ was added to the mixed solution, magnetically stirred for 2 h at room temperature, and rotated at 1,000 rpm. After the stirring is completed, the mixture was allowed to stand for 12 h in the dark to defoam to obtain a 3D printing light-curing resin solution and stored in the dark at room temperature for later use. Using the Moai SLA 3D printer, the above mixed solution was poured into the resin tank. Setting parameters: the main emission wavelength is 405 nm, the layer thickness is 0.1 mm, the ultraviolet laser power is 58 W, and the printing speed is 40 mm·h⁻¹. After selecting the digital model and printing, the sample size is 80 mm × 10 mm × 4 mm. Figure 2 shows the SLA 3D printing process. Figure 3 shows the curing process of 3D printing materials. The action mechanism of KH-570 modified TiO₂ is shown in Figure 4.

Figure 2

SLA 3D printing process.

Figure 3

Curing process of 3D printing materials.

Figure 4

Curing mechanism of nano-TiO₂-modified resin.

2.4 Testing and characterization

Moai-type SLA 3D printer (Hong Kong Peopoly Moai Company) is used for photosensitive resin molding. Setting parameters: the main emission wavelength is 405 nm, the layer thickness is 0.1 mm, the ultraviolet laser power is 58 W, the printing speed is 40 mm·h⁻¹, and the sample size is 80 mm × 10 mm × 4 mm; S-4,800 field emission scanning electron microscope (Hitachi, Japan) was used to observe the morphology of TiO₂. Samples of appropriate size were placed on the conductive adhesive, and the samples were sprayed with gold before observation; Bruker Fourier transform infrared spectrometer (Bruker company, Germany) was used to study the changes of organic functional groups in the samples, and the test range was 4,000–400 cm⁻¹; XRD-7,000s X-ray diffractometer (Shimadzu company, Japan) was used to study the powder structure. The scanning angle was 10–80°, and the speed was 8°·min⁻¹; Ndj-8s Digital Viscometer was used to measure the viscosity of the resin Shanghai (Yueping Scientific Instrument Co., Ltd.). About 100 mL of the evenly mixed resin was taken in a beaker, and the No. 2 rotor of the Ndj-8s digital viscometer was used to measure the resin viscosity, the speed was set at 12–60 rpm, and the temperature at 25°C. The viscosity of each sample was measured at five different points and averaged. Volume shrinkage: a pycnometer was used to measure the density ρ ₁ of a uniformly mixed resin system at 25°C, then the resin system was put in the SLA 3D printer, the density ρ ₂ of the resin system was tested after curing and molding, and the following formula was used to calculate volume shrinkage S _V:

(1) S V = ρ 2 − ρ 1 ρ 2 × 100%

The resin glass transition temperature was measured using a DSC25 differential scanning calorimeter; the temperature rise and cooling rate were both 10°C·min⁻¹, the test temperature range was from room temperature to 200°C; and the test was carried out in a nitrogen atmosphere with a nitrogen flowrate of 50 mL·min⁻¹. According to GB/T 1040.2-2006 standard, a DL-D5000N rubber tensile test machine was used to test the spline, the tensile speed was 50 mm·min⁻¹, and the determination temperature was room temperature.

3 Results and discussion

3.1 Characterization of modified nano-TiO₂

Figure 5 shows the Fourier transform infrared (FT-IR) spectrum of nano-TiO₂ before and after modification. Curves “a,” “b,” and “c” correspond to infrared spectrum curves of KH-570 and TiO₂ before and after modification, respectively. At 2949.7 and 2841.7 cm⁻¹ of the “a” curve are the stretching vibration absorption peaks of –CH₃ and –CH₂ in KH570, respectively. At 1086.2 and 823.0 cm⁻¹ are the symmetric stretching vibration absorption peaks of Si–O–C, respectively. Compared with the “b” and “c” curves, there are obvious stretching vibration absorption peaks of –OH at 3426.5 and 3412.0 cm⁻¹, which indicates that hydrophilic group –OH also exists on the surface of TiO₂. After the surface organic modification of KH-570, the –OH on the surface of TiO₂ particles is replaced by the organic group in the product silanol hydrolyzed by KH-570. The formation of silanol produces a part of –OH, which makes the position of –OH absorption peak shift red. Compared with “a” and “c” curves, the characteristic absorption peaks corresponding to KH-570 appeared at 1722.1 and 1638.2 cm⁻¹ in “c” curve, which indicated that KH570 was successfully grafted onto the surface of TiO₂. At the same time, the symmetric stretching vibration absorption peak of Si–O–C in KH-570 did not appear in “c” curve, which indicated that Si–O–C was replaced and formed a new structure with –OH on the surface of TiO₂. The organic modification of nano-TiO₂ was realized.

Figure 5

FT-IR diagram of nano-TiO₂ before and after modification.

Figure 6 shows the X-ray diffraction (XRD) of nano-TiO₂ before and after surface modification. The characteristic peaks of TiO₂ are 25.281°, 37.8°, 48.049°, 53.89°, 55.06°, 68.76°, 70.30°, and 75.029°, respectively. Comparing the curves in the figure, it is found that the diffraction peak value and diffraction intensity of TiO₂ before and after modification with KH-570 do not change, and with the gradual increase in KH-570 content, this result does not change, indicating that silane coupling agent KH-570 has little effect on the crystal form of TiO₂.

Figure 6

XRD of nano-TiO₂ before and after modification.

Figure 7 shows the static contact angle between the surface of modified nano-TiO₂ and water. a–f is the static contact angle between the surface and water of nano-TiO₂ modified by KH-570 with different mass fractions (0, 5, 10, 15, 20, and 25%). When the amount of silane coupling agent KH-570 is 0, the contact angle between the surface of the powder and water is 30° and the static contact angle between the surface of TiO₂ and water increases with the increase of the content of KH-570, which achieves the transition from hydrophilic to superhydrophobic and can be better dispersed in the resin. When the mass fraction of KH-570 is 20%, it shows a good superhydrophobic property. When the mass ratio of KH-570 reaches 25%, the hydrophobic property of TiO₂ decreases, which indicates that the content of the modifier should not be too much.

Figure 7

Static contact angle between modified nano-TiO₂ surface and water: (a) 0% KH570, (b) 5% KH570, (c) 10% KH570, (d) 15% KH570, (e) 20% KH570, and (f) 25% KH570.

Figure 8 shows the scanning electron microscope observation of nano-TiO₂ before and after modification. The morphology of nano-TiO₂ modified by KH-570 with different mass fractions (0, 5, 10, 15, 20, and 25%) was studied. It can be seen from Figure 8a that the unmodified nano-TiO₂ powder is irregular spherical particle stacking, and the agglomeration phenomenon is more serious. After being modified by KH570, the agglomeration phenomenon is improved, and with the increase in silane coupling agent KH570 content, the agglomeration gradually decreases.

Figure 8

Scanning electron microscopic photos of surface modified TiO₂: (a) unmodified TiO₂, (b) 5% KH570, (c) 10% KH570, (d) 15% KH570, (e) 20% KH570, and (f) 25% KH570.

3.2 Effect of nano-TiO₂ content on curing shrinkage of resin

Figure 9 shows the effect of different content of TiO₂ particles on the curing shrinkage of resin. It can be seen from the figure that with the increase of the content of nano-TiO₂ particles, the curing shrinkage of the composite resin gradually decreases, and all keep below 6%. Before the curing of photosensitive resin, the main force between resins is the van der Waals force, and the intermolecular distance is van der Waals distance. After curing, the intermolecular distance changes from van der Waals distance to covalent bond distance, and the distance becomes shorter, so the resin shrinks. TiO₂ is an inorganic non-shrinking component, which can be added to the resin to fill the gaps caused by the shrinkage of organic components.

Figure 9

Effect of different content of TiO₂ particles on curing shrinkage of resin.

3.3 Effect of TiO₂ content on resin viscosity

Figure 10 shows the effect of nano-TiO₂ content on resin viscosity. It can be seen from the figure that the viscosity of the system increases with the increase in the content of TiO₂ particles. The surface of the modified TiO₂ contains organic groups. After mechanical blending with the resin, it is easy to form a cross-linking network between the molecular chains, which makes it difficult to slip between the molecular chains; thus, the viscosity of the system increases. On the other hand, because of the large specific surface area and high specific surface energy of nano-TiO₂ particles, when the amount of nano-TiO₂ particles is too high, it will interact with prepolymer and diluent monomer in the resin to form a physical cross-linking point, which hinders the movement of the molecular chain and increases the viscosity of the system.

Figure 10

Effect of TiO₂ content on the viscosity of resin.

3.4 Effect of nano-TiO₂ content on mechanical properties of molded parts

Figure 11 shows the change of mechanical properties of the resin-modified by adding different content of TiO₂. It can be seen from the figure that the mechanical properties of the resin are enhanced by adding surface-treated TiO₂. When the amount of TiO₂ is 1.5 wt%, the comprehensive mechanical properties of the molded parts are the best. The tensile strength, impact strength, and elongation at break were increased by 51.1, 43.8, and 10.8, respectively. It can be seen from Figure 11d that with the increase in the amount of TiO₂ in the system, the hardness has no obvious change, indicating that the mechanical properties of TiO₂ itself will enhance the mechanical properties of the cured resin.

Figure 11

Effect of different TiO₂ content on mechanical properties of molded parts: (a) tensile strength, (b) impact strength, (c) elongation at break, and (d) hardness.

3.5 Characterization of tensile fracture surface morphology of resin modified by nano-TiO₂

Figure 12 shows the micro-morphology of the tensile section of the modified resin. The fracture surface of pure epoxy resin is relatively flat and smooth, which is a typical characterization of brittle fracture. Compared with Figure 12a and b, after adding unmodified TiO₂, the wrinkle and roughness of the cross-section increase, and an obvious delamination phenomenon appears, which is due to the poor dispersion of unmodified TiO₂ particles in the resin. Compared with Figure 12a, c, and d, the cross-section becomes rough, the surface cracks and folds increase obviously, the crack arrangement direction is regular, the delamination of the cross-section decreases, and there is an obvious ductile depression area, which indicates that the addition of TiO₂ blurs the interface of the printing layer and makes the cracks deflect. In Figure 12e and f, the cross-section of the resin has a large undulation, and the crack propagation direction is relatively concentrated because, with the increase of the content of TiO₂ particles, the sedimentation and agglomeration phenomenon will occur, the viscosity of the system will gradually increase, and the transmittance of the printing time will be reduced.

Figure 12

Scanning electron microscopic of tensile section of the parts before and after modification: (a) blank resin, (b) unmodified TiO₂, (c) 1 wt% TiO₂, (d) 1.5 wt% TiO₂, (e) 2 wt% TiO₂, and (f) 2.5 wt% TiO₂.

3.6 Effect of nano-TiO₂ content on thermogravimetric behavior of resin

Figure 13 shows the TGA curve of EA and TiO₂-modified photosensitive resin, corresponding to T _50%, T _max, and residual mass data at 800°C. The decomposition of oligomers, photoinitiators, small molecular diluents, and modifiers that are not fully involved in the crosslinking UV curing reaction is mainly at room temperature −300°C, and the decomposition of EA segments is mainly at 300–500°C. Table 1 shows that the T _max and carbon residue rate of the modified resin are relatively high when the TiO₂ content is 1.5%, which is increased by 6.34°C and 25.3%, respectively. When the TiO₂ content is 1.5%, the molded parts of the modified resin are higher than those of the unmodified resin at T _50% and T _max.

Figure 13

Thermogravimetric curve of TiO₂-modified resin: (a) TG and (b) DTG.

Table 1

Thermogravimetric data of TiO₂-modified resin

Sample	T _50% (°C)	T _max (°C)	Residue (%)
EA	422	424	8
EA/silicone	424	430	8
0.5 wt% TiO₂	420	428	11
1.0 wt% TiO₂	424	432	10
1.5 wt% TiO₂	425	432	10
2.0 wt% TiO₂	425	432	10
2.5 wt% TiO₂	422	430	9

3.7 Effect of nano-TiO₂ content on glass transition temperature of resin

Figure 14 shows the influence curve of modified TiO₂ on the glass transition temperature of the resin. It can be seen from the figure that with the increase of TiO₂ content, the glass transition temperature of the molded parts increases after adding TiO₂ particles. When the content of epoxy resin is 1.5%, the glass transition temperature is 92.31°C, which is 14.08°C higher than that of unmodified epoxy resin.

Figure 14

Glass transition temperature curve of TiO₂-modified resin.

4 Conclusions

FT-IR and XRD analyses showed that KH570 was successfully grafted onto the surface of TiO₂, and the crystal form of TiO₂ did not change before and after modification. The hydrophobicity of the modified nano-TiO₂ is obviously enhanced, and the agglomeration phenomenon of the particles is obviously weakened, so the nano-TiO₂ has better dispersion performance. When the content of silane coupling agent is 20%, the agglomeration of TiO₂ particles is less, the dispersion is better, and the contact angle is the largest. At this content, it has good two-phase compatibility with epoxy resin, improves its dispersion in the resin, and avoids the degradation of mechanical properties of cured materials due to phase separation.
The mechanical test shows that when the mass fraction of TiO₂ is 1.5%, the mechanical properties of the molded parts are better. The tensile strength, impact strength, and elongation at break are increased by 51.1%, 43.8%, and 10.8%, respectively, and the hardness value is maintained at 81-83HD. It can be seen from the tensile cross-section morphology of the composite that when the mass fraction of TiO₂ is within 1.5%, the cracks of the cross-section are more regular, and there are obvious ductile concave areas, which indicates that adding the appropriate amount of TiO₂ can improve the fracture brittleness of the resin, ensure the printing accuracy, and play a certain role in toughening.
The analysis of thermal stability and glass transition temperature showed that the addition of modified TiO₂ could improve the heat resistance of the resin. When the content of TiO₂ is 1.5%, the T _50%, T _max, and carbon residue of pure epoxy resin are increased by 3.44%, 6.34%, and 25.3%, respectively. The glass transition temperature reaches the maximum when the content of TiO₂ is 2.5%, which is 14.08.

Funding information: Authors state no funding involved.
Author contributions: Yingying Liu: writing – original draft, writing – review and editing, methodology, formal analysis; Jin Chen: writing – original draft, visualization; Lei Ning: resources, formal analysis; Jianke Sun: project administration; Lu Liu: supervision, validation; Kun Zhao: software.
Conflict of interest: Authors state no conflict of interest.

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Received: 2021-09-12

Revised: 2022-03-03

Accepted: 2022-03-07

Published Online: 2022-08-18

This work is licensed under the Creative Commons Attribution 4.0 International License.

Articles in the same Issue

https://doi.org/10.1515/epoly-2022-0037

Keywords for this article

modified nano-TiO2; 3D printing photosensitive resin; mechanical properties; enhanced phase shrinkage; epoxy resin

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Preparation and properties of nano-TiO2-modified photosensitive materials for 3D printing

Article

Abstract

1 Introduction

2 Materials and methods

2.1 Raw materials

2.2 Surface modification of TiO2

2.3 Photosensitive resin molding

2.4 Testing and characterization

3 Results and discussion

3.1 Characterization of modified nano-TiO2

3.2 Effect of nano-TiO2 content on curing shrinkage of resin

3.3 Effect of TiO2 content on resin viscosity

3.4 Effect of nano-TiO2 content on mechanical properties of molded parts

3.5 Characterization of tensile fracture surface morphology of resin modified by nano-TiO2

3.6 Effect of nano-TiO2 content on thermogravimetric behavior of resin

3.7 Effect of nano-TiO2 content on glass transition temperature of resin

4 Conclusions

References

Articles in the same Issue

Articles in the same Issue

Articles in the same Issue

Preparation and properties of nano-TiO₂-modified photosensitive materials for 3D printing

2.2 Surface modification of TiO₂

3.1 Characterization of modified nano-TiO₂

3.2 Effect of nano-TiO₂ content on curing shrinkage of resin

3.3 Effect of TiO₂ content on resin viscosity

3.4 Effect of nano-TiO₂ content on mechanical properties of molded parts

3.5 Characterization of tensile fracture surface morphology of resin modified by nano-TiO₂

3.6 Effect of nano-TiO₂ content on thermogravimetric behavior of resin

3.7 Effect of nano-TiO₂ content on glass transition temperature of resin