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Article

Preparation of Glass-Ceramics in the R2O-Bi2O3-B2O3-SiO2 System Applied in Automobile Glass Enamel

by
Tiangui Zhao
1,2,
Wei Wang
1,
Kun Liu
1,
Li Liu
2,
Weixia Dong
1,
Qifu Bao
1,*,
Heliang Xu
2 and
Jianer Zhou
1,*
1
School of Materials Science and Engineering, Jingdezhen Ceramic University, Jingdezhen 333403, China
2
Jiangsu Baifu Technology Co., Ltd., Yixing 214200, China
*
Authors to whom correspondence should be addressed.
Inorganics 2023, 11(4), 166; https://doi.org/10.3390/inorganics11040166
Submission received: 8 March 2023 / Revised: 11 April 2023 / Accepted: 13 April 2023 / Published: 14 April 2023
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Abstract

:
Environmental deterioration has put higher requirements on the acid resistance of automotive glass enamel. The present paper aims to prepare acid-resistant glass-ceramics used in automobile glass enamel. Base glasses with the compositions 15R2O-xBi2O3-10B2O3-(75-x) SiO2 (R2O is a mixture of Li2O, Na2O, and K2O (1:1:1, molar ratio), where x = 10, 15, 20, 25, and 30, respectively) was prepared by the melt-quenching method, and glass-ceramics were prepared by their controlling crystallization heat treatment. Crystallization behavior and crystallization ability of base glasses were investigated using the thermal stability parameter (S), the crystallization kinetics calculation results of base glasses, as well as the phase identification results of the heat-treated samples. The effects of the heat treatment temperature on the micromorphology and acid resistance of the heat-treated glasses were also investigated. Then, the optimized glass ceramic was used to prepare automotive glass enamel. The results indicate that: (I) with the increase of Bi2O3/SiO2 ratio, the characteristic temperature of the base glass decreases, the coefficient of thermal expansion (CTE) and crystallization ability increases significantly, the crystallization temperature range becomes wider; (II) the crystallization activation energy of base glasses are in the range of 169~264 kJ/mol; (III) Bi2SiO5 and Bi2O2SiO3 metastable phases are mainly precipitated when the crystallization temperature is between 530 °C and 650 °C, while only Bi4Si3O12 phase is precipitated when the crystallization temperature is above 650 °C; (IV) crystallinity of base glass increases significantly with increasing heat treatment temperature, which is beneficial to improve the acid resistance of heat treated products; (V) automotive glass enamel was prepared by mixing 15R2O-25Bi2O3-10B2O3-50SiO2 glass-ceramic powder with copper-chrome black and varnish, and then printed on the automobile glass substrate. All the properties of the sintered enamel can meet the market requirements, and the acid resistance of our product is better than that of market products.

1. Introduction

Since 2009, China has become the world’s largest producer and seller of automobiles, and the number of automobiles in China will reach 260 million by 2022 [1,2,3,4]. The huge automotive market has driven the demand for glass enamel, a supporting product for automobiles [5]. Enamel paste consists of low melting point glass powder, inorganic black pigment, and varnish, usually printed around the glass of the car, commonly known as the “black frame” [6,7]. Automotive glass enamel not only has a decorative function but can also enhance the bonding between the glass and car body and reduce ultraviolet transmittance [7,8]. Glass enamel contains 55–70 wt.% low melting point glass powder, whose properties determine the sintering temperature, color, and chemical stability of the glass enamel [9,10]. Currently, most glass enamels used in the market are prepared from lead-based glass powder [11,12]. Lead-based glass has the advantages of a low glass transition temperature (Tg), a wide range of adjustable coefficient of thermal expansion (CTE), and a high refractive index [13,14]. However, the volatilization of PbO in the process of lead-based glass production and the leaching of Pb2+ ions after the disposal of lead-containing products will cause serious harm to human health and the environment [15,16,17,18]. With the gradual deterioration of the atmospheric environment, the acid rain phenomenon appears in different degrees all over the world, which puts forward higher requirements for the chemical stability of automotive glass enamel, especially acid resistance [19,20]. Nevertheless, the acid resistance of the existing automobile glass enamel on the market is generally not high, and problems such as fading or shedding often occur during service [5,7]. In order to solve the above problems, it is urgent to develop a new type of lead-free enamel with excellent acid resistance and CTE similar to that of automobile glass substrate. Bismuth and lead have very similar properties because they are adjacent, have a similar molecular weight, and have a similar electronic structure [21,22,23]. The structure and properties of bismuth glass have been studied in depth in order to investigate the possibility of bismuth glass replacing lead-based glass. Studies have shown that bismuth glass with low Tg is usually not chemically stable, which makes it difficult to meet the requirements of automotive glass enamel [24,25]. Thus far, there are two main methods to improve the chemical stability of bismuthate glasses. One method is to strengthen the glass network by doping with oxide, especially rare metal doping, and to hinder the migration of metal ions with lower valence. For example, by adding 1~10% Ta2O5 or 2~6% Y2O3 to Na2O-ZnO-Bi2O3-B2O3-Al2O3-SiO2 glass, the resistance of the glass to 10% citric acid corrosion can be sharply improved from grade 4~5 to grade 1 (the highest grade) [26,27]. Adding 2% WO3 to 20Li2O-20Bi2O3-60B2O3 glass can reduce its dissolution rate (DRWater) in water at 90 °C by two orders of magnitude (from 10−4 g·cm−2·min−1 to 10−6 g·cm−2·min−1) [20]. Although the chemical stability of bismuthate glass can be obviously improved by doping rare metal oxides, the cost of enamel production is increased due to the limited source of rare metal oxides. Another method to improve the chemical stability of bismuth-based low-melting-point glasses is to prepare their corresponding glass-ceramics. As we all know, compared with the corresponding base glass, the mechanical properties, thermal stability, and chemical stability of glass ceramic will usually be improved to a certain degree, and the degree of improvement depends on the type of precipitated phase, the crystallinity, and the microscopic morphology of the crystalline phase [28,29,30,31]. The dissolution rates (DRAcid) of (65-x)Bi2O3-xZnO-30B2O3-5BaO (x = 40~60 mol%) glass-ceramics, with a large number of needle-like Bi2ZnB2O7 crystals, in a 6 wt.% nitric acid solution at 90 °C are near 10−3 g·cm−2·min−1 [32]. However, the DRAcid of 40Bi2O3-30B2O3-(30-x)ZnO-xSrO (x = 0~15 mol%) glass-ceramics in sulfuric acid (6 wt.%) at 90 °C is as low as 10−5 g·cm−2·min−1 [33]. Although these Bi2O3-B2O3-ZnO-SrO glass-ceramics have excellent acid resistance, they are not suitable for preparing glass enamel because their α30~300 °C values are near 11.15 × 10−6/°C, which is much higher than that of automobile glass (α30~300 °C = (8~10) × 10−6/°C).
In fact, low melting point glass for glass enamel does not need to have a very low softening temperature because the plate glass used to print enamel needs to undergo a tempering process in order to improve strength before being used as window glass. The tempering process needs to be held at 720 °C for 210~300 s [34]. Glass with a drastically low softening temperature will be over-sintered at 720 °C, leading to the formation of air bubbles that reduce the adhesion of the enamel layer. Generally, bismuth silicate glass is more suitable for preparing glass enamel than bismuth borate glass since it has much higher chemical stability and softening temperature [23,35]. The structure and properties of bismuth-silicate glasses, mainly the Bi2O3-B2O3-SiO2-RxOy (R = Na, K, Zn, and Ca) systems, have been reported [36,37,38]. According to our knowledge, bismuth-silicate glasses and glass-ceramics are mainly used as sealing materials, and their application in glass enamel is rare. Defects can affect the number of carriers in glass, thereby affecting its electrical and optical properties [39,40,41], but this aspect of performance does not need to be considered when applied to enamels. In the present paper, glasses in the R2O-Bi2O3-B2O3-SiO2 system are proposed as the base glasses to prepare the corresponding glass-ceramics. R2O-Bi2O3-B2O3-SiO2 glass-ceramic powder is homogeneously mixed with inorganic pigment and varnish, and the mixture is screen printed on the flat glass. The flat glass is then tempered. The possibility of practical application of the enamel in automotive windows will be evaluated by studying the various properties of the enamel products.

2. Experimental Procedure

2.1. Preparation of Automotive Glass Enamel

15R2O-xBi2O3-10B2O3-(75-x)SiO2 (x = 10, 15, 20, 25, and 30) glasses were prepared by the melt-cooling method; their detailed compositions are listed in Table 1. R2O is a mixture of Li2O, Na2O, and K2O (1:1:1, molar ratio). All raw materials are analytically pure; alkali oxides (R2O) were introduced with the corresponding carbonate; B2O3 was introduced with boric acid; and Bi2O3 and SiO2 were introduced in the form of oxides. According to the stoichiometric ratio of each sample in Table 1, a 200 g batch was prepared and melted in a corundum crucible. The batch was melted at 1250 °C for 1 h. Homogeneous melt was cast into a preheated stainless-steel mold, annealed at Tg for 1 h to release the residual stress, and then bulk glass was prepared after cooling. The bulk glass was crushed through a 200-mesh sieve to obtain glass powder for phase identification and differential thermal analysis. The corresponding glass-ceramics were prepared by controlled heat treatment on bulk glasses. The heat treatment schedule of each sample was determined according to its differential thermal analysis (DTA) curve.
The enamel paste was obtained by mixing glass-ceramic fine powder (D90 = 7~8 μm), inorganic black pigment (CuCr2O4, D90 = 1.5~2.0 μm), and varnish (acrylic resin, glycerol, and diethylene glycol butyl ether mixed) at a mass ratio of 60:20:20. The enamel was printed on the automobile glass substrate through a 250-mesh screen, and the thickness of the enamel layer was controlled at 22~24 μm. The glass substrate printed with enamel was tempered at 720 °C for about 210 s to obtain the final product. The preparation process and application of automobile glass enamel are shown in Figure 1.

2.2. Performance Testing and Characterization of Materials

Phase identification of base glasses and heat-treated glasses was carried out by an X-ray diffractometer (Bruker D8 advance, Germany), and the scanning range of 2θ angle was 10~80°. The CTE of bulk base glasses and some glass-ceramics was measured by a coefficient of thermal expansion instrument (DIL 402C, NETZSCH, Germany) with a heating rate of 5 °C/min. The average CTE values from 30 °C to 300 °C (α30~300 °C) of samples were used to investigate their dependence on the compositions. The glass transition temperature (Tg(Dil)) and softening temperature (Tf) of each base glass were derived from its CTE curve, and their methods of evaluation are indicated in the curve.
Differential thermal analysis (DTA) curves were recorded by an analyzer (ZCT-B, Beijing Jingyi Gaoke Instrument company) at a heating rate of 5 °C/min from 25 °C to 900 °C with Al2O3 as the reference material. Glass transition temperature (Tg(DTA)), onset crystallization temperature (Tx), and the crystallization peak temperature of base glass were determined according to the DTA curve, and their methods of evaluation are indicated in the curve. The thermal stability parameter (S) was used to judge the thermal stability of each base glass, and its calculation equation is shown in Equation (1) [42,43,44]. The larger the S value, the higher the thermal stability. It is generally considered that glass with S ≥ 100 °C has relatively high thermal stability [45,46].
S = T x − T g ( DTA )
In order to study the crystallization kinetics of A4 base glass, its DTA curves were measured at heating rates of 5 °C/min, 10 °C/min, 15 °C/min, and 20 °C/min, respectively. Kissinger’s equation (Formula (2)) [47] was used to calculate its crystallization activation energy, and Formula (3) [47,48] was used to calculate its crystal growth index (n). In Equation (2), Ec is the crystallization activation energy, β is the heating rate, R is the gas constant, and Tp is the crystallization peak temperature. A straight line can be obtained by plotting ln ( β T p 2 ) to 1/RTp, and the crystallization activation energy Ec can be obtained according to the slope of this line. In Equation (3), ΔT is the half-peak width of the crystallization exothermic peak, which can be obtained by Gaussian fitting.
ln ( β T p 2 ) = − E c R T p + c o n s t a n t
n = 2.5 Δ T ⋅ T c 2 ( E c / R )
Glass-ceramics and the tempered automotive glass printed with enamel were immersed in a 6 wt.% HNO3 solution at 90 °C for 48 h. The acid resistance is evaluated according to the leaching rate value (DRAcid) of each sample in an acid solution. The smaller the DRAcid value indicates the better the acid resistance of the sample, which is calculated by Equation (4) [32,33], where ∆W is the mass difference between the glass-ceramic before and after acid immersion (g), A is the surface area of the sample (cm2), and t is the immersion time (min). The microstructure of each heat-treated sample before and after corrosion in an acid solution was observed by a scanning electron microscope (JSM-6700F, Nippon Electronics).
D R A c i d = Δ W A × t
The Cross-Cut Tester (5152, BYK, Germany) was used to test the adhesion of the sintered enamel. The smaller the ISO grade, the better the bonding between the enamel layer and the glass, and grade 0 was the optimal grade. The colorimeter (CM-26d, Konica Minolta, Japan) was used to test the chroma (L, a, and b) of the enamel after sintering through the glass surface. The smaller the L value, the darker the color. The optical density meter (PRO-361, Xianyang Prospect Instrument Company) was used to test the covering rate of the sintered enamel. A larger OD value means lower transmittance of the enamel layer and stronger shading ability. An intelligent gloss meter (KGZ-1C, Xiangtan Xiangyi Company) was used to test the gloss of sintered enamel. The roughness of the enamel surface after sintering was tested by a roughness meter (SL-030B, Beijing Jitai Company). The surface tension of the sintered enamel was tested with a Dyne Pen (Aisa, USA).

3. Results and Discussion

3.1. Glass Forming Ability and Thermal Properties

The XRD patterns of the samples prepared by the melt-cooling method are shown in Figure 2. As shown in Figure 2, all samples are vitreous because a wide scattering peak in the range of 2θ = 25~35° can be observed in each pattern, indicating that all samples were not crystallized during the preparation process [49]. It also reflects that each composition in Table 1 has strong glass-forming ability. Figure 3 shows the CTE curves for all glass samples, and the α30~300 °C, Tg(Dil), and Tf values are listed in Table 2. Tg reflects the tightness of the glass network structure [50], and the decrease in its value indicates that the integrity of the glass network structure becomes worse. The bond energy of Bi-O is lower than that of Si-O. As Bi2O3 gradually replaces SiO2, the content of the Bi-O bond and non-bridged oxygen bond in the glass gradually increases, leading to a decrease in the tightness of the glass network connection, thereby reducing the characteristic temperature of the glass and increasing the CTE.
Figure 4 shows the DTA curves of all base glasses; their Tg(DTA), Tx, TP, and S values are listed in Table 3. As the Bi2O3/SiO2 ratio increases from 1:6.5 in A1 to 1:1.5 in A5, the thermal properties of base glasses show a regular variation: Tg(DTA) decreases from 442 °C to 421 °C, and the variation trends of Tg(DTA) and Tg(Dil) are quite similar; the Tx decreases significantly from 617 °C to 539 °C; the number of crystallization exothermic peaks varies from 1 in A1 to 2 in A2 to 3 in A3–A5, indicating that the range of crystallization temperatures of samples is obviously wider; and the value of S decreases from 175 °C to 118 °C, indicating that the thermal stability of the base glass decreases significantly and it becomes easy to crystallize. It is well known that Bi3+ has high polarizability, and glasses with high contents of Bi2O3 are easy to crystallize [51,52]. It is worth noting that the S values of A1–A5 base glasses are greater than 100 °C, which indicates they have relatively good thermal stability and strong glass-forming ability. This result is consistent with the XRD identification results of base glasses. The difference between Tg(DTA) and Tg(Dil) is mainly due to the fact that the DTA and CTE tests were carried out on bulk and powder glass samples, respectively.
It is well known that the CTE values of flat glasses fluctuate within a certain range with variations in their compositions. α30~300 °C values of flat glass and tempered glass are usually in the range of (8~10) × 10−6/°C [53]. The α30~300 °C values of the glass samples prepared in the present paper basically fall in this range, indicating that the CTE of R2O-Bi2O3-B2O3-SiO2 glass and flat glass are basically matched. If A1–A5 base glasses are used for automotive enamel, they need to be tempered at 720 °C, and their softening temperatures (450~500 °C range) are relatively low. Therefore, we considered preparing R2O-Bi2O3-B2O3-SiO2 glass-ceramics through controlled crystallization heat treatment of base glasses. In the Bi2O3-SiO2 system, glass ceramic is more heat-resistant than its base glass, while its CTE value is usually lower than that of the corresponding base glass. The residual glassy phases that exist in glass-ceramic can play a role in firmly adhering black pigment to the automobile glass matrix. This is the main reason that we use R2O-Bi2O3-B2O3-SiO2 glass-ceramic powder to prepare enamel.

3.2. Crystallization Kinetics Analysis of Base Glass

With increasing Bi2O3/SiO2 ratio, S value gradually decreases, indicating that the crystallization trend of the glass increases, which is unfavorable to the preparation of the glass but beneficial to the preparation of the glass-ceramics. Before the preparation of R2O-Bi2O3-B2O3-SiO2 glass-ceramics, we took an A4 sample as an example to investigate its crystallization kinetics. DTA tests were carried out on A4 glass powder at 5 °C/min, 10 °C/min, 15 °C/min, and 20 °C/min, respectively. DTA curves obtained at different heating rates are shown in Figure 5. The peak temperatures of each sample’s crystallization exothermic peak originated from DTA curves in Figure 5 and are listed in Table 4. As shown in Figure 5 and Table 4, with the increase in heating rate from 5 °C/min to 20 °C/min: (I) the intensity of the crystallization exothermic peak is obviously enhanced; (II) the shape of each DTA curve is quite similar, and each curve has three exothermic peaks, and their relative strength varies little; (III) the peak temperature of each crystallization exothermic peak increases obviously, which is mainly due to the hysteresis effect of heat transfer [54]. The dependence of ln ( β T c 2 ) on 1/RTp is shown in Figure 6. The calculation result of crystallization activation energy corresponding to each crystallization exothermic peak of the A4 sample is Ec1 = 208.4 kJ/mol, Ec2 = 169.4 kJ/mol, and Ec3 = 263.4 kJ/mol, respectively. The three Avrami indexes calculated are n1 = 2.06, n2 = 2.58, and n3 = 2.23, respectively. Crystal growth index calculation results indicate that the crystals are volume nucleated, grow in two dimensions, and crystallize simultaneously on the surface and inside the glass [47,55].

3.3. Preparation and Properties of Glass-Ceramics

3.3.1. Phase Identification of Heat-Treated Base Glasses

According to the DTA curves of base glasses in Figure 4, their crystallization heat treatment schedules were determined. For each base glass, it was heated at the onset crystallization temperature and the crystallization peak temperature, respectively. The XRD patterns of all heat-treated samples are shown in Figure 7. The detailed heat treatment schedules and crystalline phases precipitated in each base glass are listed in Table 5. The samples prepared by heating the base glass near the onset crystallization temperature for 2 h are amorphous, such as the A2-1, A3-1, A4-1, and A5-1 samples. A small amount of crystallization was detected in A1-1. For A2–A5 base glasses with multiple crystallization and exothermic peaks, the crystallinity of the samples obtained after heat treatment at Tp1 for 2 h is significantly higher than that of the samples heated at Tx for the same time. However, the crystallinity was still very low, and the prepared samples were not strictly glass-ceramics, such as the A2-2, A3-2, A4-2, and A5-2 samples. If the crystallinity is to be improved, the heating time under Tp1 should be extended. The main crystalline phase of these samples heated at Tp1 is Bi2O2SiO3, and a small amount of Bi2SiO5 crystals were detected in them except for A2-2. For A3-A5-based glass, when the heat treatment temperature is increased to Tp2, the crystallinity of each sample is significantly improved, and a new crystalline phase (Bi4Si3O12) is precipitated. The crystallization degree of A3-3, A4-3, and A5-3 samples is relatively high, and they have three kinds of crystalline phases, including Bi2O2SiO3, Bi2SiO5, and Bi4Si3O12. All samples obtained by heating base glasses at the peak temperature of the last crystallization exothermic peak for 2 h have high crystallinity, including A1-2, A2-3, A3-4, A4-4, and A5-4 samples. These samples are glass-ceramics, and only Bi4Si3O12 crystals are detected.
In summary, the type of crystalline phase in heat-treated base glass depends on the number of crystallization exothermic peaks. According to the XRD results of heated samples, it is reasonably concluded that Bi2SiO5 and Bi2O2SiO3 crystals are metastable transition phases [56,57], and all of them transform into stable Bi4Si3O12 crystal phases with the increase of heat treatment temperature. Combined with XRD and crystallization kinetics analysis, we infer that the first crystallization exothermic peak (Tp1) in the DTA curve of the A4 sample is caused by the precipitation of Bi2SiO5 crystal phase; the second crystallization exothermic peak (Tp2) results from the precipitation of Bi2O2SiO3 crystal phase; and the third crystallization exothermic peak (Tp3) is due to the precipitation of Bi4Si3O12 crystal phase. Bi2SiO5 and Bi2O2SiO3 crystals have lower activation energies, and they are easy to precipitate. Bi4Si3O12 crystals have a higher activation energy, and their precipitation from the base glass requires a much higher temperature.

3.3.2. Microstructure and Properties of Heat-Treated Base Glasses

DRAcid values of all heat-treated base glasses are shown in Table 5 and Figure 8. DRAcid value decreases by an order of magnitude with increasing heat treatment temperature. It reduces from 10−5 g·cm−2·min−1 to 10−6 g·cm−2·min−1 for A1~A4 heat-treated glasses, while decreasing from 10−4 g·cm−2·min−1 to 10−5 g·cm−2·min−1 for A5 heat-treated glass. The great decrease in DRAcid value indicates a significant improvement in acid resistance. It may be related to the apparent increase in the crystal volume fraction with increasing heat treatment temperature, as indicated by the XRD results. This phenomenon indicates that acid resistance can be greatly improved by controllable crystallization heat treatment on R2O-Bi2O3-B2O3-SiO2 base glass. Therefore, R2O-Bi2O3-B2O3-SiO2 glass-ceramic powder was used to prepare automotive glass enamel in order to significantly improve the acid resistance of the enamel.
SEM results of heated A4 samples and their SEM after corrosion (see Figure 9) have been taken as an example in order to further study the microstructure of the samples obtained by heating the same base glass at different heat treatment temperatures and to study the effect of acid corrosion on the surface microstructure of these samples. Micrographs of heated A4 samples before and after acid corrosion are shown in the a and b series of Figure 9, respectively. No crystals are observed in Figure 9a1, indicating that the A4-1 sample is vitreous, which is consistent with its XRD identification result. A small number of star-shaped crystals are precipitated in the A4-2 sample (see Figure 9a2), and these star-shaped crystals grow and increase in number and size in the A4-3 sample, as shown in Figure 9a3. It can be presumed that the star-shaped crystals are Bi2O2SiO3 crystals since this phase is the major crystalline phase in A4-2 and A4-3 samples, as indicated by the XRD result. As shown in Figure 9a4, instead of star-shaped crystals, a large number of intermeshing crystals are observed in A4-4 samples. They are Bi4Si3O12 crystals since only the Bi4Si3O12 phase is identified in this sample.
In comparison with micrographs of the a and b series in Figure 9, when the heat treatment temperature is below 600 °C, there is a great difference between the surface morphology of heated A4 base glass before and after corrosion, such as in the A4-1 and A4-2 samples. It may result from the high content of glassy phases in them. After the corrosion of the glassy phase, a large number of fine pits were formed (see Figure 9(b1,b2)), which led to a significant increase in the surface roughness. The actual surface area of the sample increased with increasing surface roughness, and the corrosion of A4-1 and A4-2 samples was ultimately accelerated. When the heat treatment temperature increased to 600 °C, corrosion was greatly slowed by the precipitation of a large number of crystals in the A4-3 sample. Corrosion also occurred on the glassy part of the A4-3 sample. As the heat treatment temperature increases to 650 °C, the volume fraction of crystals is quite high in the A4-4 sample. At the grain boundaries, there is a small amount of residual glassy phase. After corroding the surface of the A4-4 sample, it is difficult for a nitric acid solution to enter its interior and cause further corrosion. Thus, A4-4 has the highest acid resistance among these heated A4-base glasses.
In order to study the effect of crystallization of base glass on CTE, the CTE of A4-4 glass-ceramic was measured, and its CTE curve is shown in Figure 10. According to Figure 10, the α30~300 °C value of A4-4 glass-ceramic is 8.19 × 10−6/°C, which is lower than that of A4 base glass (9.05 × 10−6/°C). The CTE of A4-4 glass-ceramic matches the CTE of automotive glass. Therefore, A4-4 glass-ceramic powder was adopted to prepare automotive enamel in the present paper.

3.4. Preparation and Properties of Glass-Ceramic Enamel

A4-4 glass-ceramic powder was mixed with black pigment and varnish to prepare automobile glass enamel paste (see Figure 11). Photos of automobile glass printed with glass enamel and sintered are shown in Figure 12. Table 6 shows the performance parameters, such as acid resistance, adhesion, color, optical density, gloss, roughness, and surface tension, of our product and similar products on the market. The acid resistance of our automobile glass enamel is much higher than that of the similar product in the market because its DRAcid value (2.9 × 10−6 g·cm−2·min−1) is an order of magnitude lower than that (6.4 × 10−5 g·cm−2·min−1) of the product in the market. The sintered enamel was cross-sectioned with a Cross-Cut Tester, and there was no peeling phenomenon, illustrating that its adhesion ISO grade was 0, which indicated that the enamel layer was fully sintered and firmly bonded to the automotive glass. The L value of our enamel is 6.39, which indicates good color, and its optical density (OD) value is 3.71, indicating low transmittance and strong shading ability. The G value of glossiness of our product is 6.5 Gs, which demonstrates that it is matte. Since the printing enamel area is the part where the automobile glass is installed and fixed, the roughness and surface tension will affect the firmness of the automotive glass installation. The roughnesses Ra and Rz of our product are 0.624 μm and 4.393 μm, respectively, and the surface tension σ is 44 mN/m. In sum, the indicators of our product meet the requirements of the current mainstream automobile manufacturers, and it has much higher acid resistance than commercial products.

4. Conclusions

(1)
For glasses in the 15R2O-xBi2O3-10B2O3-(75-x)SiO2 system, their Tg, Tf, and S values decrease regularly, their crystallization ability is improved, their crystallization temperature range is widened, and the number of crystallization exothermic peaks varies from one to two or even three with increasing Bi2O3/SiO2 ratio.
(2)
The three crystallization exothermic peaks (Tp1, Tp2, and Tp3) in the DTA curve of A4 base glass correspond to the crystallization of Bi2SiO5, Bi2O2SiO3, and Bi4Si3O12 crystals, respectively. The crystallization activation energies of the three types of crystalline phases are 208.4 kJ/mol (Ec1), 169.4 kJ/mol (Ec2), and 263.6 kJ/mol (Ec3), respectively. The crystallization of A4 base glass is bulk crystallization.
(3)
When the crystallization temperature is in the range of 530–650 °C, the metastable Bi2SiO5 and Bi2O2SiO3 crystalline phases are mainly precipitated. Above 650 °C, only Bi4Si3O12 crystalline phases are precipitated, and Bi4Si3O12 crystals are intermingled with each other. The crystallinity of the base glass increases significantly with the increase in heat treatment temperature. The CTE of the glass-ceramic is significantly lower than that of the corresponding base glass. DRAcid values of the heat-treated base glasses are in the range of 10−5~10−6 g·cm−2·min−1. In comparison with base glass, the DRAcid values of base glass heated at temperatures higher than 650 °C decrease by an order of magnitude. It proves that increasing the heat treatment temperature is beneficial for improving the acid resistance of base glass. Enamel was prepared by mixing A4-4 glass-ceramic powder with copper-chromium black and varnish, then printed on automotive glass substrates, and then sintered. The indicators of our product meet the requirements of the current mainstream automobile manufacturers, and it has much higher acid resistance than commercial products.

Author Contributions

Conceptualization, T.Z.; Methodology, T.Z., W.W. and J.Z.; Validation, K.L. and W.D.; Investigation, W.W.; Resources, L.L.; Data curation, T.Z.; Writing—original draft, T.Z.; Writing—review & editing, T.Z.; Visualization, Q.B.; Supervision, H.X.; Project administration, K.L., Q.B. and J.Z.; Funding acquisition, W.D. All authors have read and agreed to the published version of the manuscript.

Funding

We would like to express our gratitude for the financial support from the Educational Major Project of Jiangxi Province in China (No. GJJ201301), the Major Project of Jingdezhen Ceramic Industry (No. 2021ZDGG004), the Jingdezhen Technology Bureau Grant (No. 2021GYZD009-18), the Jiangxi Province Key R&D Program in China (No. 20202BBE53012), the 2021 Open Project “State Key Laboratory of Silicon Materials” (No. SKL2021-04), and Jingdezhen Technology Bureau (No. 20224GY008-16).

Data Availability Statement

The raw data required to reproduce these findings cannot be shared at this time as the data also forms part of an ongoing study.

Conflicts of Interest

The authors declare no conflict of interest.

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Inorganics 11 00166 g001 550
Figure 1. The preparation process and application of automobile glass enamel.
Figure 1. The preparation process and application of automobile glass enamel.
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Figure 2. XRD patterns of A1–A5 samples.
Figure 2. XRD patterns of A1–A5 samples.
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Figure 3. CTE curves of base glasses.
Figure 3. CTE curves of base glasses.
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Figure 4. DTA curves of A1–A5 base glasses.
Figure 4. DTA curves of A1–A5 base glasses.
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Figure 5. DTA curves of the A4 glass heated at different rates.
Figure 5. DTA curves of the A4 glass heated at different rates.
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Figure 6. Kissinger kinetic plots of A4 glass.
Figure 6. Kissinger kinetic plots of A4 glass.
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Figure 7. XRD patterns of all heat-treated base glasses. (a) A1, (b) A2, (c) A3, (d) A4, (e) A5.
Figure 7. XRD patterns of all heat-treated base glasses. (a) A1, (b) A2, (c) A3, (d) A4, (e) A5.
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Figure 8. (a) Dissolution rates of all heat-treated glasses in acid solutions; (b) Dissolution rates of A4 heat-treated glasses in acid solutions.
Figure 8. (a) Dissolution rates of all heat-treated glasses in acid solutions; (b) Dissolution rates of A4 heat-treated glasses in acid solutions.
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Figure 9. SEM of A4-1~A4-4 samples before (serial a) and after (serial b) corrosion in nitric acid solution. Among them, (a1,b1) correspond to sample A4-1, (a2,b2) correspond to sample A4-2, (a3,b3) correspond to sample A4-3, and (a4,b4) correspond to sample A4-4.
Figure 9. SEM of A4-1~A4-4 samples before (serial a) and after (serial b) corrosion in nitric acid solution. Among them, (a1,b1) correspond to sample A4-1, (a2,b2) correspond to sample A4-2, (a3,b3) correspond to sample A4-3, and (a4,b4) correspond to sample A4-4.
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Figure 10. CTE curve of A4-4 glass-ceramics.
Figure 10. CTE curve of A4-4 glass-ceramics.
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Figure 11. Photo of glass enamel paste to be printed on automobile glass.
Figure 11. Photo of glass enamel paste to be printed on automobile glass.
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Figure 12. Photos of automobile glass printed with glass enamel and sintered: (a) front windshield; (b) sunroof windshield; and (c,d) side windshield.
Figure 12. Photos of automobile glass printed with glass enamel and sintered: (a) front windshield; (b) sunroof windshield; and (c,d) side windshield.
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Table
Table 1. Compositions of base glasses.
Table 1. Compositions of base glasses.
Sample CodesR2O (mol%)Bi2O3 (mol%)B2O3 (mol%)SiO2 (mol%)
A115101065
A215151060
A315201055
A415251050
A515301045
Table
Table 2. α30~300 °C, Tg (Dil), and Tf values of base glasses.
Table 2. α30~300 °C, Tg (Dil), and Tf values of base glasses.
Sample Codesα30~300 °C (±0.2 × 10−6/°C)Tg(Dil) (±5 °C)Tf (±5 °C)
A17.93449497
A28.32441484
A38.77435473
A49.05430462
A59.89419446
Table
Table 3. Characteristic temperatures and thermal stability parameters of base glasses.
Table 3. Characteristic temperatures and thermal stability parameters of base glasses.
Sample CodesTg(DTA) (±5 °C)Tx (±5 °C)Tp1 (±5 °C)Tp2 (±5 °C)Tp3 (±5 °C)S (±5 °C)
A1442617653//175
A2437578615654/141
A3427554585611651127
A4426545574606659119
A5421539573602681118
Table
Table 4. Tp, Ec, and n values of A4 base glass heated at different rates.
Table 4. Tp, Ec, and n values of A4 base glass heated at different rates.
Heating Rates (°C/min)Tp1 (±5 °C)Tp2 (±5 °C)Tp3 (±5 °C)
5574606659
10593630681
15604646688
20613658696
Ec and n values
Ec (kJ/mol)Ec1 = 208.4Ec2 = 169.4Ec3 = 263.6
n2.062.582.23
Table
Table 5. Heat treatment schedules of A1–A5 base glasses, DRAcid values, and crystalline phases in heated base glass.
Table 5. Heat treatment schedules of A1–A5 base glasses, DRAcid values, and crystalline phases in heated base glass.
Base Glass CodesHeat Treatment SchedulesHeated Base Glass CodesCrystalline PhasesDRAcid (×10−5 g·cm−2·min−1)
A1610 °C/2 hA1-1Bi4Si3O122.01
650 °C/2 hA1-2Bi4Si3O120.38
A2570 °C/2 hA2-1No crystals3.32
610 °C/2 hA2-2Bi2O2SiO31.38
650 °C/2 hA2-3Bi4Si3O120.38
A3550 °C/2 hA3-1No crystals6.30
2.66
1.82
0.52
580 °C/2 hA3-2Bi2O2SiO3 (major phase); Bi2SiO5 (minor phase)2.66
610 °C/2 hA3-3Bi2O2SiO3 (major phase); Bi2SiO5 (secondary phase); Bi4Si3O12 (minor phase)1.82
650 °C/2 hA3-4Bi4Si3O120.52
A4540 °C/2 hA4-1No crystals9.63
570 °C/2 hA4-2Bi2O2SiO3 (major phase); Bi2SiO5 (minor phase)4.14
600 °C/2 hA4-3Bi2O2SiO3 (major phase); Bi2SiO5 (secondary phase); Bi4Si3O12 (minor phase)2.95
650 °C/2 hA4-4Bi4Si3O120.83
A5530 °C/2 hA5-1No crystals12.24
570 °C/2 hA5-2Bi2O2SiO3 (major phase); Bi2SiO5 (minor phase)8.14
600 °C/2 hA5-3Bi2O2SiO3 (major phase); Bi2SiO5 (secondary phase); Bi4Si3O12 (minor phase)5.61
680 °C/2 hA5-4Bi4Si3O122.45
Table
Table 6. Properties of sintered enamel.
Table 6. Properties of sintered enamel.
PropertiesOur ProductsSimilar Product in Market
DRAcid (g·cm−2·min−1)2.9 × 10−66.4 × 10−5
Adhesive force,
(ISO grade)		00
Chroma (L, a, and b)L: 6.39, a: −0.08, b: −0.08L: 6.17, a: −0.10, b: −0.09
Optical density, (OD)3.713.55
Glossiness, G (Gs)6.57.8
Roughness, Ra, Rz (μm)Ra: 0.624
Rz: 4.393		Ra: 0.611
Rz: 4.256
Surface tension, σ (mN/m)4444
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Zhao, T.; Wang, W.; Liu, K.; Liu, L.; Dong, W.; Bao, Q.; Xu, H.; Zhou, J. Preparation of Glass-Ceramics in the R2O-Bi2O3-B2O3-SiO2 System Applied in Automobile Glass Enamel. Inorganics 2023, 11, 166. https://doi.org/10.3390/inorganics11040166

AMA Style

Zhao T, Wang W, Liu K, Liu L, Dong W, Bao Q, Xu H, Zhou J. Preparation of Glass-Ceramics in the R2O-Bi2O3-B2O3-SiO2 System Applied in Automobile Glass Enamel. Inorganics. 2023; 11(4):166. https://doi.org/10.3390/inorganics11040166

Chicago/Turabian Style

Zhao, Tiangui, Wei Wang, Kun Liu, Li Liu, Weixia Dong, Qifu Bao, Heliang Xu, and Jianer Zhou. 2023. "Preparation of Glass-Ceramics in the R2O-Bi2O3-B2O3-SiO2 System Applied in Automobile Glass Enamel" Inorganics 11, no. 4: 166. https://doi.org/10.3390/inorganics11040166

APA Style

Zhao, T., Wang, W., Liu, K., Liu, L., Dong, W., Bao, Q., Xu, H., & Zhou, J. (2023). Preparation of Glass-Ceramics in the R2O-Bi2O3-B2O3-SiO2 System Applied in Automobile Glass Enamel. Inorganics, 11(4), 166. https://doi.org/10.3390/inorganics11040166

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