Wanli Zhou,
Shaosi Ji,
Pengqing Liu,
Mengjin Jiang and
Jianjun Xu*
State Key Laboratory of Polymer Materials and Engineering, College of Polymer Science and Engineering, Sichuan University, No. 24 South Section 1, Yihuan Road, Chengdu, Sichuan 610065, China. E-mail: xujj@scu.edu.cn; Tel: +86 02885462013
First published on 21st March 2016
To improve the flame resistance of polyvinyl alcohol (PVA) fibers, the well-designed permanent flame-retardant coatings were introduced on the surface of PVA fibers. Acrylonitrile (AN) was firstly grafted on the PVA fiber surface and then the grafted fibers (PVA-g-AN fibers) were reacted with hydrazine hydrate and copper sulfate solution to form the coatings with flame retardant performance. The structure of the fibers was characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. The flame-retardant performance of the fibers was evaluated by limiting oxygen index (LOI) and micro calorimeter (MCC) tests. It was found that the coatings were effective in improving the flame resistance of PVA fibers. SEM photos of char residues and the results of the TG-IR technique revealed that flame retardance is mainly provided through the barrier action of the coatings with the partial effect of gaseous phase.
Therefore, post-treatment method, which is very convenient and effective, seems to be an available alternative to obtain flame-resistant PVA fibers. It has been reported that the flame resistance of many fibers or fabrics, such as, cotton, silk, viscose rayon, polyacrylonitrile (PAN) fibers, etc., was highly improved after being grafted with flame retardants onto their surface.8–14 However, documents about PVA fibers grafting with flame retardants were few reported. Therefore, it is interesting to attempt to improve the flame resistance of PVA fibers by grafting flame retardants onto their surface.
In addition, it has been reported that the flame resistance of PAN fibers was highly improved after being modified in hydrazine hydrate and copper sulfate solution.15–19 These modified PAN fibers decompose with negligible output of smoke and toxic gases, and form stable chars without melting and shrinking when exposed to a naked flame. It has been proved by many researchers that the excellent flame retardancy of these modified PAN fibers was mainly attributed to the promoting effect of the metal ions on charring processing with partial effect on reducing the generation of combustible gases during burning.17,20,21 However, the reported tensile strength of those fibers is only about 1.50 cN per dtex, which severely limits their wide application.22–24 In our previous work, PVA as reinforcing agent was added into the spinning solution of PAN to improve the tensile strength of the modified PAN fibers.25 As expected, the tensile strength of the blend PAN/PVA fiber after flame retardant modification was much higher than that of the neat PAN fiber after the same modification processes. Energy-dispersive spectroscopy revealed that metal ions were mainly distributed around the surface of those modified PAN/PVA fibers, which indicated that the flame retardant modification basically occurred on the surface layer of the blend fibers, i.e., the inner PAN was not participated in the modification and thus did not contribute to the flame resistance. Therefore, it is possible to construct a novel flame-retardant fiber with PVA substrates and modified PAN coatings, which has the favorable tensile strength and flame retardance. The tensile strength of this designed material is mainly provided by PVA fiber and the flame resistance is planed to be given by the high flame-resistant metal-contained PAN coatings. Actually, many kinds of metal complexes have been synthesized and blended into PVA films as flame retardants by a lot of researchers, and those metal complexes were proved to be quite effective to improve the flame resistance of PVA films.3,4,26 Hu prepared a kind of nickel-contained flame retardant based on chitosan, which improved the flame resistance of PVA films significantly by promoting the dehydration processes of PVA and accelerating the formation of char residues during burning.26 However, these blend methods may not be used to improve the flame resistance of PVA fibers for the rigorous preparation requirement of PVA fibers as has been mentioned above.
In this paper, PVA fibers grafted with a thin layer of PAN were obtained by using the method reported in many literatures,27–31 then the grafted fibers (PVA-g-AN fibers) were successively reacted with hydrazine hydrate and copper sulfate solution to promote the flame retardant performance. The structure, appearance and mechanical properties of the fibers were investigated by Fourier transform infrared spectroscopy, scanning electron microscopy, and tensile strength testing, respectively. Flame retardant performance of the fibers was measured by limiting oxygen index and microcalorimetry tests.
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The solid–liquid ratio of the reaction system of each step was 1:
20, and after each stage of treatment, the fibers were washed to neutral with distilled water and dried in vacuum oven at 80 °C.
Mechanical properties were measured using a single fiber tensile tester (Model LLY-06, Laizhou Electron Instrument Co., Ltd., China) with a 10 cN load cell. Tests were conducted on single fiber specimens using a crosshead velocity of 20 mm min−1 and a gauge length of 20 mm. All the tensile tests were carried out at the constant temperature of 25 °C and relative humidity of 70%. Twenty single fiber specimens were measured to make an average.
LOI values were measured on a LOI analyzer (Model JF-3, Jiangning Co., China) according to ISO 4589-2. And an average of at least five replicas was adopted.
Thermal gravimetric analysis (TGA) was carried on a TA instrument Q600. The fiber samples were cut into powder and dried in a vacuum oven at 80 °C for 12 h. The measured temperature was varied from 100 °C to 800 °C at a heating rate of 10 °C min−1 under nitrogen atmosphere.
Thermal gravimetric analysis/infrared spectrometry (TG-FTIR) was performed to analyze the volatilized products after the pyrolysis of samples under a nitrogen flow of 35.0 mL min−1. All samples were approximately 10 mg and were kept at 100 °C for 5 min first to remove the absorbed water, then were heated up to 800 °C at a heating rate of 10 °C min−1.
Microcalorimetry (MCC) tests were conducted on a FTT0001 micro calorimeter instrument (FTT, UK). The dried powdered fiber samples, placed in a 40 μL alumina crucible, were heated from 100 °C to 750 °C at a heating rate of 1 °C s−1 in a stream of nitrogen flowing at 80 mL min−1. Then, the mixer of the volatile anaerobic thermal degradation products and nitrogen gas stream was mixed with a 20 mL min−1 stream of oxygen gas before entering to a 900 °C combustor. All samples were approximately 5 mg.
The content of copper ions absorbed by the fibers was determined by an ICPS-8100 inductively coupled plasma emission spectrometer (Shimadzu, Japan). The samples were immersed into sulfuric acid solution for 48 h at 25 °C with stirring so that all the copper ions of the samples were replaced by H+ and released into the solution. Then, the content of copper ions in the acid solution was tested by ICP.
Scanning electron micrographs (SEM) of the samples were obtained by a JSM-5900LV scanning electron microscope (JEOL). The accelerated voltage was 20 kV.
Fig. 3 shows SEM photographs of PVA-g-AN-55% fiber (PVA-g-AN fiber with 55% grafting degree, similarly hereinafter) after being modified in HHA for 4 h and copper sulfate solution for 1 h. It can be seen that the surface of the fibers after modification is still very rough, which suggests the coatings are very stable and could not fall off from fibers during modification. Moreover, there appears many cracks in the interior of H-PVA-g-AN and Cu-PVA-g-AN fibers, as is shown in Fig. 3c and d, which implies that flame-resistant modification may cause the decrease of the tensile strength of fibers.
Sample | Breaking force/(cN) | Linear density/(dtex) | Tensile strength/(cN per dtex) |
---|---|---|---|
PVA | 7.19 ± 0.10 | 1.15 ± 0.04 | 6.26 ± 0.13 |
PVA-g-AN-35% | 7.74 ± 0.08 | 1.55 ± 0.06 | 4.99 ± 0.14 |
PVA-g-AN-45% | 7.91 ± 0.11 | 1.64 ± 0.05 | 4.82 ± 0.08 |
PVA-g-AN-55% | 8.00 ± 0.10 | 1.78 ± 0.07 | 4.49 ± 0.12 |
PVA-g-AN-65% | 8.10 ± 0.09 | 1.92 ± 0.06 | 4.22 ± 0.08 |
PVA-g-AN-85% | 7.99 ± 0.12 | 2.13 ± 0.07 | 3.75 ± 0.07 |
PVA-g-AN-110% | 7.75 ± 0.09 | 2.42 ± 0.08 | 3.20 ± 0.07 |
In order to observe the influence of HHA modification on the mechanical properties of the fibers, the mechanical properties of PVA-g-AN-55% fibers after being treated in HHA for different time was tested and the results are shown in Table 2. It can be seen that the breaking force of PVA-g-AN-55% fibers drops significantly from 8.00 cN to about 7.22 cN after being treated for 1 h, but further decreases only a little after a long time reaction, for example, the breaking force still retains about 7.20 cN after 3 h treatment. Correspondingly, the tensile strength of PVA-g-AN-55% fiber is also basically unchanged after a significant decrease at beginning. This may be because the modification of HHA mainly occurred on the coatings of PVA-g-AN-55% fibers, and the structure of the coatings was destroyed during modification but the structure of the PVA substrates was not damaged. As a result, the breaking force of PVA-g-AN-55% fiber after modification in HHA is close to that of PVA fiber, as is given in Table 1. However, further treatment in HHA may also cause some damage to PVA substrate, as is proved by the SEM photographs shown in Fig. 3, so the breaking force decreases to 7.10 cN after 4 h treatment in HHA. Importantly, the long time reaction in HHA may generate more chelating groups on the surface of the fibers, which helps to absorb more copper ions and thus improve the flame resistance of the fibers more effectively. Taking into account the decrease of mechanical properties and increase of chelating groups with treatment time, the treatment time of PVA-g-AN fibers in HHA is chosen to be 4 h in this paper.
Treating time/(h) | Breaking force/(cN) | Linear density/(dtex) | Tensile strength/(cN per dtex) |
---|---|---|---|
0 | 8.00 ± 0.10 | 1.78 ± 0.07 | 4.49 ± 0.12 |
1 | 7.22 ± 0.12 | 1.80 ± 0.08 | 4.01 ± 0.11 |
2 | 7.25 ± 0.13 | 1.80 ± 0.07 | 4.03 ± 0.09 |
3 | 7.20 ± 0.11 | 1.81 ± 0.08 | 3.98 ± 0.11 |
4 | 7.10 ± 0.12 | 1.82 ± 0.10 | 3.90 ± 0.13 |
After 4 h treatment in HHA, the fibers were put into copper sulfate solution for 1 h to absorb copper ions, the mechanical properties of these Cu-PVA-g-AN fibers with different grafting degree was tested and the results are given in Table 3. As expected, the tensile strength of the fibers decreases with the increasing of grafting degree. Nonetheless, the tensile strength of Cu-PVA-g-AN fiber with grafting degree as high as 110% is about 2.79 cN per dtex, which is still much higher than that of acrylic fiber modified by similar methods reported in literatures.15 Empirically, to be used in woven form, the tensile strength of fibers should be above 2.50 cN per dtex. Otherwise, the low tensile strength will restrict the application of the fibers, thus the grafting degree should be limited to 110%.
Sample | Breaking force/(cN) | Linear density/(dtex) | Tensile strength/(cN per dtex) |
---|---|---|---|
Cu-PVA-g-AN-35% | 6.92 ± 0.15 | 1.58 ± 0.08 | 4.38 ± 0.12 |
Cu-PVA-g-AN-45% | 7.08 ± 0.16 | 1.68 ± 0.08 | 4.22 ± 0.10 |
Cu-PVA-g-AN-55% | 7.10 ± 0.15 | 1.85 ± 0.08 | 3.84 ± 0.08 |
Cu-PVA-g-AN-65% | 7.28 ± 0.13 | 2.01 ± 0.10 | 3.62 ± 0.12 |
Cu-PVA-g-AN-85% | 7.33 ± 0.14 | 2.26 ± 0.12 | 3.24 ± 0.11 |
Cu-PVA-g-AN-110% | 7.48 ± 0.16 | 2.68 ± 0.12 | 2.79 ± 0.06 |
In summary, the flame resistance of Cu-PVA-g-AN fibers increases greatly with the increasing of grafting degree and the content of copper ions. However, as has been discussed above that the increasing of grafting degree also causes the tensile strength of the fibers decrease dramatically. Therefore, the mechanical properties and flame resistance of the fibers should be controlled by the adjustment of the grafting degree.
Fig. 6 presents HRR curves of PVA-g-AN, H-PVA-g-AN and Cu-PVA-g-AN fibers, and the corresponding experimental data are summarized in Table 4. It can be seen that PVA-g-AN-55% fiber created much combustible gases during heating, with a THR as high as 16.6 kJ g−1 and a pHRR of 162.8 W g−1. After being treated in HHA for 4 h, THR and pHRR decrease slightly to 16.0 kJ g−1 and 151.8 W g−1, respectively, indicating that the modification of HHA almost did not reduce the generation of combustible gases and was not effective in slowing the release of combustible gases during heating. However, after absorbing copper ions, THR and pHRR of the fibers reduce dramatically, which means fire hazard of the fibers is reduced with less combustible gases generated and much slower release of these combustible gases during heating. Understandably, THR and pHRR of Cu-PVA-g-AN fibers decrease with the increasing of grafting degree, as is shown in Fig. 6 and Table 4. It also can be seen that both of PVA-g-AN and H-PVA-g-AN fibers have two heat release peaks. The first peak at relatively low temperature may be contributed to the volatile gases released by the elimination of the side chains of the fibers, and the second peak at about 390 °C is caused by the further degradation of the fibers. However, the first peak is totally disappeared and the second peak shifts to a higher temperature after absorbing copper ions, besides, Tmax2 of Cu-PVA-g-AN fibers increases with the increasing of grafting degree. The reason may be that copper ions make the coatings more stable, and the decomposition products of the coatings would participate in charring process rather than form into volatile gases after absorbing copper ions.21 The carbon residues of the coatings may work as barriers and delay the degradation of PVA substrates. In the process of pyrolysis, the combustible gases generated by the elimination of side chains at the initial stage are obstructed by the carbon layer. Therefore, the first heat release peak of Cu-PVA-g-AN fibers at low temperature is disappeared. With the heat barrier action of carbon layer, the degradation of Cu-PVA-g-AN fibers was delayed. However, with the increasing of temperature, the carbon layer was finally broken with the releasing of combustible gases. Furthermore, the coatings become more and more thicker with the increasing of grafting degree, as a result the carbon layer left by the coatings become thicker as the grafting degree increases. Thicker carbon layer may have a better barrier effect, therefore, Tmax2 of Cu-PVA-g-AN fibers increases with the increasing of grafting degree.
Sample | Tmax1/(°C) | pHRR1/(W g−1) | Tmax2/(°C) | pHRR2/(W g−1) | THR/(kJ g−1) |
---|---|---|---|---|---|
PVA-g-AN-55% | 289.3 | 42.8 | 392.5 | 162.8 | 16.6 |
H-PVA-g-AN-55% | 304.3 | 36.6 | 390.1 | 151.8 | 16.0 |
Cu-PVA-g-AN-35% | — | — | 391.2 | 125.1 | 13.6 |
Cu-PVA-g-AN-55% | — | — | 409.2 | 106.5 | 12.1 |
Cu-PVA-g-AN-85% | — | — | 417.9 | 98.0 | 10.0 |
Cu-PVA-g-AN-110% | — | — | 424.6 | 65.0 | 6.7 |
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Fig. 7 TG and DTG curves of PVA-g-AN, H-PVA-g-AN and Cu-PVA-g-AN fibers with 55% grafting degree tested under nitrogen atmosphere. |
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Fig. 8 TG and DTG curves of a series of Cu-PVA-g-AN fibers with different grafting degree tested under nitrogen atmosphere. |
It also can be seen that the peak temperature of the first two weight-loss stages shifts to high temperature after absorbing copper ions (T = 314 °C, 378 °C). It may because the coatings delayed the decomposition of the substrates and slows the releasing of volatile gases, which is consistent with the results of MCC results. Besides, the third weight-loss stage originated from the decomposition of the main chains is not obvious after absorbing copper ions, leaving a large amount of carbon residues, which verifies that copper ions affect the degradation of the coatings and is beneficial to form carbon residues during heating.
It can be found from Fig. 8 that the amount of char residues of Cu-PVA-g-AN fibers increases with the increasing of grafting degree, but less rapidly when grafting degree becomes very high; this may due to the less rapid growth of copper ions when grafting degree becomes very high, as has been discussed above. Moreover, the first weight-loss stage shifts to high temperature with the increasing of grafting degree and overlaps with the second decomposition stages, which may because of the better barrier action of the thicker coatings.
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Fig. 9 SEM photographs of char residues of PVA-g-AN (a), H-PVA-g-AN (b) and Cu-PVA-g-AN (c) fibers after burning in a naked flame. |
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Fig. 10 Volatile gases spectra measured by TG-FTIR for PVA-g-AN (a), H-PVA-g-AN (b), and Cu-PVA-g-AN (c) fibers. |
Wavenumber (cm−1) | Peak (cm−1) | Group | Vibration | Product |
---|---|---|---|---|
3800–3500 | 3735 | O–H | Stretch | H2O |
1580–1480 | 1508 | H–O–H | Bending | |
3020–2600 | 2936 | C–H | Stretch | Hydrocarbon |
3020–2600 | 3016 | ![]() |
Stretch | |
1500–1300 | 1456 | C–H | Bending | |
2400–2200 | 2358, 2320 | C![]() |
Stretch | CO2 |
680–660 | 669 | C![]() |
Bending | |
3500–3300 | 3333 | N–H | Stretch | NH3 |
1650–1580 | 1626 | N–H | Bending | |
1000–900 | 965, 930 | N–H | Bending | |
1760–1660 | 1716 | C![]() |
Stretch | Aldehyde |
3000–2600 | 2822, 2726 | C–H | Stretch | |
1760–1660 | 1745 | C![]() |
Stretch | Acid |
3800–3500 | 3735 | O–H | Stretch |
Carbon dioxide (2358 cm−1), aldehydes (1716 cm−1), ammonia (965 cm−1), acids (1745 cm−1) and hydrocarbons (2934 cm−1) are selected to study for revealing their changes at different temperature and the results are shown in Fig. 11. The intensities of absorbance were all normalized to the samples' weight.
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Fig. 11 Peak intensities of aldehydes, acids, CO2, NH3 and hydrocarbons released by the three kinds of fibers at different temperature. |
It can be clearly seen from Fig. 11 that aldehydes, carbon dioxide, acids and ammonia released by all the fibers began to be detected at about 200 °C, however, the hydrocarbons became detectable at relatively high temperature about 320 °C. It can be comprehended that the volatile gases containing oxygen or nitrogen were mainly contributed to the elimination of the side chains, and the hydrocarbons were mainly released by the main chains of the fibers. This indicates that the side chains of the fibers were much more easily decomposed during heating. Notably, there are two peaks in the release curves of aldehydes and acids of PVA-g-AN and H-PVA-g-AN fibers. Their release peaks of aldehydes and acids at about 300 °C can well explain the results of MCC tests shown in Fig. 6 that both of them exhibit a small heat release peak at relatively low temperature. With a little amount of aldehydes and acids released at this temperature, the first heat release peak of Cu-PAN-g-AN fibers is disappeared. Moreover, both of PVA-g-AN and H-PVA-g-AN fibers show the release peaks of hydrocarbons at about 447 °C, while Cu-PVA-g-AN fiber exhibits the peak at a higher temperature about 459 °C. It indicates that the barrier action of the coatings delayed the degradation of the PVA substrates, which is consistent with the results of MCC tests.
It also can be found from Fig. 11 that the amount of combustible gases including aldehydes, acids and hydrocarbons is largely reduced after being modified in HHA, while the amount of noncombustible carbon dioxide and ammonia is improved, simultaneously. Moreover, after absorbing copper ions, aldehydes, acids and hydrocarbons are further reduced, and carbon dioxide and ammonia are further improved. Therefore, the flame resistance of the fibers is improved with the decrease of combustible gases and the increase of noncombustible gases.
It can be concluded from the results above that the flame resistance of Cu-PVA-g-AN fibers is mainly provided through the effect of barrier action with the partial effect of gaseous phase.
This journal is © The Royal Society of Chemistry 2016 |