Polymer Degradation and Stability 79 (2003) 139145 www.elsevier.

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Flame retardants for polypropylene based on lignin

A. De Chiricoa, M. Armaninia, P. Chinib, G. Cioccolob, F. Provasolia, G. Audisioa,*
b a Istituto per lo Studio delle Macromolecole del C.N.R., via E. Bassini, 15, 20133 Milano, Italy A. M., Centro Sperimentale di Volo, Reparto chimico, Aeroporto di Pratica di Mare, 00040-Pomezia (RM), Italy

Received 20 December 2001; received in revised form 1 August 2002; accepted 5 August 2002

Abstract Lignin has been investigated as ame retardant for isotactic polypropylene (PP) by means of thermogravimetric analysis in nitrogen and cone calorimetry with incident heat ux exposure at 25 kW/m2. Lignin has been used in synergism with aluminium hydroxide, poly(vinyl alcohol), melamine phosphate, monoammonium phosphate and ammonium polyphosphate. These ame retardants, based on lignin, increase the thermal degradation temperature, the combustion time and the char yield of PP, and decrease the rate of heat release and the weight loss rate during combustion. Dynamic mechanical analysis shows that lignin addition does not reduce elastic modulus E0 of PP/lignin blends in the range from 30 to 100  C in comparison with pure PP until 15% of lignin addition. # 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Lignin; Flame retardant; PP; Dynamic mechanical analysis; Thermogravimetry; Cone calorimeter

1. Introduction In our previous papers [1,2] we reported our rst results from thermogravimetric analyses and cone calorimetric measurements on some ame retardants for polypropylene (PP), based both on lignin alone and on lignin mixed with other compounds such triglycidylisocyanurate, monoammonium phosphate and melamine. These additives increase the thermal degradation temperature of PP, give rise to the formation of char in nitrogen and strongly reduce the rate of heat release of the PP during the cone calorimetric tests. Lignin is an amorphous polyphenolic plant constituent and represents 2030 wt.% of the wood. Lignin degrades on heating in nitrogen atmosphere and shows a thermal degradation temperature of 440  C but its aromatic chemical structure is able to give a very high char yield which is still high, around to 3538%, at 900  C. It is well known that the ability to form char during the thermal degradation is a basic aspect of ame retardant additives since the char reduces the combustion rate of

* Corresponding author. E-mail address: dir@icm.mi.cnr.it (G. Audisio).

polymeric materials because it does not allow the oxygen to reach the combustion zone easily [3]. Lignin begins to degrade at about 190  C, both in air and in nitrogen, i.e. several degrees before the PP degradation temperature. When PP degradation starts, its hydrocarbon radicals are formed in the presence of charring lignin and the interactions between them could lead to shield formation which reduces the PP combustion rate. For this reason, it was our opinion that lignin could be a candidate as a ame retardant for PP [1,2]. In fact, PP/lignin blend containing only 15 wt.% of lignin burns in a cone calorimeter with a rate of heat release lower than that of pure PP and its complete combustion occurs in a time twice greater than that of pure PP. A recent study on thermal degradation and on charring process of lignin demonstrate by means of X-ray photoelectron spectroscopy and FTIR experiments that lignin in nitrogen above 300  C forms a highly conjugated system with char formation [4]. The rate of heat release in a cone calorimeter by a product is the most important property predicting hazard in a re situation, because the assumption is that the rate of heat release is a measure of the intensity of re [5]. Lignin re retardancy is also increased by small amounts of other known re retardant compounds as reported previously

0141-3910/02/$ - see front matter # 2002 Elsevier Science Ltd. All rights reserved. PII: S0141-3910(02)00266-5

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[1,2,4]. Thus it has been the aim of our research based on thermogravimetric analysis and mainly on cone calorimetric measurements to know the role played by lignin in synergism with other non-halogenated re retardants to reduce the ammability of PP. We also put particular attention to the CO and CO2 evolution and the opacity of the combustion smokes. Moreover, recent research [6,7] about the eect on mechanical properties of the PP blended with lignin have shown that up to 20 wt.% of lignin does not reduce the Izod impact resilience, the heat distortion temperature or the melt ow index of PP, although a decrease of tensile strength has been noticed. We have carried out dynamic mechanic investigations in the range of lignin contents from 020 wt.% in order to study other aspects of the physical properties of PP mixed with lignin.

3  C/min. The tested solid samples, made of pure PP and PP/LIG blends with a variable LIG content equal to 5, 10, 15 and 20 wt.%, had average dimensions of 40146 mm; a Poissons ratio of 0.4 was used as a sample constant. 2.2.3. Cone calorimeter The cone calorimeter (CC) is a bench scale instrument able to determine the rate of heat release by measuring oxygen concentration in the gas ow stream of combustion products and air [5]. An external incident radiant ux of 25 kW/m2 was used with an air ux of 24 l/s. We have followed the procedure dened in ISO 5660 using a Stanton Redcroft cone calorimeter at CESIs Laboratories of Milano (Italy) made according to ASTM E135490. The heat released is calculated on basis of oxygen consumption of 13.1 MJ for 1 kg of oxygen. Each additive was mixed with PP at a ratio of 80 wt.% of PP, 14 wt.% of lignin and 6 wt.% of other compounds. The slabs for cone calorimeter tests were obtained by hot pressing of the mixed powders at 40 atm and 210  C. Slabs 1001006 mm with a mass of 5560 g were exposed to heat in horizontal orientation. The recorded result is the average value of four experiments. The most important results obtained during the combustion for each sample have been: time to ignition, tign, in seconds, total burn time, ttot, in seconds, rate of heat release, RHR, in kW/m2, weight loss rate, in wt.%, smoke opacity, in m2/kg, CO2 and CO emission yields, in kg/kg.

2. Experimental 2.1. Materials The materials used for preparing the dierent blends were: Aldrich hydrolytic lignin (LIG), isotactic PP, Moplen FLP 20 from Himont with MFI of 12 g/10 min at 230  C, Aldrich poly(vinyl alcohol) 99% hydrolysed with MW of 89 000 (PVA), melamine phosphate (MeP), aluminium hydroxide (Al(OH)3) and monoammonium phosphate (AHP), all reagent grade products used without further purication, while as ammonium polyphosphate (APP) the ame retardant Hostaam AP 422 from Hoechst A.G. was used. The selected blends were prepared by mixing the weighed parts as powders by using a lab mill for 4 h. 2.2. Analyses 2.2.1. Thermogravimetric analyses Thermogravimetric analysis (TGA) were carried out on samples of about 10 mg in nitrogen atmosphere with a ow rate of 30 ml/min on a temperature range from 40 to 950  C at a scanning rate of 20  C/min by a PerkinElmer TGS-2 thermogravimetric analyser. Experimental error is about 5  C and 1 wt.% for thermal degradation temperature and char yield, respectively. 2.2.2. Dynamic mechanical analysis Dynamic mechanical analyses (DMA) were carried out with a Du Pont 983 Dynamic Mechanical Analyser, using a exural oscillatory motion, both in resonant frequency mode of operation and in the xed mode of operation. Measurement of viscoelastic parameters, such as storage modulus E 0 , the loss modulus E 00 , the loss factor tan  as a function of the temperature were taken from 30 to 100  C, in air, with a scanning rate of

3. Results and discussion 3.1. Dynamic mechanical analyses After our rst results on re retardancy of LIG for PP, in forecasting a future application of this class of re retardants, our interest has been to contribute to better knowledge of the mechanical properties of PP/ LIG blends already partially described in recent papers [6,7]. We have carried out dynamic mechanical experiments on both PP and PP/LIG blends from 5 to 20 wt.% of LIG in a temperature range from 30 to 100  C. We have observed that the storage modulus E 0 , the real part of the complex Youngs modulus E*, both for pure PP and for LIG+PP decreases with increasing temperature similarly to the PP modulus in both the resonance and xed frequency conditions. Fig. 1 shows the storage modulus E 0 in resonance mode of pure PP and of PP/LIG blends as a function of the temperature; the trend for the PP/LIG blends ts well with that for pure PP. This result conrms that the addition of LIG up to an amount of 15 wt.% blended with PP does not decrease the elastic storage modulus E 0 of PP / LIG blends respect to pure PP on the whole range of temperature. Table 1

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Fig. 1. Storage modulus E 0 , in resonance mode, as a function of the temperature for PP and for PP/lignin blends from 5 to 20% lignin content.

collects the values at 30  C of modulus E 0 at the two chosen frequencies for the examined PP/LIG blends and the Tmin, the temperatures where the loss tangents, Tan , reach their minimum values. Tan  is given by the ratio of loss modulus, E 00 , to storage modulus, E 0 , i.e. tan =E 00 /E 0 , and it reaches its minimum value when sample deformation is mainly due to the elastic component E 0 of the material. Over the whole temperature range of our analysis, the measured tan  values of our materials remain always low ( < 0.08) and, as shown in Table 1, the Tmin values for PP/LIG blends are found to be slightly higher than or equal to that of pure PP. These results conrm that the dominant solid-like behaviour of pure PP does not change when it is blended with LIG. The dierent values of Tmin observed for each material are connected to the two dierent frequencies of oscillation used in the experiments. These temperatures are around the room temperature and are actually equal to that of pure PP. These results are fairly in accord with the Williams, Landel and Ferry equation valid for polymeric materials [8,9]. 3.2. Thermogravimetry In order to evaluate LIG contribution as FR for PP before carrying out CC tests we have compared the

thermal degradation temperatures and the char amounts obtained by TGA when the PP is modied only with some known FRs and with the same FRs and LIG. We have used as FRs melamine phosphate (MeP), ammonium polyphosphate (APP), aluminium hydroxide (Al(OH)3) and poly(vinyl alcohol) (PVA). Fig. 2 shows four basic thermal degradation curves, measured in nitrogen as a function of increasing temperature. We can see in Fig. 2 rst the large LIG degradation curve with its very high char yield, the rapid PP thermal degradation curve at the temperature of 470  C without char formation and then the two curves observed for the PP/LIG and PP/LIG/APP blends with higher thermal degradation temperatures compared to pure PP and with a char yield. Table 2 reports the thermal degradation temperatures at which the 5 wt.%, T 0.5%, and the half amount of the initial mass, Ttd, are lost and the percentage of char produced at 700  C for all the examined samples. We can see in Table 2 that pure PP degrades completely without any char formation and incorporation of 10 wt% of the indicated FRs, without LIG, generally increases the thermal degradation temperature by about 15  C with an average char yield of about 5 wt.%. Char is made of aluminium oxide and phosphoric anhydride coming from the degradation of the used FRs which reduces the PP degradation rate. PVA is not able to give any char. LIG has a thermal degradation temperature 70  C less than that of PP and it produces a very high char amount in inert atmosphere as is shown in Fig. 2. When PP blended with lignin begins to degrade, the charring aromatic radicals coming from lignin [4] reduce the PP degradation rate increasing the PP thermal degradation temperature by 30 and giving a char. We think this could be the role played by LIG as FR for PP and probably for other polymers. A synergism occurs when LIG is blended with the above indicated FRs giving thermal degradation temperature, Ttd, higher by about 32 with respect to pure PP and a char content of 9 wt.% since the resulting eect of two components taken together is greater than their individual eects [3]. These TGA results indicated that the LIG with the chosen FRs could be a valid FR for PP and that the CC tests could give a more complete picture of its validity.

Table 1 Storage modulus E0 at 30  C and Tmin, the temperature of the minimum value of loss tangent, tan , at resonant and xed frequency for some PP/LIG blends PP (%) 100 95 90 85 80 Lignin (%) 0 5 10 15 20 Modulus E 0 30  C, resonance (GPa) 1.33 1.45 1.42 1.64 1.48 Tmin of tan resonance ( C) 50 52 58 55 58 Modulus E0 30  C, xed frequency (GPa) 1.05 1.11 1.31 1.47 1.15 Tmin of tan  xed frequency ( C) 35 35 45 40 35

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Fig. 2. Thermal degradation curves versus temperature for LIG, pure PP and two blends made respectively, with 85 wt.% PP and 15 wt.% LIG and with 80 wt.% PP, 14 wt.% LIG and 6 wt.% APP.

3.3. Cone calorimeter results Distinctly separated among them, Fig. 3 shows the most interesting curves of the rates of heat release (RHR) as a function of combustion time of some PPs containing our FR systems based on LIG in comparison with the RHR curve of pure PP. The RHR curve of pure PP shows a very rapid combustion giving one
Table 2 Comparison of the thermal degradation temperatures T in nitrogen and char wt.% formed by the listed samples Samples PP PP 90%+MeP 10% PP 90%+APP 10% PP 90%+Al (OH)3 10% PP 90%+PVA 10%

0.5%

and Ttd

T 0.5%  C Ttd  C Char wt.% at 700  C 405 430 440 365 335 470 495 485 470 485 400 500 515 510 500 485 0 4 9 6 0 40 7 8 11 10 6

LIG 260 PP 85%+LIG 15% 400 PP 80%+LIG 14%+MeP 6% 390 PP 80%+LIG 14%+APP 6% 400 PP 80%+LIG 14%+Al (OH)3 6% 390 PP 80%+LIG 14%+PVA 6% 360

combustion peak with a maximum at 1400 kW/m2 and a total burning time of 380 s. PP/LIG blend with LIG amount of 15 wt.% shows a slower combustion rate giving a bimodal RHR curve with a peak reduced to 410 kW/m2, a quarter of that of pure PP, and a total combustion time of 660 s. When PP is modied with the same amount of LIG and with 6 wt.% of APP, the RHR values decrease further, the second peak moves to higher temperature and the total combustion time increases to 850 s. PVA seems to decrease LIG re retardancy though TGA results had shown char formation coming evidently from PP/LIG interaction only, without any PVA contribution. All RHR curves of LIG-containing PPs show that as the burning proceeds, there is LIG char layer formation and the PP combustion goes on slowly with a very reduced RHR till the second peak of the bimodal RHR curve. The second peak corresponds to the end of ame burning with the complete destruction of the charred material. Further CC results concerning PP containing our FRs are given in Table 3. Fig. 4 shows weight loss as a function of combustion time for the pure PP in comparison with PP containing LIG alone, LIG/PVA and LIG/APP blends. They are integral bimodal curves which follow the corresponding

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Fig. 3. Rate of heat release as a function time for pure polypropylene and for polypropylene with the indicated ame retardants based on lignin.

Table 3 Time to ignition (tign), total combustion time (ttot), average rate of heat release (RHR), maximum rate of heat release (q 00 max), char (wt.%), average specic extinction area (SEA), average carbon oxide (CO) and carbon dioxide (CO2) yields for pure PP and for samples having 80 wt.% PP, 14 wt.% LIG and 6 wt.% of already named FR additives Additive None LIG LIG+Al (OH)3 LIG+PVA LIG +MeP LIG+AHP LIG+APP tign (s) 96 69 55 72 57 47 70 ttot (s) 385 663 500 610 740 545 850 RHR (Kw/m2) 670 280 270 350 240 226 220 q 00 max (kW/m2) 1400 410 310 500 370 325 395 Char (wt.%) 0 6 9 3 7 10 10 SEA (m2/kg) 273 235 310 238 355 437 410 CO (kg/kg) 0.03 0.03 0.03 0.03 0.05 0.05 0.10 CO2 (kg/kg) 2.8 2.5 2.6 2.6 2.5 2.5 2.1

RHR dierential curves plotted in Fig. 3. We can see that when pure PP is completely burnt at 380 s, the PPs containing the indicated FR blends are still not burnt for 4050% of their original weights. The char formed at the end of combustion in CC tests decreases gradually from PP containing LIG/APP to pure PP. Table 3 reports all the main data relative to RHR curves obtained from our CC measurements as a function of FR composition. The samples examined were pure PP and PP containing LIG alone and LIG with aluminium hydroxide, poly(vinyl alcohol), melamine

phosphate, monommonium phosphate and ammonium polyphosphate. All the PPs containing LIG alone or blended with the FRs here indicated show slower combustion rates, average RHR values reduced to one third of that of pure PP and longer total burning times, twice that of pure PP. The times to ignition of modied PP in Table 3, as well as those reported in our previous paper on LIG re retardancy [2], are smaller than that of pure PP and this could be due to initial combustion of the LIG which in this manner plays its charring role in the materials.

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Fig. 4. Weight loss during cone calorimeter combustion as a function of time for pure PP and for PP with the indicated ame retardants based on lignin.

The longer total combustion times, the lower RHR maximums, q00 max, and the higher char yields at end of the burning reported in Table 3 are connected to the FR ability of the products chosen. During combustion, LIG blended with Al(OH)3, AHP and with MeP and APP is able to give both inorganic compounds as well as Al2O3, P2O5 and polyphosphoric acid (PPA) and organic char that strongly reduce the rate of heat release during PP combustion. PPA produced by thermally decomposing APP and MeP is a strong acid which promotes char formation [10,11] and further catalyses LIG char formation [4]. In fact, longer combustion times for PP have been obtained by the FR blends based on LIG with APP and MeP. Moreover, we can notice that there are some connections between TGA and CC tests: the higher degradation temperature, Ttd, obtained by means of TGA (see third column of Table 2), the longer the total combustion time obtained during the CC tests (see third column of Table 3) and the char yield obtained by means of TGA is equal to that obtained by means of CC burning tests. These results support the use of TGA as a rst screening for evaluating FR properties of a product in the laboratory [3] but TGA results need always to be conrmed by means of more direct burning

rate measurements as well as UL-94, oxygen index and cone calorimeter tests. Average smoke chemical composition for both CO and CO2 are given in Table 3 for each sample and they range respectively, for CO from 0.03 to 0.1 kg/kg and for CO2 from 2.1 to 2.6 kg/kg . They are comparable to the smoke composition of pure PP and there is no negative contribution from our FRs based on LIG to increased CO yield which is the main cause of death during re. Smoke opacity, here given as average specic extinction area (SEA), of PP containing LIG, Al(OH)3 and PVA is comparable to that of pure PP whereas it increases when chemicals like MeP, APP and AHP are used.

4. Conclusions The TGA and CC results conrm the role of LIG as FR for isotactic PP both alone and in synergism with some phosphate compounds and Al(OH)3. The amount of 15 wt.% of LIG used in our research is low compared to the usual amount used in PP re retardancy but the results observed in synergism with other FRs are interesting and

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stimulating for further research. The PP containing LIG alone and with Al(OH)3 and PVA give a very low smoke opacity and low CO yield during combustion but with a lower average RHR and with shorter total combustion times with respect to those obtained by using phosphates. Longer combustion times are obtained with lignin and phosphate compounds. It is our opinion that better formulation based on LIG could be investigated to increase further the FR activity for PP. For this purpose, work is in progress to investigate the eect of LIG on the morphology, structure, crystallisation kinetics and melting properties of isotactic PP.

References
[1] Audisio G, De Chirico A, Focher B, Gallina G. Fourth European Workshop on Lignocellulosics and Pulp, Extended Abstracts, Stresa, Italy, 811 September 1996. p. 528. [2] Gallina G, Bravin E, Badalucco C, Audisio G, Armanini M, De Chirico A, et al. Fire Mater 1998;22:15. [3] Pearce EM, Khanna YP, Raucher D. Thermal analysis in polymer ammability. In: Thermal-characterization of polymeric materials, Chap. 8, Academic Press; 1981. [4] Li J, Li B, Zhang XC, Su RZ. Polym Degrad Stab 2001;72:493. [5] Babrauskas V. J Fire Sci 1986;4:148. [6] Kharade AY, Kale DD. J Appl Polym Sci 1999;72:1321. [7] Alexy P, Kosikova B, Podstranska G. Polymer 2000;41:4901. [8] Williams ML, Landel RF, Ferry JD. J Am Chem Soc 1955; 77:3701. [9] Ferry JD. Viscoelastic properties of polymers. 3rd ed. New York: Wiley & Sons; 1980. [10] Camino G, Costa L, Martinasso G. Polym Degrad Stab 1989; 23:359. [11] Costa L, Camino G, Luda di Cortemiglia MP. In: Nelson GL, editor. Fire and polymers, Chap. 15. ACS Symposium Series 425. Washington, DC: American Chemical Society; 1990

Acknowledgements This work on thermogravimetric and cone calorimetric investigation was supported by Italian National Research Council, Rome.