Condition monitoring of a thermally aged elastomer by 1H‐NMR T2 relaxation measurements of solvent‐swelled samples

The aging of polymers is often monitored by mechanical property measurements such as those of Young's modulus or tensile elongation at break; new methods are required, however, in situations where traditional mechanical methods cannot be employed. A hydroxy‐terminated polybutadiene/isophorone diisocyanate elastomer is commonly used as a propellant binder. The thermal degradation of the binder is believed to be an important parameter governing the performance of the propellant. Classical mechanical methods cannot be used to monitor the condition of this material when it has been aged in situ as a highly dispersed binder. In this study, the ¹H‐NMR spin‐spin relaxation times, T₂, of solvent‐swelled samples decreased substantially as thermally induced oxidation led to additional crosslinking. A time–temperature superposition analysis of the relaxation times was performed on samples that had been aged at temperatures ranging from 50 to 125°C. The acceleration factors derived from the relaxation measurements agreed with those reported earlier for tensile elongation at break and oxygen consumption. The dependence of T₂ on tensile elongation at break was independent of the temperature at which the sample was aged. A shortened version of the experiment, requiring only two spin‐echo delay times, is presented. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3636–3641, 2002     

Glass‐transition temperature of poly(vinylidene fluoride)‐poly(methyl acrylate) blends: Influence of aging and chain structure

The glass‐transition temperature (T_g) of the poly(vinylidene fluoride) (PVF₂)‐poly(methyl acrylate) (PMA) blends increase with aging time. The T_g versus log(time) plots are straight lines whose slope values depend on the head to head (H–H) defect content of PVF₂ samples and on the composition of the blends. The values of polymer–polymer interaction parameters (χ) increase with an increase in the H–H defect of PVF₂ for a fixed composition of the blend. Consequently, the T_g of the blend decreases with an increase in the H–H defect of the PVF₂ sample. However, after aging for longer times this decrease of the T_g with H–H defects is lower than those of the unaged blends. The possible reasons are discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1541–1548, 2001     

Monitoring the degradation of a thermally aged EPDM terpolymer by H NMR relaxation measurements of solvent swelled samples

¹H nuclear magnetic resonance (NMR) relaxation times were investigated as a method for monitoring the degradation of polymeric materials. The properties of an ethylene-propylene-diene (EPDM) terpolymer, oven aged at 140°C, were first characterized by traditional mechanical and solution measurements including ultimate tensile elongation, tensile strength, tensile modulus, gel fraction, solvent uptake and density. The elongation and density results provided a characteristic lifetime for this material at 140°C. The other measurements demonstrated that the EPDM terpolymer undergoes predominately chain scission during the early stages of the degradation process and predominately cross-linking during the latter stages. ¹H NMR spin-spin relaxation times, T₂, of the solid polymer were insensitive to the degree of aging until the polymer was very heavily cross-linked after long exposure times. The ¹H NMR T₂s of the polymer swelled in deutero-chloroform were as sensitive to aging as any of the classical measurements cited above. The NMR measurements have the advantage of being rapid, requiring minimal amounts of sample and being applicable for unconventional sample forms such as films, foams and powders.     

Effects of supercritical carbon dioxide treatment on the morphology of poly(l‐lactide)

Synthetic l ‐lactide random copolymers can be employed as controlled release materials when prepared using supercritical carbon dioxide (scCO₂), since they are biodegradable via hydrolysis. To determine the effects of thermal properties on polymer performance following scCO₂ processing, three types of poly(l ‐lactide) having different properties were assessed. The T_m of one poly(l ‐lactide) sample (H‐100) was found to be approximately 170 °C over the processing pressure range from 8 to 18 MPa, while a second sample (H‐440) also showed a constant value of approximately 152 °C. In contrast, the poly(l ‐lactide) REVODE exhibited a T_m of 146 °C prior to processing but a higher value of 147 °C following treatment at 8 MPa. Unlike the H‐100 and H‐440, the T_m value of the REVODE tended to decrease with increasing pressure. The T_g values increased greatly under mild conditions of 8 MPa pressure and a temperature of 40 °C. In particular, the T_g values for the H‐440 and REVODE increased by 4 °C and 5 °C, respectively. All T_g values were lowest at 12 MPa and increased with increasing processing pressure, although the effect of processing temperature was minimal. The Χ_{c DSC} of the H‐100 was 18% initially but increased to 20% upon scCO₂ processing at 40 °C and 14 MPa, and showed further increases at higher processing temperatures. Although the relationship between processing temperature and Χ_{c DSC} values for the H‐440 showed the same trend as observed with the H‐100, a different trend was seen for the REVODE. The Χ_{c XRD} values obtained from the XRD analyses differed from the values generated by DSC analysis, and showed a maximum degree of crystallinity following processing at 80 °C both with and without scCO₂ treatment. ATR FT‐IR analyses identified peaks due to semicrystalline regions in poly(l ‐lactide) samples treated with scCO₂, even when applying low temperatures. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44006.     

Condition monitoring of a thermally aged hydroxy‐terminated polybutadiene (HTPB)/isophorone diisocyanate (IPDI) elastomer by nuclear magnetic resonance cross‐polarization recovery times

A hydroxy‐terminated polybutadiene (HTPB)/isophorone diisocyanate (IPDI) elastomer is commonly used as propellant binder material. The thermal degradation of the binder is believed to be an important parameter governing the performance of the propellant. The aging of these binders can be monitored by mechanical property measurements, such as modulus or tensile elongation. These techniques, however, are not easily adapted to binder agents that are dispersed throughout a propellant. In this paper we investigated solid‐state nuclear magnetic resonance (NMR) relaxation times as a means to predict the mechanical properties of the binder as a function of aging time. Proton (¹H) spin–lattice and spin–spin relaxation times were insensitive to the degree of thermal degradation of the elastomer. Apparently, these relaxation times depend on localized motions that are only weakly correlated with mechanical properties. A strong correlation was found between the ¹³C cross‐polarization (CP) NMR time constant, T_cp, and the tensile elongation at break of the elastomer as a function of aging time. A ramped‐amplitude CP experiment was less sensitive to imperfections in setting critical instrumental parameters for this mobile material. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 453–459, 2001     

Sensitivity of proton NMR relaxation times in a HTPB based polyurethane elastomer to thermo-oxidative aging

Solid-state ¹H NMR relaxometry studies were conducted on a hydroxy-terminated polybutadiene (HTPB) based polyurethane elastomer thermo-oxidatively aged at 80 °C. The ¹H T₁, T₂, and T_1ρ relaxation times of samples thermally aged for various periods of time were determined as a function of NMR measurement temperature. The response of each measurement was calculated from a best-fit linear function of the relaxation time vs. aging time. It was found that the T_2,H and T_1ρ,H relaxation times exhibited the largest response to thermal degradation, whereas T_1,H showed minimal change. All of the NMR relaxation measurements on solid samples showed significantly less sensitivity to thermal aging than the T_2,H relaxation times of solvent-swollen samples.     

Poly(L‐lactide): v. effects of storage in swelling solvents on physical properties and structure of poly(L‐lactide)

The effects of storage at 25°C in swelling solvents having different solubility parameter (δ_s) values of 16.8–26.0 J^0.5 cm^−1.5 on the physical properties and structure of as‐cast poly(L ‐lactide) (PLLA) films was investigated by the degree of swelling (DS), differential scanning calorimetry (DSC), and tensile tests. It was found that PLLA film shows durabity to swelling solvents having δ_s values much lower or higher than the value range of 19–20.5 J^0.5 cm^−1.5 and that the polymer solubility parameter (δ_p) for PLLA is in the value range of 19–20.5 J^0.5 cm^−1.5. The decrease in the glass transition temperature (T_g) and tensile properties and the increase in melting temperature (T_m) and crystallinity (x_c) were larger for PLLA films swollen in solvents having a high DS at 7 days (DS_7days). The slight increase in T_m and x_c for PLLA films after swelling in solvents with high DS_7days values was due to the crystallization of PLLA that occurred during swelling, while the small increase in T_g and elongation at break (ε_B) for PLLA films after immersion in the solvents having low DS_7days values was ascribed to stabilized chain packing in the amorphous region. The T_g, ε_B, and Young's modulus of the PLLA films after swelling in the solvents varied in the ranges of 47–57°C, 4–8%, and 55–77 kg/mm², depending on their DS_7days or δ_s values. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1582–1589, 2001     

Limits to expanding the PN‐F series of polyphosphazene elastomers

Mixed‐substituent fluoroalkoxyphosphazene polymers bearing ～15% 1H,1H,2H,2H‐perfluorooctan‐1‐oxy or 1H,1H,2H,2H‐perfluorodecan‐1‐oxy side groups together with trifluoroethoxy cosubstituent groups were synthesized. The low reactivity of the long‐chain fluoroalkoxides and their limited solubility in organic solvents prevented higher levels of substitution. Moreover, the sodium alkoxides with two methylene residues adjacent to the oxygen proved to be unstable in solution due to elimination of NaF and precipitation of side products, and this limited the time available for chlorine replacement reactions. The resulting cosubstituent polymers were characterized by proton nuclear magnetic resonance (¹H‐NMR), ³¹P‐NMR, ¹⁹F‐NMR, gel‐permeation chromatography, and differential scanning calorimetry. Unlike homo‐ or mixed‐substituent fluoroalkoxyphosphazene polymers, such as [NP(OCH₂CF₃)₂]_n (a microcrystalline thermoplastic, T_g ～ ?63°C, T_m ～ 242°C) or [NP(OCH₂CF₃)(OCH₂(CF₂)_xCF₂H)]_n (PN‐F, a rubbery elastomer, T_g ～ ?60°C, but no detectable T_m), the new polymers are gums (T_g ～ ?50°C, but no detectable T_m) with molecular weights in the 10⁵ g/mol rather than the 10⁶ g/mol range. POLYM. ENG. SCI., 54:1827–1832, 2014. © 2013 Society of Plastics Engineers     

Vinyl polymerization of norbornene with dinuclear diimine nickel dichloride/MAO

Vinyl‐addition polymerization of norbornene was accomplished by two novel dinuclear diimine nickel dichloride complexes in combination with methylaluminoxane (MAO). The activities were moderate. The catalyst structure, Al/Ni molar ratio, solvents, and polymerization temperature all affected the catalytic activities. The obtained polynorbornenes were characterized by ¹H‐NMR, ¹³C‐NMR, FTIR, DSC, WAXD, and intrinsic viscosity measurements. The vinyl‐addition polymers were amorphous but with a short‐range order and high packing density. The polynorbornenes showed glass transition temperatures (T_g) above 240°C and decomposed above 400°C. The catalyst structure and polymerization conditions have effects on the molecular weight and the microstructure of the polymers. The nickel complex with bulkier substituents in the ligand produced polynorbornene with a higher packing density and higher regularity and, therefore, with higher T_g. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 3273–3278, 2003     

Correlation between artificial and natural weathering tests on polystyrene‐block‐polybutadiene‐block‐polystyrene block copolymer

The effects of artificial and natural weathering tests on the structure and mechanical properties of polystyrene‐block‐polybutadiene‐block‐polystyrene (SBS) block copolymer were studied by spectrophotometry, Fourier Transform Infrared (FTIR) Spectroscopy, hardness measurements, and tensile testing. The correlation between artificial and natural weathering tests was also investigated. The results showed that the surface of SBS became yellow with increasing aging time. FTIR spectra confirmed the formation of carbonyl group in the aging process. The elongation at break, the tensile strength, and the tear strength decreased rapidly in the initial stage of the aging process and then leveled off, while the hardness increased with aging time. The correlation between artificial and natural weathering tests in Wanning and Hailaer, in China, could be expressed in terms of t₁ = 2.50t₀^1.99 and t₂ = 1.92t₀^2.56, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008.     

Influence of solvent on size of poly(p‐oxybenzoyl) whiskers prepared from p‐acetoxybenzoic acid

Poly(p‐oxybenzoyl) (POB) crystals are prepared by the polymerization of p‐acetoxybenzoic acid (p‐ABA) at 320°C in various solvents to clarify the influence of miscibility between oligomer and solvent on the morphology as well as the size of the crystal. Concerning the morphology, whiskers are formed in less miscible solvents such as liquid paraffin and Barrel process oil B27. On the other hand, bundle‐like aggregates of fibrillar crystals tend to be formed in the solvents having higher miscibility such as Therm S 900 and 800, which are aromatic heat exchange media. Further, the solvents having higher temperature at which p‐ABA is completely dissolved during polymerization (T_s) yield a larger number of the whiskers with smaller width. The higher supersaturation of oligomers in less miscible solvents causes the formation of a larger number of nuclei with smaller size. Bundle‐like aggregates are formed in the solvents whose T_s is lower than 140°C by the fibrillation of pillar‐like crystals during polymerization owing to the reorganization. This shows a clear relationship between the width and T_s, and between the number of the crystals and T_s. Hence, the size of the whisker such as the length and the width can be predicted by the calculation with T_s, which is very valuable for the preparation of POB whiskers for use as industrial materials. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1129–1136, 2003     

Structural changes of bulk polyethylene by stress impact as studied by solid‐state NMR

Solid‐state ¹³C‐ and ¹H‐NMR spectra of bulk high‐density polyethylene samples, cylindrical in form, to which stress impacts were applied with a home‐made stress‐impact apparatus, were measured. The fraction of the noncrystalline component increases with an increase in the stress‐impact strength. In the crystalline region, the monoclinic crystalline component appear with the stress impact, in addition to the major orthorhombic crystalline component. Furthermore, dynamic characterization was carried out on the basis of the observed values of the relaxation parameters ¹H T₂ and T_CH of the ¹H and ¹³C nuclei. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2268–2272, 2001     

Effect of water‐miscible solvents on the organic solvent‐resistant tyrosinase from Streptomyces sp. REN‐21

The effect of various water‐miscible organic solvents (ethanol, methanol, acetone, acetonitrile, N,N‐dimethylformamide (DMF) and dimethylsulfoxide (DMSO)) on the kinetics of 4‐tert‐butylcatechol (tBC) oxidation in the presence of different samples of organic solvent‐resistant tyrosinase (OSRT) has been studied. In contrast to mushroom tyrosinase the enzyme shows a high relative stability in solutions of organic solvents and increased activity toward the bulky and hydrophobic substrate, tBC, in respect to catechol. Rates of the studied OSRT‐catalyzed reactions are however reduced by the presence of organic solvents and for all studied samples of OSRT decrease exponentially with the content of an organic solvent. The effect has been satisfactorily described by the effect of organic solvents on the thermodynamic activity of tBC. The correlation of the inhibition parameters with the hydrophobicity of a particular solvent (log P), its intrinsic molar volume, V_i, and the Dimroth–Reichardt parameter, E_T(30), are shown. The results allow also the prediction of OSRT activity in aqueous solutions of water‐miscible organic solvents. Copyright © 2003 Society of Chemical Industry     

Diffusion process of amino acids in polymer supports for solid‐phase peptide synthesis as studied by pulsed‐field‐gradient spin‐echo proton nuclear magnetic resonance

The diffusion coefficient (D) values of tert‐butyloxycarbonyl‐glycine, tert‐butyloxycarbonyl‐L ‐tryptophan, tert‐butyloxycarbonyl‐L ‐phenylalanine (Boc‐Phe), and 9‐fluorenylmethoxycarbonyl‐L ‐phenylalanine in Merrifield polystyrene (MPS) gels, poly(ethylene glycol)‐grafted polystyrene (PEG–PS) gels, and crosslinked ethoxylate acrylate (CLEAR) gels, as used in solid‐phase peptide synthesis, were determined by the pulsed‐field‐gradient spin‐echo ¹H‐NMR method. From these experimental results, it was found that the amino acids in MPS gels, PEG–PS gels, and CLEAR gels with N,N‐dimethylformamide‐d₇ (DMF‐d₇) as a solvent had multidiffusion components within a measurement timescale of 10 ms. The D value of Boc‐Phe in polystyrene gels (1% divinylbenzene crosslinked) with tetrahydrofuran‐d₈ was much larger than that in the same gels with DMF‐d₇. Furthermore, the required time in which an amino acid transferred from a reactive site to a reactive site was estimated, within which the solvents and amino acids in the polymer supports diffused in the swollen beads.© 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 413–421, 2003     

Evaluation of isomeric composition of resol‐type phenol formaldehyde matrix resins for silica–phenolic composites and its effect on cure characteristics of the resin

The isomeric composition of several samples of resol‐type phenol formaldehyde resins used for silica–phenolic composites was evaluated by ¹H‐ and ¹³C‐NMR spectroscopy and reverse‐phase HPLC techniques. The variations in the isomeric compositions were attributed to inadvertent variations in the process parameters. A mathematical relation was determined for calculation of free phenol from ¹H‐NMR measurements. The samples were cured at 160°C for 8 h in an inert atmosphere of N₂. The extent of cure in the hardened samples was measured by FTIR analysis. The effect of isomeric composition on the extent of cure was studied. Free phenol and p‐hydroxymethyl phenol, exhibiting a linear correlation, were found to have a pronounced effect on the extent of cure. The cure kinetics were derived by dynamic DSC measurements. Activation energy (E) for curing exhibited a near linear correlation independently with free phenol content and the extent of cure. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2517–2524, 2003     

Highly enhanced accelerating effect of melt‐recrystallized stereocomplex crystallites on poly(L‐lactic acid) crystallization: effects of molecular weight of poly(D‐lactic acid)

The effects of the molecular weight of poly(D ‐lactic acid) (PDLA), which forms stereocomplex (SC) crystallites with poly(L ‐lactic acid) (PLLA), and those of processing temperature T_p on the acceleration (or nucleation) of PLLA homocrystallization were investigated using PLLA films containing 10 wt% PDLA with number‐average molecular weight (M_n) values of 5.47 × 10⁵, 9.67 × 10⁴ and 3.67 × 10⁴ g mol^–1 (PDLA‐H, PDLA‐M and PDLA‐L, respectively). For the PLLA/PDLA‐H and PLLA/PDLA‐M films, the SC crystallites that were ‘non’‐melted and those that were ‘completely’ melted at T_p values just above their endset melting temperature and recrystallized during cooling were found to act as effective accelerating (or nucleation) agents for PLLA homocrystallization. In contrast, SC crystallites formed from PDLA‐L, having the lowest M_n, were effective accelerating agents without any restrictions on T_p. In this case, the accelerating effects can be attributed to the plasticizer effect of PDLA‐L with the lowest M_n. The accelerating effects of SC crystallites in the PLLA/PDLA‐H and PLLA/PDLA‐M films was dependent on crystalline thickness for T_p values below the melting peak temperature of SC crystallites, whereas for T_p values above the melting peak temperature the accelerating effects are suggested to be affected by the interaction between the SC crystalline regions and PLLA amorphous regions.     

Synthesis and proton conductivity of poly(styrene sulfonic acid)/heterocycle‐based membranes

BACKGROUND: High proton conduction through anhydrous polymer electrolyte membranes is crucial for the application to chemical energy conversion devices such as fuel cells. In this context, novel proton conductors were produced by doping poly(styrene sulfonic acid) (PSSA) with 1H‐1,2,4‐triazole (Tri) and 1.12‐diimidazol‐2‐yl‐2,5,8,11‐tetraoxadodecane (imi3), and their physicochemical properties were investigated. RESULTS: Different polymer electrolyte membranes were produced by doping of PSSA with Tri and imi3. PSSATri_x and PSSAimi3_x electrolytes were obtained where x is the doping ratio describing moles of Tri or imi3 per mole of ? SO₃H unit. The membranes demonstrated adequate thermal stability at least up to 200 °C and the dopants acted as plasticizers shifting the T_g values to lower temperatures. PSSATri₁ has a maximum proton conductivity of 0.016 S cm^?1 at 150 °C and the proton conductivity of PSSAimi3_0.5 is approximately 10^?4 S cm^?1 at room temperature. CONCLUSIONS: Transparent, homogeneous and freestanding films of PSSATri_x and PSSAimi3_x were produced. It was demonstrated that both Tri and imi3 are efficient proton solvents in PSSA host matrix, and they yielded promising defect‐type conductivities compared to benzimidazole. Tri‐doped membranes clearly showed better conductivity performance at higher temperatures (T > 100 °C). Both PSSATri_x and PSSAimi3_x polymer electrolytes can be suggested for fuel cell applications. Copyright © 2007 Society of Chemical Industry     

Dynamic mechanical study of epoxy,epoxy/glass,and glass/epoxy/wood hybrid composites aged in various media

It was proposed and subsequently established that wrapping of red oak wood crossties with epoxy impregnated glass fiber composites will impart longer service life and better stiffness and strength characteristics to these hybrid ties than conventional ones and will help them better withstand environmental extremes. The objective was to understand the degrading effects of aqueous (distilled water), saline (NaCl), acidic (HCl), and alkaline (NaOH) solutions, as well as accelerated aging and freeze/thaw cycling environments on the dynamic and static mechanical properties of these hybrid materials (i.e., wood, wrapped with fiber reinforced resin) and their components. Also micrographs of composite samples, obtained through scanning electron microscopy (SEM), were studied to determine the failure mechanism of composite specimens aged in different environments. Results showed that immersion in aging media lowered the glass transition temperature (T_g) and enhanced apparent phase separation in the samples because of polymer plasticization. In water immersion, the T_g and the stiffness increased with time owing to continued resin curing. At ambient temperature, sustained load had little effect on the mechanical behavior of the aged samples. The extent of degradation was the least for samples aged in salt solution. Soaking in room‐temperature acid solution was most damaging to pure red oak wood samples. Six‐cycle aging did not damage the neat resin or the hybrid samples, whereas it damaged pure wood specimens. Therefore, the composite wrapping around the wood core of the hybrid sample protected it sufficiently, thereby preventing damage to the hybrid specimen during the aging process. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Effects of physical aging and carbon dioxide absorption in bisphenol-A polycarbonate

Thermal and mechanical behavior of bisphenol-A polycarbonate was studied as a function of thermal history and absorbed mass fraction of CO₂. Physical aging at 120°C for one week produced dramatic changes in both the thermal and mechanical behavior. Gas absorption studies indicated that although initial diffusion was somewhat retarded in the aged samples, both aged and unaged polycarbonate samples showed identical equilibrium absorbed gas values at 6500 K Pa and identical gas desorption behavior. Absorbed CO₂ was shown to dramatically reduce the glass transition of polycarbonate indicating that CO₂ plasticizes polycarbonate. Additionally, samples which had been aged and absorbed a mass fraction of 0.07–0.10 of CO₂ showed thermal and mechanical behavior identical to that of a glass quenched from above T_g with identical absorbed mass fraction. Once the absorbed gas was desorbed, the thermal and mechanical properties were similar to those of a glass freshly quenched from above T_g. This study demonstrates that sufficient CO₂ gas absorption followed by desorption reverses physical aging in polycarbonate. © 1995 John Wiley & Sons, Inc.     

Miscibility and morphology of chiral semicrystalline poly‐(R)‐(3‐hydroxybutyrate)/chitosan and poly‐(R)‐(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)/chitosan blends studied with DSC, 1H T1 and T1ρ CRAMPS

The phase structure of poly‐(R)‐(3‐hydroxybutyrate) (PHB)/chitosan and poly‐(R)‐(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (P(HB‐co‐HV))/chitosan blends were studied with ¹H CRAMPS (combined rotation and multiple pulse spectroscopy). ¹H T₁ was measured with a modified BR24 sequence that yielded an intensity decay to zero mode rather than the traditional inversion‐recovery mode. ¹H T_1ρ was measured with a 40‐kHz spin‐lock pulse inserted between the initial 90° pulse and the BR24 pulse train. The chemical shift scale is referenced to the methyl group of PHB as 1.27 ppm relative to tetramethylsilane (TMS) based on ¹H liquid NMR of PHB. Single exponential T₁ decay is observed for the β‐hydrogen of PHB or P(HB‐co‐HV) at 5.4 ppm and for the chitosan at 3.7 ppm. T₁ values of the blends are either faster than or intermediate to those of the plain polymers. The T_1ρ decay of β‐hydrogen is bi‐exponential. The slow T_1ρ decay component is interpreted as the crystalline phase of PHB or P(HB‐co‐HV). The degree of crystallinity decreases with increasing wt % of chitosan in the blend. The fast T_1ρ of β‐hydrogen and the T_1ρ of chitosan in the blends either follow the same trend as or faster than the weight‐averaged values based on the T_1ρ of the plain polymers. Together with the observation by differential scanning calorimeter (DSC) of a melting point depression and one effective glass transition temperature in the blends, the experimental evidence strongly suggests that chitosan is miscible with either PHB or P(HB‐co‐HV) at all compositions. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1253–1258, 2002